Method for producing modified resin

Abstract

A method for producing a modified resin according to the present invention includes a step in which a twin screw extruder that has in-system decompression equipment is charged with a modifying material that has a molecular weight of 2000 or less, a thermoplastic resin that has, in a side chain, a modifiable site capable of reacting with the modifying material, and a reaction catalyst, and a modification reaction of the side chain of the thermoplastic resin is performed at a temperature of 190°C or greater and a pressure of 101.0 kPa or less.

Description

Modified resin manufacturing method

[0001] The present invention relates to a method for producing a modified resin.

[0002] In recent years, attention has been drawn to latent heat storage materials that utilize latent heat based on a phase transition between liquid and solid, a phase transition between crystal and amorphous, or a phase transition of crystalline polymorphism, etc. An example of the use of latent heat storage materials is in a home where nighttime electricity is used to store heat in a latent heat storage material at night, and the stored heat is used as a multipurpose heat source during the day, thereby reducing daytime electricity consumption.

[0003] As a polymer applicable to a heat storage material, Patent Document 1 considers providing a polymer that can provide a heat storage material excellent in moisture permeability and shape retention after the polymer undergoes a phase transition from crystalline to amorphous, and that has excellent moldability.

[0004] International Publication No. 2016 / 098674

[0005] The polymer described in Patent Document 1 can be produced by modifying a thermoplastic resin having a modified moiety with a compound having a specific structure (e.g., an alcohol having an alkyl group having 14 to 30 carbon atoms). However, when such a polymer is produced continuously, the modification reaction does not proceed sufficiently, and unreacted raw materials are contained in the product. Therefore, one aspect of the present invention aims to provide a method for producing a modified resin in which the amount of unreacted raw materials is reduced.

[0006] In some aspects of the present invention, the following [1] to [8] are provided. [1] A method for producing a modified resin, comprising the steps of: feeding a modifying agent having a molecular weight of 2,000 or less, a thermoplastic resin having a side chain containing a modifying moiety capable of reacting with the modifying agent, and a reaction catalyst into a twin-screw extruder having an in-system pressure reducing device; and carrying out a modification reaction of the side chain of the thermoplastic resin at a temperature of 190°C or higher and a pressure of 101.0 kPa or lower. [2] The method according to [1] above, in which the modification reaction is carried out at a temperature of 190°C or higher and a pressure of 70.0 kPa or lower. [3] The method according to [1] or [2] above, in which the modification reaction is a transesterification reaction. [4] The method according to any one of [1] to [3] above, in which the thermoplastic resin is a thermoplastic resin having an ester bond in the side chain. [5] The method according to any one of [1] to [4] above, in which the modifying agent is a compound having a hydroxy group. [6] The method according to any one of [1] to [5] above, wherein the amount of the reaction catalyst added is 0.05 equivalents or less relative to the modified site of the thermoplastic resin. [7] The method according to any one of [1] to [6] above, wherein the amount of the modifying agent is 30 to 70 parts by mass relative to 100 parts by mass of the total amount of the modifying agent and the thermoplastic resin. [8] The method according to any one of [1] to [7] above, wherein the reaction consumption rate of the modifying agent is 85% or more. [9] The method according to any one of [1] to [8] above, wherein the modified resin is a polymer having a structural unit represented by the following formula (1): [(In formula (1), R １ represents a hydrogen atom or a methyl group, L １１ represents a single bond, —CO—O—, —O—CO—, or —O—; L １２ is a single bond, -CH ２ -, -CH ２ -CH ２ -, -CH ２ -CH ２ -CH ２ -, -CH ２ -CH(OH)-CH ２ - or -CH ２ -CH(CH ２ OH)—, L １３is a single bond, -CO-O-, -O-CO-, -O-, -CO-NH-, -NH-CO-, -CO-NH-CO-, -NH-CO-NH-, -NH-, or -N(CH ３ )-, L １６ represents an alkyl group having 14 to 30 carbon atoms.

[0007] According to the present invention, it is possible to provide a method for producing a modified resin in which the amount of unreacted raw materials is reduced.

[0008] Hereinafter, several embodiments of the present invention will be described in detail, but the present invention is not limited to the following embodiments.

[0009] In this specification, the term "step" refers not only to an independent step, but also to a step that is not clearly distinguishable from other steps, as long as the intended effect of the step is achieved. In this specification, a numerical range indicated using "to" indicates a range that includes the numerical values ​​before and after "to" as the minimum and maximum values, respectively. In the numerical ranges described in stages in this specification, the upper or lower limit of a numerical range of a certain step may be replaced with the upper or lower limit of a numerical range of another step. Furthermore, in the numerical ranges described in this specification, the upper or lower limit of the numerical range may be replaced with a value shown in the examples.

[0010] The method for producing a modified resin according to this embodiment includes the steps of feeding a modifying agent having a molecular weight of 2000 or less, a thermoplastic resin having a modifying moiety in a side chain that can react with the modifying agent, and a reaction catalyst into a twin-screw extruder having a pressure reducing device in the system, and carrying out a modification reaction of the side chain of the thermoplastic resin at a temperature of 190°C or higher and a pressure of 101.0 kPa or lower.

[0011] A twin-screw extruder is a device capable of melt-kneading a resin using two screws in a cylinder. Examples of twin-screw extruders include a twin-screw continuous reactor manufactured by Kurimoto, Ltd., a twin-screw extruder manufactured by The Japan Steel Works, Ltd., a twin-screw kneading extruder manufactured by Shibaura Machine Co., Ltd., and a twin-screw extruder manufactured by Coperion.

[0012] The twin-screw extruder may melt-knead the resin and perform the modification reaction in a single device, or two or more devices may be used. For example, melt-kneading may be performed in a first-stage device and the modification reaction may be performed in a second-stage device. Furthermore, the modification reaction may be performed using two or more devices, and the devices may be set to the same temperature and pressure conditions to ensure reaction time, or different temperature and pressure conditions to efficiently proceed with the reaction. The pressure reducing equipment may be a vent connected to a vacuum pump or the like. The vent may be located in the middle or end of the twin-screw extruder, or multiple vents may be installed. The pressure may be uniform throughout the twin-screw extruder, or multiple pressures may be set in the twin-screw extruder. Furthermore, the present invention is not limited to the use of a specific twin-screw extruder. To balance productivity and reaction rate, a single-screw extruder, a three-screw or more extruder, a static mixer, a thin-film evaporator, or a combination of these may be used.

[0013] The amount of unreacted modifier contained in the product can be reduced by carrying out the modification reaction between a modifier having a molecular weight of 2000 or less and a thermoplastic resin at a temperature of 190°C or higher and a pressure of 101.0 kPa or lower using a twin-screw extruder equipped with a pressure reducing device. The lower limit of the temperature may be 195°C or higher, 200°C or higher, 205°C or higher, 210°C or higher, or 230°C or higher. The upper limit of the temperature may be 350°C or lower, 300°C or lower, 290°C or lower, 285°C or lower, or 280°C or lower. The lower limit of the pressure may be 0.1 kPa or more, 1.0 kPa or more, 5.0 kPa or more, 0.8 kPa or more, or 10.0 kPa or more, and the upper limit of the pressure may be 100.0 kPa or less, 98.0 kPa or less, 96.0 kPa or less, 80.0 kPa or less, 70.0 kPa or less, or 50.0 kPa or less.

[0014] The temperature in the modification reaction is preferably 190 to 350 ° C., more preferably 190 to 300 ° C., even more preferably 190 to 285 ° C., even more preferably 200 to 285 ° C., particularly preferably 200 to 280 ° C., 210 to 285 ° C., or 230 to 285 ° C. From the viewpoint of the reaction rate of the modification reaction and the prevention of the modifier from scattering into the reduced pressure equipment, the pressure in the modification reaction is preferably 0.1 to 101.0 kPa, more preferably 1.0 to 98.0 kPa, 1.0 to 96.0 kPa, or 1.0 to 80.0 kPa, even more preferably 1.0 to 70.0 kPa, even more preferably 5.0 to 70.0 kPa, particularly preferably 10.0 to 50.0 kPa.

[0015] The method for producing a modified resin according to this embodiment may include the steps of: feeding a modifying agent having a molecular weight of 2000 or less, a thermoplastic resin having a modifying moiety in a side chain that can react with the modifying agent, and a reaction catalyst into a twin-screw extruder having a pressure-reducing device in the system, and carrying out a modification reaction of the side chain of the thermoplastic resin at a temperature of 190°C or higher and a pressure of 70 kPa or lower. By carrying out the modification reaction of the modifying agent having a molecular weight of 2000 or less and the thermoplastic resin using a twin-screw extruder having a pressure-reducing device at a temperature of 190°C or higher and a pressure of 70 kPa or lower, the amount of unreacted modifying agent contained in the product can be reduced.

[0016] The method for producing a modified resin according to this embodiment may include a first step of feeding a modifying agent having a molecular weight of 2000 or less, a thermoplastic resin having a modifying moiety in a side chain that can react with the modifying agent, and a reaction catalyst into a twin-screw extruder having a pressure reducing device in the system, and performing a modification reaction of the side chain of the thermoplastic resin at a temperature of 190°C or higher and a pressure of more than 70.0 kPa and 100.1 kPa or lower, and a second step of performing the modification reaction at a temperature of 190°C or higher and a pressure of 70.0 kPa or lower.

[0017] The temperature in the first and second steps may be 190 to 350°C, 190 to 300°C, 190 to 285°C, 200 to 285°C, 200 to 280°C, 210 to 285°C, or 230 to 285°C from the viewpoint of improving the modification reaction rate. The pressure in the first step may be 71.0 to 101.0 kPa, 75.0 to 100.0 kPa, 80.0 to 98.0 kPa, or 85.0 to 96.0 kPa from the viewpoint of improving the reaction consumption rate while suppressing the modification material from scattering into the pressure reducing equipment. The pressure in the second step may be 1.0 to 70.0 kPa, 5.0 to 60.0 kPa, 10.0 to 55.0 kPa, or 15.0 to 50.0 kPa from the viewpoint of reducing unreacted modification material.

[0018] Materials that can be used to produce the modified resin according to this embodiment will be described in detail below.

[0019] (Thermoplastic Resin) The thermoplastic resin according to this embodiment is not particularly limited as long as it is a polymer having a modifying moiety in a side chain that can react with a modifying agent.

[0020] Examples of thermoplastic resins include acrylic acid polymers, methacrylic acid polymers, vinyl alcohol polymers, methyl acrylate polymers, ethyl acrylate polymers, n-propyl acrylate polymers, n-butyl acrylate polymers, methyl methacrylate polymers, ethyl methacrylate polymers, n-propyl methacrylate polymers, n-butyl methacrylate polymers, vinyl formate polymers, vinyl acetate polymers, vinyl propionate polymers, vinyl (n-butylate) polymers, methyl vinyl ether polymers, ethyl vinyl ether polymers, n-propyl vinyl ether polymers, n-butyl vinyl ether polymers, maleic anhydride polymers, glycidyl acrylate polymers, glycidyl methacrylate polymers, 3-(dimethylamino)propyl acrylate polymers, 3-(dimethylamino)propyl methacrylate polymers, ethylene-acrylic acid copolymers, ethylene-methacrylic acid copolymers, ethylene-vinyl alcohol copolymers, ethylene-methyl acrylate copolymers, ethylene Examples of the copolymer include ethylene-ethyl acrylate copolymer, ethylene-n-propyl acrylate copolymer, ethylene-n-butyl acrylate copolymer, ethylene-methyl methacrylate copolymer, ethylene-ethyl methacrylate copolymer, ethylene-n-propyl methacrylate copolymer, ethylene-n-butyl methacrylate copolymer, ethylene-vinyl formate copolymer, ethylene-vinyl acetate copolymer, ethylene-vinyl propionate copolymer, ethylene-vinyl (n-butylate) copolymer, ethylene-methyl vinyl ether copolymer, ethylene-ethyl vinyl ether copolymer, ethylene-n-propyl vinyl ether copolymer, ethylene-n-butyl vinyl ether copolymer, ethylene-maleic anhydride copolymer, ethylene-glycidyl acrylate copolymer, ethylene-glycidyl methacrylate copolymer, ethylene-3-(dimethylamino)propyl acrylate copolymer, and ethylene-3-(dimethylamino)propyl methacrylate copolymer.

[0021] The thermoplastic resin is a polymer having at least one structural unit (sometimes referred to as structural unit C) selected from the group consisting of structural units represented by the following formula (2) and structural units represented by the following formula (3) as a structural unit having a modified moiety in a side chain (wherein, in formula (2), L ２１ may be —CO—O—, —O—CO—, or —O—).

[0022] In formula (2), R ２ represents a hydrogen atom or a methyl group, L ２１ represents a single bond, —CO—O—, —O—CO—, or —O—; L ２４ is C １～８ represents an alkylene group represented by the formula: ２５ represents a hydrogen atom, an epoxy group, -CH(OH)-CH ２ OH, a carboxy group, a hydroxy group, an amino group, or C １～４ It is to be noted that L represents an alkylamino group represented by the formula: ２１ In each of the horizontally written chemical formulas in the explanation of the chemical structure, the left side corresponds to the upper side of formula (2) (the main chain side of the polymer), and the right side corresponds to the lower side of formula (2) (the terminal side of the side chain of the polymer).

[0023] In formula (2), R ２ is preferably a hydrogen atom. ２１ is preferably —CO—O—, —O—CO—, or —O—, more preferably —CO—O— or —O—CO—, and even more preferably —CO—O—.

[0024] In formula (2), L ２４ C as １～８ Examples of the alkylene group in formula (2) include a methylene group, an ethylene group, an n-propylene group, a 1-methylethylene group, an n-butylene group, a 1,2-dimethylethylene group, a 1,1-dimethylethylene group, a 2,2-dimethylethylene group, an n-pentylene group, an n-hexylene group, an n-heptalene group, an n-octylene group, and a 2-ethyl-n-hexylene group. ２４ is preferably a methylene group, an ethylene group, or an n-propylene group, and more preferably a methylene group.

[0025] In formula (2), L ２５ C as １～４ Examples of the alkylamino group include a methylamino group, an ethylamino group, a propylamino group, a butylamino group, a dimethylamino group, and a diethylamino group. ２５ is preferably a hydrogen atom, an epoxy group, or —CH(OH)—CH ２ It is OH, and more preferably a hydrogen atom.

[0026] Examples of the structural unit represented by formula (2) include propylene, butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, acrylic acid, methacrylic acid, vinyl alcohol, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, and vinyl formate. , vinyl acetate, vinyl propionate, vinyl (n-butyrate), vinyl (isobutyrate), methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, sec-butyl vinyl ether, tert-butyl vinyl ether, glycidyl acrylate, glycidyl methacrylate, 2,3-dihydroxypropyl acrylate, 2,3-dihydroxypropyl methacrylate, 3-(dimethylamino)propyl acrylate, and 3-(dimethylamino)propyl methacrylate.

[0027] The thermoplastic resin according to this embodiment may be a thermoplastic resin having an ester bond in the side chain from the viewpoint of ease of industrial use. In this case, R ２ , L ２１ , L ２４ , L ２５The combination is preferably:

[0028] The thermoplastic resin according to this embodiment may be a polymer further having a structural unit derived from ethylene (sometimes referred to as structural unit A).

[0029] The melt flow rate (MFR) of the thermoplastic resin measured in accordance with JIS K7210 at a temperature of 190°C and a load of 21 N is preferably 0.1 to 500 g / 10 min, more preferably 1 to 100 g / 10 min, and even more preferably 5 to 50 g / 10 min.

[0030] Examples of methods for producing thermoplastic resins include coordination polymerization, cationic polymerization, anionic polymerization, and radical polymerization, with radical polymerization being preferred, and radical polymerization under high pressure being more preferred.

[0031] (Modifying material having a molecular weight of 2000 or less) The modifying material according to this embodiment has a molecular weight of 2000 or less and has a functional group that reacts with the modified site of the thermoplastic resin. Examples of the functional group include a hydroxy group, an amino group, a carboxy group, an isocyanate group, a halogen atom, a carbamate group, an amide group, and a urea bond.

[0032] The modifying material may be, for example, a compound having a hydroxy group (e.g., C １４～３０ Alcohols having an alkyl group of C １４～３０ amines having an alkyl group of C １４～３０ a carboxylic acid having an alkyl group of C １４～３０ isocyanates having alkyl groups of the formula C １４～３０ alkyl halides having an alkyl group of the formula C １４～３０ Carbamic acids having alkyl groups of C １４～３０ and carboxylic acid amides having an alkyl group of C １４～３０ The alkyl urea compound may be at least one compound selected from the group consisting of alkyl ureas having the alkyl groups listed above.

[0033] C １４～３０ Examples of alcohols having a straight-chain alkyl group include n-tetradecyl alcohol, n-pentadecyl alcohol, n-hexadecyl alcohol, n-heptadecyl alcohol, n-octadecyl alcohol, n-nonadecyl alcohol, n-eicosyl alcohol, n-heneicosyl alcohol, n-docosyl alcohol, n-tricosyl alcohol, n-tetracosyl alcohol, n-pentacosyl alcohol, n-hexacosyl alcohol, n-heptacosyl alcohol, n-octacosyl alcohol, n-nonacosyl alcohol, and n-triacontyl alcohol.

[0034] C １４～３０ Examples of alcohols having a branched alkyl group include isotetradecyl alcohol, isopentadecyl alcohol, isohexadecyl alcohol, isoheptadecyl alcohol, isooctadecyl alcohol, isononadecyl alcohol, isoeicosyl alcohol, isoheneicosyl alcohol, isodocosyl alcohol, isotricosyl alcohol, isotetracosyl alcohol, isopentacosyl alcohol, isohexacosyl alcohol, isoheptacosyl alcohol, isooctacosyl alcohol, isononacosyl alcohol, and isotriacontyl alcohol.

[0035] C １４～３０ Examples of amines having a linear alkyl group include n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecylamine, n-octadecylamine, n-nonadecylamine, n-eicosylamine, n-heneicosylamine, n-docosylamine, n-tricosylamine, n-tetracosylamine, n-pentacosylamine, n-hexacosylamine, n-heptacosylamine, n-octacosylamine, n-nonacosylamine, and n-triacontylamine.

[0036] C １４～３０Examples of amines having a branched alkyl group include isotetradecylamine, isopentadecylamine, isohexadecylamine, isoheptadecylamine, isooctadecylamine, isononadecylamine, isoeicosylamine, isoheneicosylamine, isodocosylamine, isotricosylamine, isotetracosylamine, isopentacosylamine, isohexacosylamine, isoheptacosylamine, isooctacosylamine, isononacosylamine, and isotriacontylamine.

[0037] C １４～３０ Examples of alkyl halides having a straight-chain alkyl group include n-tetradecyl iodide, n-pentadecyl iodide, n-hexadecyl iodide, n-heptadecyl iodide, n-octadecyl iodide, n-nonadecyl iodide, n-eicosyl iodide, n-heneicosyl iodide, n-docosyl iodide, n-tricosyl iodide, n-tetracosyl iodide, n-pentacosyl iodide, n-hexacosyl iodide, n-heptacosyl iodide, n-octacosyl iodide, n-nonacosyl iodide, and n-triacontyl iodide.

[0038] C １４～３０ Examples of alkyl halides having a branched alkyl group include isotetradecyl iodide, isopentadecyl iodide, isohexadecyl iodide, isoheptadecyl iodide, isooctadecyl iodide, isononadecyl iodide, isoeicosyl iodide, isoheneicosyl iodide, isodocosyl iodide, isotricosyl iodide, isotetracosyl iodide, isopentacosyl iodide, isohexacosyl iodide, isoheptacosyl iodide, isooctacosyl iodide, isononacosyl iodide, and isotriacontyl iodide.

[0039] C １４～３０Examples of carboxylic acids having a linear alkyl group include n-tetradecanoic acid, n-pentadecanoic acid, n-hexadecanoic acid, n-heptadecanoic acid, n-octadecanoic acid, n-nonadecanoic acid, n-eicosanoic acid, n-heneicosanoic acid, n-docosanoic acid, n-tricosanoic acid, n-tetracosanoic acid, n-pentacosanoic acid, n-hexacosanoic acid, n-heptacosanoic acid, n-octacosanoic acid, n-nonacosanoic acid, and n-triacontanoic acid.

[0040] C １４～３０ Examples of carboxylic acids having a branched alkyl group include isotetradecanoic acid, isopentadecanoic acid, isohexadecanoic acid, isoheptadecanoic acid, isooctadecanoic acid, isononadecanoic acid, isoeicosanoic acid, isoheneicosanoic acid, isodocosanoic acid, isotricosanoic acid, isotetracosanoic acid, isopentacosanoic acid, isohexacosanoic acid, isoheptacosanoic acid, isooctacosanoic acid, isononacosanoic acid, and isotriacontanoic acid.

[0041] C １４～３０ Examples of carboxylic acid amides having a linear alkyl group include n-tetradecanoic acid amide, n-pentadecanoic acid amide, n-hexadecanoic acid amide, n-heptadecanoic acid amide, n-octadecanoic acid amide, n-nonadecanoic acid amide, n-eicosanoic acid amide, n-heneicosanoic acid amide, n-docosanoic acid amide, n-tricosanoic acid amide, n-tetracosanoic acid amide, n-pentacosanoic acid amide, n-hexacosanoic acid amide, n-heptacosanoic acid amide, n-octacosanoic acid amide, n-nonacosanoic acid amide, and n-triacontanoic acid amide.

[0042] C １４～３０Examples of carboxylic acid amides having a branched alkyl group include isotetradecanoic acid amide, isopentadecanoic acid amide, isohexadecanoic acid amide, isoheptadecanoic acid amide, isooctadecanoic acid amide, isononadecanoic acid amide, isoeicosanoic acid amide, isoheneicosanoic acid amide, isodocosanoic acid amide, isotricosanoic acid amide, isotetracosanoic acid amide, isopentacosanoic acid amide, isohexacosanoic acid amide, isoheptacosanoic acid amide, isooctacosanoic acid amide, isononacosanoic acid amide, and isotriacontanoic acid amide.

[0043] C １４～３０ Examples of carboxylic acid halides having a linear alkyl group include n-tetradecanoic acid chloride, n-pentadecanoic acid chloride, n-hexadecanoic acid chloride, n-heptadecanoic acid chloride, n-octadecanoic acid chloride, n-nonadecanoic acid chloride, n-eicosanoic acid chloride, n-heneicosanoic acid chloride, n-docosanoic acid chloride, n-tricosanoic acid chloride, n-tetracosanoic acid chloride, n-pentacosanoic acid chloride, n-hexacosanoic acid chloride, n-heptacosanoic acid chloride, n-octacosanoic acid chloride, n-nonacosanoic acid chloride, and n-triacontanoic acid chloride.

[0044] C １４～３０ Examples of carboxylic acid halides having a branched alkyl group include isotetradecanoic acid chloride, isopentadecanoic acid chloride, isohexadecanoic acid chloride, isoheptadecanoic acid chloride, isooctadecanoic acid chloride, isononadecanoic acid chloride, isoeicosanoic acid chloride, isoheneicosanoic acid chloride, isodocosanoic acid chloride, isotricosanoic acid chloride, isotetracosanoic acid chloride, isopentacosanoic acid chloride, isohexacosanoic acid chloride, isoheptacosanoic acid chloride, isooctacosanoic acid chloride, isononacosanoic acid chloride, and isotriacontanoic acid chloride.

[0045] C １４～３０Examples of carbamic acids having a straight-chain alkyl group include n-tetradecylcarbamic acid, n-pentadecylcarbamic acid, n-hexadecylcarbamic acid, n-heptadecylcarbamic acid, n-octadecylcarbamic acid, n-nonadecylcarbamic acid, n-eicosylcarbamic acid, n-heneicosylcarbamic acid, n-docosylcarbamic acid, n-tricosylcarbamic acid, n-tetracosylcarbamic acid, n-pentacosylcarbamic acid, n-hexacosylcarbamic acid, n-heptacosylcarbamic acid, n-octacosylcarbamic acid, n-nonacosylcarbamic acid, and n-triacontylcarbamic acid.

[0046] C １４～３０ Examples of carbamic acids having a branched alkyl group include isotetradecylcarbamic acid, isopentadecylcarbamic acid, isohexadecylcarbamic acid, isoheptadecylcarbamic acid, isooctadecylcarbamic acid, isononadecylcarbamic acid, isoeicosylcarbamic acid, isoheneicosylcarbamic acid, isodocosylcarbamic acid, isotricosylcarbamic acid, isotetracosylcarbamic acid, isopentacosylcarbamic acid, isohexacosylcarbamic acid, isoheptacosylcarbamic acid, isooctacosylcarbamic acid, isononacosylcarbamic acid, and isotriacontylcarbamic acid.

[0047] C １４～３０ Examples of alkyl ureas having a straight-chain alkyl group include n-tetradecyl urea, n-pentadecyl urea, n-hexadecyl urea, n-heptadecyl urea, n-octadecyl urea, n-nonadecyl urea, n-eicosyl urea, n-heneicosyl urea, n-docosyl urea, n-tricosyl urea, n-tetracosyl urea, n-pentacosyl urea, n-hexacosyl urea, n-heptacosyl urea, n-octacosyl urea, n-nonacosyl urea, and n-triacontyl urea.

[0048] C １４～３０Examples of alkyl ureas having a branched alkyl group include isotetradecyl urea, isopentadecyl urea, isohexadecyl urea, isoheptadecyl urea, isooctadecyl urea, isononadecyl urea, isoeicosyl urea, isoheneicosyl urea, isodocosyl urea, isotricosyl urea, isotetracosyl urea, isopentacosyl urea, isohexacosyl urea, isoheptacosyl urea, isooctacosyl urea, isononacosyl urea, and isotriacontyl urea.

[0049] C １４～３０ Examples of isocyanates having a linear alkyl group include n-tetradecyl isocyanate, n-pentadecyl isocyanate, n-hexadecyl isocyanate, n-heptadecyl isocyanate, n-octadecyl isocyanate, n-nonadecyl isocyanate, n-eicosyl isocyanate, n-heneicosyl isocyanate, n-docosyl isocyanate, n-tricosyl isocyanate, n-tetracosyl isocyanate, n-pentacosyl isocyanate, n-hexacosyl isocyanate, n-heptacosyl isocyanate, n-octacosyl isocyanate, n-nonacosyl isocyanate, and n-triacontyl isocyanate.

[0050] C １４～３０ Examples of isocyanates having a branched alkyl group include isotetradecyl isocyanate, isopentadecyl isocyanate, isohexadecyl isocyanate, isoheptadecyl isocyanate, isooctadecyl isocyanate, isononadecyl isocyanate, isoeicosyl isocyanate, isoheneicosyl isocyanate, isodocosyl isocyanate, isotricosyl isocyanate, isotetracosyl isocyanate, isopentacosyl isocyanate, isohexacosyl isocyanate, isoheptacosyl isocyanate, isooctacosyl isocyanate, isononacosyl isocyanate, and isotriacontyl isocyanate.

[0051] When the modification reaction is a transesterification reaction, it is preferable to use a compound having a hydroxy group as the modifying agent from the viewpoint of ease of industrial use.１４～３０ It is more preferable to use an alcohol having a linear alkyl group of the formula:

[0052] The amount of the modifying agent used in the modification reaction is preferably 30 to 70 parts by mass, more preferably 30 to 65 parts by mass, and even more preferably 30 to 60 parts by mass, relative to 100 parts by mass of the total amount of the modifying agent and the thermoplastic resin, from the viewpoint of the number of reactive modification sites in the thermoplastic resin.

[0053] The reaction consumption rate of the modifying agent in the modification reaction is preferably 85% or more, more preferably 88% or more, and even more preferably 90% or more, from the viewpoint of efficiently reacting while suppressing the raw material cost of the modifying agent.

[0054] The amount of unreacted modifier in the modification reaction is preferably 5% by mass or less, more preferably 4% by mass or less, and even more preferably 3% by mass or less, from the viewpoint that the unreacted modifier bleeds out onto the surface of the modified resin during storage, causing defects in appearance.

[0055] (Reaction Catalyst) Examples of the reaction catalyst include alkali metal salts and Group 4 metal complexes. Examples of the alkali metal salts include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide, and alkali metal alkoxides such as lithium methoxide and sodium methoxide. Examples of the Group 4 metal complexes include tetra(isopropyl) orthotitanate, tetra(n-butyl) orthotitanate, and tetraoctadecyl orthotitanate.

[0056] The amount of the reaction catalyst added is preferably 0.050 equivalents or less, and may be 0.025 equivalents or less, 0.020 equivalents or less, 0.015 equivalents or less, or 0.010 equivalents or less, relative to the modified site of the thermoplastic resin, from the viewpoint of the effect on the reaction rate at the initial stage of the reaction and the yellowness of the modified resin.

[0057] (Modified Resin) The modified resin can be synthesized by reacting a modifying material with the modified portion of a thermoplastic resin, and has a structural unit derived from the above-mentioned modifying material in the side chain.

[0058] In one embodiment of the modified resin, the carbon number is 14 to 30 (C １４～３０ ) is an example of a polymer having a structural unit containing an alkyl group. The modified resin preferably has a structural unit represented by the following formula (1) (sometimes referred to as structural unit B). Structural unit B can be formed by reacting structural unit C contained in the thermoplastic resin with a modifying material.

[0059] In formula (1), R １ represents a hydrogen atom or a methyl group, L １１ represents a single bond, —CO—O—, —O—CO—, or —O—; L １２ is a single bond, -CH ２ -, -CH ２ -CH ２ -, -CH ２ -CH ２ -CH ２ -, -CH ２ -CH(OH)-CH ２ - or -CH ２ -CH(CH ２ OH)—, L １３ is a single bond, -CO-O-, -O-CO-, -O-, -CO-NH-, -NH-CO-, -CO-NH-CO-, -NH-CO-NH-, -NH-, or -N(CH ３ )-, L １６ represents an alkyl group having 14 to 30 carbon atoms. １１ , L １２ , and L １３ In each of the horizontally written chemical formulas, the left side corresponds to the upper side of formula (1) (the main chain side of the polymer), and the right side corresponds to the lower side of formula (1) (the terminal side of the side chain of the polymer).

[0060] R １ is preferably a hydrogen atom. １１ is preferably —CO—O—, —O—CO—, or —O—, more preferably —CO—O— or —O—CO—, and even more preferably —CO—O—. １２ is preferably a single bond, —CH ２ -, -CH ２ -CH ２ - or -CH ２ -CH２ -CH ２ -, and more preferably a single bond. １３ is preferably a single bond, —O—CO—, —O—, —NH—, or —N(CH ３ )-, more preferably a single bond.

[0061] L in formula (1) １６ C is used so that the composition containing the modified resin has good moldability. １４～３０ is an alkyl group of the formula: １４～３０ The alkyl group of １４～３０ and C １４～３０ Examples of branched alkyl groups include: ６ is preferably C １４～３０ and more preferably a straight chain alkyl group of C １４～２４ and more preferably C １６～２２ is a straight chain alkyl group.

[0062] C １４～３０ Examples of the straight-chain alkyl group include an n-tetradecyl group, an n-pentadecyl group, an n-hexadecyl group, an n-heptadecyl group, an n-octadecyl group, an n-nonadecyl group, an n-eicosyl group, an n-heneicosyl group, an n-docosyl group, an n-tricosyl group, an n-tetracosyl group, an n-pentacosyl group, an n-hexacosyl group, an n-heptacosyl group, an n-octacosyl group, an n-nonacosyl group, and an n-triacontyl group.

[0063] C １４～３０ Examples of the branched alkyl group include an isotetradecyl group, an isopentadecyl group, an isohexadecyl group, an isoheptadecyl group, an isooctadecyl group, an isononadecyl group, an isoeicosyl group, an isoheneicosyl group, an isodocosyl group, an isotricosyl group, an isotetracosyl group, an isopentacosyl group, an isohexacosyl group, an isoheptacosyl group, an isooctacosyl group, an isononacosyl group, and an isotriacontyl group.

[0064] When the modification reaction is a transesterification reaction, R １ , L １１ , L １２ , L １３As a combination of １ is a hydrogen atom, and L １１ , L １２ , and L １３ is a single bond, and L １６ is C １４～３０ and R １ is a hydrogen atom or a methyl group, and L １１ is —CO—O—, and L ２ and L ３ is a single bond, and L １６ is C １４～３０ The alkyl group may be a combination of the above.

[0065] R in formula (1) １ , L １１ , L １２ , and L １３ The combination is preferably:

[0066] The modified resin is preferably a polymer having a structural unit B represented by formula (1). Examples of polymers having a structural unit B represented by formula (1) include polymers consisting of structural unit B, polymers having structural unit B and structural unit A, polymers having structural unit B and structural unit C, and polymers having structural unit B, structural unit A, and structural unit C.

[0067] Examples of the "polymer consisting of structural unit B" include R １ is a hydrogen atom or a methyl group, and L １１ , L １２ , and L １３ is a single bond, and L １６ is C １４～３０ a polymer comprising a structural unit B represented by formula (1), which is an alkyl group represented by R １ is a hydrogen atom or a methyl group, and L １１ -CO-O-, L １２ and L １３ is a single bond, L １６ is C １４～３０ Examples of suitable polymers include polymers comprising a structural unit B represented by formula (1), which is an alkyl group represented by the following formula:

[0068] Examples of the "polymer having the structural unit B and the structural unit A" include R１ is a hydrogen atom or a methyl group, and L １１ , L １２ , and L １３ is a single bond, and L １６ is C １４～３０ Examples of suitable polymers include a polymer having a structural unit B represented by formula (1), which is an alkyl group represented by the formula (1), and a structural unit A. In this case, it is preferable that the total number of structural units A and B is 90% or more, relative to 100% of the total number of all structural units contained in the polymer.

[0069] Examples of "polymers having structural units B, A, and C" include R １ is a hydrogen atom or a methyl group, and L １１ is —CO—O—, and L １２ and L １３ is a single bond, and L １６ is C １４～３０ A structural unit B represented by formula (1) which is an alkyl group represented by formula (1), a structural unit A, and R ２ is a hydrogen atom or a methyl group, and L ２１ is —CO—O—, and L ２４ is a methylene group, and L ２５ and a structural unit C represented by formula (2) in which R is a hydrogen atom. In this case, the total number of structural units A, B, and C is 90% or more relative to 100% of the total number of all structural units contained in the polymer.

[0070] Examples of the "modified resin having the structural unit B and the structural unit C" include R １ is a hydrogen atom or a methyl group, and L １１ is —CO—O—, and L １２ and L １３ is a single bond, and L １６ is C １４～３０ A structural unit B represented by formula (1) which is an alkyl group, and R ２ is a hydrogen atom or a methyl group, and L ２１ is —CO—O—, and L ２４ is a methylene group, and L ２５and a structural unit C represented by formula (2) in which R is a hydrogen atom. In this case, it is preferable that the number of structural units B is 80% or more relative to 100% in total of the structural units B and C contained in the polymer.

[0071] In one embodiment of the modified resin, the number of structural units A is usually 0 to 99%, and the total number of structural units B and C is usually 1 to 100%, relative to 100% of the total number of structural units B and C. The number of structural units B is usually 1 to 100%, and the number of structural units C is usually 0 to 99%, relative to 100% of the total number of structural units B and C.

[0072] In one embodiment, the number of structural units A in the modified resin is 1 to 99% relative to the total number of structural units A, B, and C (100%), and is preferably 70 to 99%, more preferably 80 to 97.5%, and even more preferably 85 to 92.5% so that a molded article containing the modified resin has good shape retention. The total number of structural units B and C in the modified resin is preferably 1 to 30%, more preferably 2.5 to 20%, and even more preferably 7.5 to 15% relative to the total number of structural units A, B, and C (100%) so that a molded article containing the modified resin has good shape retention.

[0073] In one embodiment, the number of structural units B in the modified resin is usually 1 to 100% relative to the total number of structural units B and C (100%), and is preferably 60 to 100%, more preferably 80 to 100%, so that the heat storage performance of a composition containing the modified resin is good.

[0074] In one embodiment, the number of structural units C in the modified resin is usually 0 to 99% relative to 100% of the total number of structural units B and C, and is preferably 0 to 40%, more preferably 0 to 20%, so that the heat storage performance of a composition containing the modified resin is good.

[0075] The number of structural units A, the number of structural units B, and the number of structural units C were measured by a known method. １３ C nuclear magnetic resonance spectrum (hereinafter, １３ C-NMR spectrum) or１ H nuclear magnetic resonance spectrum (hereinafter, １ It is determined from the integral value of the signals assigned to each structural unit (H-NMR spectrum).

[0076] If the modified resin after production contains unreacted modifier, the modifier may bleed out from the resin, resulting in poor appearance. From the viewpoint of suppressing bleed-out of the modifier, the content of unreacted modifier contained in the modified resin is preferably 3.5% by mass or less, and more preferably 3.0% by mass or less.

[0077] If the modified resin has a large yellowish color, the yellowish color may affect molded articles of the modified resin. Therefore, the yellow index (YI), which indicates the yellowness of the modified resin, is preferably 30 or less, and more preferably 25 or less.

[0078] 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 these examples.

[0079] I. Amount of structural units contained in thermoplastic resin (mol % and mass %) The amounts of structural units derived from ethylene and structural units derived from methyl acrylate contained in the ethylene-methyl acrylate copolymer, which is a thermoplastic resin, were determined from NMR spectra measured using a nuclear magnetic resonance spectrometer (NMR) under the measurement conditions shown below. １３ C-NMR measurement conditions) Apparatus: AVANCE III 600HD manufactured by Bruker Biospin Co., Ltd. Measurement probe: 10 mm cryoprobe Measurement solvent: 1,2-dichlorobenzene / 1,1,2,2-tetrachloroethane-d2 = 85 / 15 (volume ratio) mixed solution Sample concentration: 100 mg / mL Measurement temperature: 135°C Measurement method: proton decoupling method Number of accumulations: 256 times Pulse width: 45 degrees Pulse repetition time: 4 seconds Measurement standard: tetramethylsilane

[0080] II. Content of unreacted modifier (mass%) The products obtained in the examples and comparative examples are mixtures of modified resin and unreacted modifier. The content of the modifier contained in the product was measured by the following method using gas chromatography (GC). The content of the unreacted modifier is the value when the total mass of the modified resin and unreacted modifier is 100 mass%.

[0081] (GC measurement conditions) GC apparatus: Shimadzu GC2010 Column: DB-1 (30 m, 0.25 mmφ, 0.25 μm) Column temperature: The column, maintained at 40°C, is heated to 300°C at a rate of 10°C / min, and then maintained at 300°C for 4 minutes. Vaporizer / detector temperature: 200°C / 300°C (FID) Carrier gas: Helium Pressure: 100 kPa Total flow rate: 50.0 mL / min Column flow rate: 1.33 mL / min Purge flow rate: 3.0 mL / min Linear velocity: 30.8 cm / sec Injection method: Split injection Injection volume: 1 μL Sample preparation: 8 mg / mL (o-dichlorobenzene solution)

[0082] (1) Preparation of a calibration curve 25 mg and 50 mg of the standard sample were weighed into 9 mL vials, 100 mg of n-tridecane was weighed therein as an internal standard, and 6 mL of o-dichlorobenzene was added as a solvent to completely dissolve the sample, thereby obtaining a standard solution for preparing a calibration curve. The standard solution for preparing a calibration curve was measured under the above GC measurement conditions, and a calibration curve was prepared with the GC area ratio between the standard sample and the internal standard on the vertical axis and the mass ratio between the standard mass and the internal standard on the horizontal axis, and the slope a of the calibration curve was determined.

[0083] (2) Measurement of the content of the substance to be measured (unreacted modifier) ​​in the sample (product) 50 mg of the sample and 100 mg of n-tridecane were weighed into a 9 mL vial, and 6 mL of o-dichlorobenzene was added thereto and the sample was completely dissolved at 80°C to obtain a sample solution.

[0084] The sample solution was measured under the GC measurement conditions described above, and the content PS of the analyte in the sample was calculated according to the following formula: PS: content (mass%) of the analyte in the sample WS: mass (mg) of the sample WIS: mass (mg) of the internal standard (IS) AS: peak area count number of the analyte AIS: peak area count number of the internal standard (IS) a: slope of the calibration curve of the analyte

[0085] III. Reaction Consumption Rate of Modifier (% by mass) The reaction consumption rate of the modifier in Examples 1 to 8 and Comparative Examples 2 and 3 was calculated by the following formula, from the proportion of structural units derived from methyl acrylate that were substituted with the modifier (conversion rate measured by NMR) and the proportion of structural units derived from methyl acrylate that were substituted with the modifier when all of the supplied modifiers were substituted with structural units derived from methyl acrylate (maximum conversion rate): Reaction Consumption Rate of Modifier (% by mass) = (Conversion rate measured by NMR / Maximum conversion rate) x 100

[0086] In Comparative Example 1, the catalyst was L １６ Since the modified material has a reactive group capable of forming the modified material, the reaction consumption rate of the modified material is calculated by calculating the ratio of the modified material to the methyl acrylate-derived structural units (conversion rate measured by NMR) and the ratio of the modified material to the methyl acrylate-derived structural units to the L possessed by the modified material and the catalyst. １６ The reaction consumption rate of the modifier (mass%) was calculated from the ratio of the methyl acrylate-derived structural units substituted with the modifier (maximum conversion rate) when all reactive groups that can constitute the modifier are substituted with structural units derived from methyl acrylate, using the following formula: Reaction consumption rate of the modifier (mass%) = (conversion rate measured by NMR / maximum conversion rate) x 100

[0087] IV. Measurement of Yellowness Index (YI) of Product (Conditions for preparing sheet samples for YI measurement) Press: Manual hydraulic vacuum heating press (IMC-19E6 type) Preheating conditions: 100°C, 5 minutes Pressing conditions: 100°C, 5 minutes, 10 MPa Cooling conditions: 20°C, 5 minutes, 3 MPa Press plate: 180mm x 180mm x 1.0mm Spacer: 180mm x 180mm x 0.5mm (inner frame 70mm x 70mm) Aluminum plate: 180mm x 180mm x 0.3mm Release film: 180mm x 180mm x 0.1mm (silicon-treated PET film, manufactured by PANAC Corporation)

[0088] (Preparation of sheet sample for YI measurement) A press plate, an aluminum plate, a spacer, a release film, 2.5 g of the product, a release film, an aluminum plate, and a press plate were stacked in this order and set in a press machine, and a sheet sample was prepared under the above-mentioned pressing conditions. After pressing, the product with the release film still attached was used as the sheet sample.

[0089] After setting the transmission measuring device on top of the main body and performing zero adjustment, the transmission measuring device was removed and a white standard plate was set on the sample stage and standard adjustment was performed. Next, the sheet sample was set on the sample stage and the white standard plate was placed and fixed on top, and measurements were performed four times under the following conditions. The measured values ​​were averaged to calculate YI. (YI measurement conditions) Model: Color computer SM-45 (manufactured by Suga Test Instruments Co., Ltd.) Measurement method: Reflection method Optical conditions: 45°C illumination, 0°C reception Irradiation hole diameter: 30 mm Light source: Halogen lamp Receiver: Silicon diode and filter Standard plate: White

[0090] V. Raw Materials The following raw materials were prepared to produce modified resins. (Thermoplastic Resins) A-1: ​​Ethylene-methyl acrylate copolymer (number of structural units derived from ethylene: 63.8% by mass, number of structural units derived from methyl acrylate: 36.2% by mass, MFR (190°C, 21N): 38 g / 10 min) A-2: Ethylene-methyl acrylate copolymer (number of structural units derived from ethylene: 72.4% by mass, number of structural units derived from methyl acrylate: 27.6% by mass, MFR (190°C, 21N): 6 g / 10 min) A-3: Ethylene-methyl acrylate copolymer (number of structural units derived from ethylene: 75.8% by mass, number of structural units derived from methyl acrylate: 24.2% by mass, MFR (190°C, 21N): 5 g / 10 min) (Modifiers) B-1: 1-hexadecanol (purity: 95% or more, molecular weight: 242) B-2: n-docosyl alcohol (a mixture containing n-eicosyl alcohol and n-octadecyl alcohol in addition to n-docosyl alcohol, purity: 80% or more, molecular weight: 326) (catalyst) C-1: tetraisopropyl orthotitanate (manufactured by Tokyo Chemical Industry Co., Ltd.) C-2: tetra(n-octadecyl) orthotitanate (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0091] VI. Apparatus To produce the modified resins of Examples 1 to 4 and Comparative Example 2, an apparatus was used in which a twin-screw extruder M1 and a continuous twin-screw reactor M2 were connected by metal piping. Twin-screw extruder M1 (Kurimoto, KEXN-30) Screw diameter D = 32 mm Effective screw length L / screw diameter D = 31.5 A vent port was provided in the middle of the extruder. Twin-screw continuous reactor M2 (Kurimoto, 8L-HB reactor) Screw diameter D = 118 mm Effective screw length L / screw diameter D = 4.5 A vent port was provided at the top of the apparatus, and the apparatus was connected via metal piping to a vacuum pump equipped with a cooling trap midway through the piping.

[0092] To produce the modified resins of Examples 5 and 6 and Comparative Examples 1 and 3, an apparatus was used in which a conical feeder M3 and a twin-screw extruder M4 were connected by metal piping. Conical feeder M3 (The Japan Steel Works, Ltd., 2TR-75): Hopper capacity = 20 L; Screw diameter D = 75 mm; Effective screw length L / Screw diameter D = 4; Twin-screw extruder M4 (The Japan Steel Works, Ltd., TEX30α): Screw diameter D = 30 mm; Effective screw length L / Screw diameter D = 77

[0093] To produce the modified resins of Examples 7 and 8, the thermoplastic resin and the modifier were quantitatively fed using gravimetric feeders, and a twin-screw extruder M5 (TEX25α III, manufactured by The Japan Steel Works, Ltd.) with a screw diameter D of 26.5 mm and an effective screw length L / screw diameter D of 70 was used.

[0094] The twin-screw extruder M5 was equipped with multiple vent ports, each of which was provided with an intermediate vent I and a terminal vent II as vent connection sections in order to operate stably at a desired pressure. Next, to suppress the vent-up phenomenon in which the modified resin leaks into the metal piping at the vent connection section, a side vent stuffer TSV (Japan Steel Works, Ltd.) was used at the vent connection section. In order to individually control the pressure for each vent, a seal ring (Japan Steel Works, Ltd.) was provided at the element configuration section corresponding to the section between the intermediate vent I and the terminal vent II as a kneading screw element to ensure the modified resin sealability within the device between the vents.

[0095] [Preparation of Modified Resin] (Example 1) Using two nitrogen-purged feeders, 100 parts by mass of A-1 was supplied from the first feeder, and 88.4 parts by mass of B-1 was supplied from the second feeder, and these were supplied to a nitrogen-purged twin-screw extruder M1. The total supply amount of A-1 and B-1 was adjusted to 5 kg / hour. 0.598 parts by mass of C-1 was supplied from the intermediate vent port of M1 using a liquid addition pump. The twin-screw extruder M1 was set at a temperature of 150°C and a rotation speed of 300 min －１ The temperature was set to 100°C and the mixture was melt-kneaded.

[0096] The melt-kneaded mixture was mixed at a temperature of 210°C and a rotation speed of 50 min. －１The pressure inside the device was adjusted to 13.3 kPa, and a product containing a modified resin, ethylene-n-hexadecyl acrylate-methyl acrylate copolymer, was obtained from the discharge port of M2.

[0097] The content (mass %) of unreacted B-1 contained in the product, the conversion rate (mol %), and the reaction consumption rate (mass %) of B-1 were calculated.

[0098] Example 2 A product was obtained in the same manner as in Example 1, except that the temperature of M2 was changed to 250° C. and the pressure was changed to 40.0 kPa.

[0099] Example 3 A product was obtained in the same manner as in Example 1, except that the temperature of M2 was changed to 250° C. and the pressure was changed to 12.0 kPa.

[0100] Example 4 A product was obtained in the same manner as in Example 1, except that the supply amount of C-1 was changed to 2.988 parts by mass, and the temperature of M2 was changed to 250° C. and the pressure was changed to 12.0 kPa.

[0101] Example 5 Using two feeders that had been previously purged with nitrogen, 100 parts by mass of A-1 was supplied from the first feeder, and 88.4 parts by mass of B-1 was supplied from the second feeder. These were then quantitatively supplied to a twin-screw extruder that had been purged with nitrogen, and a mixture of A-1 and B-1 was recovered.

[0102] The mixture was fed into a conical feeder M3 filled with nitrogen gas and adjusted to a temperature of 110 to 120°C, and melt-kneaded. The melt-kneaded mixture was then continuously fed into a twin-screw extruder M4, the atmosphere of which had been replaced with nitrogen, at a rate of 3 kg / hour. 0.598 parts by mass of C-1 was fed into the intermediate vent port of M4 using a liquid addition pump.

[0103] M4 temperature 230℃, rotation speed 60min －１ The pressure inside the apparatus was adjusted to 26.7 kPa, and a product containing an ethylene-n-hexadecyl acrylate-methyl acrylate copolymer was obtained from the discharge port M4. The content (mass%) of unreacted B-1 contained in the product, the conversion rate (mol%), and the reaction consumption rate (mass%) of B-1 were calculated.

[0104] (Example 6) The amount of the molten mixture supplied to M4 was changed to 5 kg / hour, the temperature of M4 was set to 260°C, and the rotation speed was set to 100 min.－１ A product was obtained in the same manner as in Example 5, except that the pressure was adjusted to 66.7 kPa.

[0105] (Example 7) Using two nitrogen-purged feeders, 100 parts by mass of A-3 was supplied from the first feeder, and 58.0 parts by mass of B-1 was supplied from the second feeder, and these were supplied to a nitrogen-purged twin-screw extruder M5. The total supply amount of A-3 and B-1 was adjusted to 3 kg / hour. 0.399 parts by mass of C-1 was supplied from the intermediate vent port of M5 using a liquid addition pump. The twin-screw extruder M5 was maintained at a temperature of 270°C and a rotation speed of 120 min －１ The pressure was adjusted to 96.0 kPa at intermediate vent I and to 21.3 kPa at intermediate vent II, and a product containing an ethylene-n-hexadecyl acrylate-methyl acrylate copolymer was obtained from the discharge port M5. The content (mass%) of unreacted B-1 contained in the product, the conversion rate (mol%), and the reaction consumption rate (mass%) of B-1 were calculated.

[0106] Example 8 A product was obtained in the same manner as in Example 7, except that the temperature of M5 was set to 285°C and the pressure was adjusted to 46.7 kPa using intermediate vent II. The conversion rate (mol %) of unreacted B-1 contained in the product and the reaction consumption rate (mass %) of B-1 were not measured.

[0107] Comparative Example 1 43.7 parts by mass of A-2 was supplied from the first feeder, and 41.4 parts by mass of B-2 was supplied from the second feeder. These were then supplied in fixed quantities to a twin-screw extruder that had been purged with nitrogen, and a mixture of A-2 and B-2 was recovered.

[0108] The above mixture and 14.9 parts by mass of C-2 were charged into a conical feeder M3 filled with nitrogen gas and adjusted to a temperature of 110 to 120°C, and melt-kneaded. Thereafter, the melt-kneaded mixture was continuously supplied to a twin-screw extruder M4, the inside of which had been substituted with nitrogen, at a rate of 5 kg / hour.

[0109] M4 temperature 180℃, rotation speed 150min －１The pressure inside the apparatus was adjusted to 1.0 kPa, and a product containing an ethylene-n-docosyl acrylate-n-eicosyl acrylate-n-octadecyl acrylate-methyl acrylate copolymer was obtained from the discharge port M4. The content (mass%) of unreacted B-2 contained in the product, the conversion rate (mol%), and the reaction consumption rate (mass%) of B-2 were calculated.

[0110] Comparative Example 2 A product was obtained in the same manner as in Example 1, except that the temperature of M2 was changed to 180° C. and the pressure was changed to 5.3 kPa.

[0111] (Comparative Example 3) The amount of the molten mixture supplied to M4 was changed to 5 kg / hour, the temperature of M4 was 170°C, and the rotation speed was 100 min. －１ A product was obtained in the same manner as in Example 5, except that the pressure was adjusted to 16.0 kPa.

[0112] The results for the modified resins prepared in Examples 1 to 8 are shown in Table 1, and the results for the modified resins prepared in Comparative Examples 1 to 3 are shown in Table 2.

[0113]

[0114]

Claims

1. A method for producing a modified resin, comprising the steps of: feeding a modifying agent having a molecular weight of 2,000 or less, a thermoplastic resin having a side chain with a modifying site capable of reacting with the modifying agent, and a reaction catalyst into a twin-screw extruder having a pressure reduction device within the system, and carrying out a modification reaction of the side chain of the thermoplastic resin at a temperature of 190°C or more and a pressure of 101.0 kPa or less.

2. The method according to claim 1, wherein the modification reaction is carried out at a temperature of 190° C. or higher and a pressure of 70.0 kPa or lower.

3. The method according to claim 1 or 2, wherein the modification reaction is a transesterification reaction.

4. The method according to claim 1 or 2, wherein the thermoplastic resin is a thermoplastic resin having an ester bond in the side chain.

5. The method according to claim 1 or 2, wherein the modifying agent is a compound having a hydroxy group.

6. The method according to claim 1 or 2, wherein the amount of the reaction catalyst added is 0.050 equivalents or less relative to the modified site of the thermoplastic resin.

7. The method according to claim 1 or 2, wherein the amount of the modifying agent is 30 to 70 parts by mass per 100 parts by mass of the total amount of the modifying agent and the thermoplastic resin.

8. The method according to claim 1 or 2, wherein the reaction consumption rate of the modifying material is 85% or more.

9. The method according to claim 1 or 2, wherein the modified resin is a polymer having a structural unit represented by the following formula (1): [(In formula (1), R １ represents a hydrogen atom or a methyl group; L １１ represents a single bond, —CO—O—, —O—CO—, or —O—; L １２ is a single bond, -CH ２ --, --CH ２ -CH ２ --, --CH ２ -CH ２ -CH ２ --, --CH ２ -CH(OH)-CH ２ - or -CH ２ -CH(CH ２ OH)—, L １３ is a single bond, -CO-O-, -O-CO-, -O-, -CO-NH-, -NH-CO-, -CO-NH-CO-, -NH-CO-NH-, -NH-, or -N(CH ３ )-, L １６ represents an alkyl group having 14 to 30 carbon atoms.

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