Production method for modified resin

Abstract

The present invention relates to a method for producing a modified resin from a thermoplastic resin (2) and a side chain modification material (1) that has a molecular weight of no more than 2000, the method including steps A–C. Step A: a step for supplying the side chain modification material (1) to a reactor. Step B: a step, after step A, for supplying the thermoplastic resin (2) to the reactor in a state in which the side chain modification material (1) can flow. Step C: a step, after step B, for modifying a side chain of the thermoplastic resin (2) by means of the side chain modification material (1).

Description

Modified resin manufacturing method

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

[0002] Polymers and their raw materials are produced by various methods (see, for example, Patent Documents 1 to 3).

[0003] International Publication No. 2021 / 241432 Special Publication No. 2015-512895 Special Publication No. 2015-514698

[0004] Meanwhile, in the method for producing a modified resin from a thermoplastic resin and a modifying material, further improvement in production efficiency is desired.

[0005] Therefore, an object of the present invention is to provide a method for producing a modified resin stably in a short time.

[0006] [1] A method for producing a modified resin from a thermoplastic resin (2) and a side-chain modifying material (1) having a molecular weight of 2,000 or less, the method comprising the following steps A to C: Step A: supplying the side-chain modifying material (1) to a reactor; Step B: after step A, supplying the thermoplastic resin (2) to the reactor while the side-chain modifying material (1) is in a flowable state; and Step C: after step B, modifying the side chain of the thermoplastic resin (2) with the side-chain modifying material (1). [2] The method according to [1], wherein step C is carried out under reduced pressure. [3] The method according to [1] or [2], wherein step C includes a step of discharging a reaction by-product produced in step C. [4] The method according to any one of [1] to [3], wherein the filling rate of the side-chain modifying material (1) and the thermoplastic resin (2) is 80% or less of the nominal volume of the reactor. [5] The method according to any one of [1] to [4], wherein the total amount of the side chain modifying material (1) and the thermoplastic resin (2) supplied to the reactor is 90% by mass or more, based on the total mass of the components supplied to the reactor. [6] The method according to [5], wherein the amount of the side chain modifying material (1) supplied is 30 parts by mass or more and 70 parts by mass or less, and the amount of the thermoplastic resin (2) supplied is 30 parts by mass or more and 70 parts by mass or less, based on 100 parts by mass of the total amount of the side chain modifying material (1) and the thermoplastic resin (2) supplied. [7] The method according to any one of [1] to [6], wherein after step C, the components in the reactor are discharged from the bottom of the reactor. [8] The method according to any one of [1] to [7], wherein step C includes a step of reacting the thermoplastic resin (2) with the side chain modifying material (1) at a temperature of 180°C or less. [9] The method according to any one of [1] to [8], wherein the reactor is equipped with a stirrer, and the stirrer has a large impeller.

[10] The method according to any one of [1] to [9], wherein the thermoplastic resin (2) has an ester bond in a side chain.

[11] The method according to any one of [1] to

[10] , wherein the thermoplastic resin (2) has a structural unit derived from ethylene.

[12] The method according to any one of [1] to

[11] , wherein the side-chain-modified material (1) has one hydroxy group in the molecule.

[13] The method according to any one of [1] to

[12] , wherein the modification in step C is carried out by transesterification.

[14] The method according to any one of [1] to

[13] , wherein the modified resin is a polymer containing a structural unit (B) represented by the following formula (1): (In formula (1), R represents a hydrogen atom or a methyl group, L １ represents a single bond, —CO—O—, —O—CO—, or —O—; L ２ 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 ３ is a single bond, -CO-O-, -O-CO-, -O-, -CO-NH-, -NH-CO-, -CO-NH-CO-, -NH-CO-NH-, -NH-, or -N(CH ３ )- represents L ６ represents an alkyl group having 14 to 30 carbon atoms; １ , L ２ , and L ３ 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 (1) and the right side corresponds to the lower side of formula (1).

[0007] According to the present invention, a method for producing a modified resin stably in a short time is provided.

[0008] FIG. 1 is a schematic diagram showing a production facility used in Examples and Comparative Examples.

[0009] Hereinafter, several embodiments of the present invention will be described in detail, but the present invention is not limited to the following embodiments.

[0010] 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 numerical ranges described in stages in this specification, the upper or lower limit value described in one numerical range may be replaced with the upper or lower limit value of another numerical range described in stages. Furthermore, in numerical ranges described in this specification, the upper or lower limit value of that numerical range may be replaced with a value shown in an example.

[0011] In this specification, unless otherwise specified, the materials exemplified below may be used alone or in combination of two or more within the range that meets the conditions. When multiple substances corresponding to each component are present, the content of each component means the total amount of the multiple substances unless otherwise specified.

[0012] (Method for Producing Modified Resin) The method for producing a modified resin of this embodiment is a method for producing a modified resin from a thermoplastic resin (2) and a side chain modifying material (1) having a molecular weight of 2000 or less.

[0013] This method includes the following steps A to C. Step A: A step of supplying a side-chain modifying material (1) to a reactor; Step B: A step of supplying a thermoplastic resin (2) to the reactor after step A while the side-chain modifying material (1) is in a flowable state; and Step C: A step of modifying the side chains of the thermoplastic resin (2) with the side-chain modifying material (1) after step B.

[0014] This method is carried out in a reactor, and may be either a batch type or a continuous type, and is not limited by the examples and comparative examples in this specification. Generally, a batch type is preferable when the reaction rate is to be increased, but it is also possible to balance productivity while suppressing a decrease in reaction rate by adjusting the residence time distribution in a continuous polymerization reactor by appropriately designing and installing the connection mode of the vessels and the stirring blades.

[0015] [Thermoplastic resin (2)] Examples of the thermoplastic resin (2) include polyethylene (PE), ethylene copolymers, polypropylene (PP), propylene copolymers, vinyl chloride homopolymers (PVC), polystyrene homopolymers (PS), cyclic olefin copolymers (COC), acrylonitrile-styrene copolymers (AS), acrylonitrile-butadiene-styrene copolymers (ABS), polymethyl methacrylate (PMMA), polymethyl acrylate (PMA), polyvinyl alcohol (PVA), polyethylene terephthalate (PET), polyacrylonitrile (PAN), polyamide 6 (PA6), polyamide 66 (PA66), polycarbonate (PC), polyphenylene sulfide (PPS), and polyether ether ketone (PEEK). Examples of such resins include those that soften and become plastic when heated.

[0016] From the viewpoint of the moldability and shape retention of the resulting modified resin, the thermoplastic resin (2) may contain, for example, a structural unit (A) derived from ethylene. The structural unit (A) is a structural unit obtained by polymerizing ethylene. The structural unit (A) may form a branched structure in the polymer.

[0017] In one example, the thermoplastic resin (2) may be a polymer having a structural unit (C) represented by the following formula (2).

[0018] In formula (2), R represents a hydrogen atom or a methyl group; １ represents a single bond, —CO—O—, —O—CO—, or —O—; L ４ represents an alkylene group having 1 to 8 carbon atoms; ５ represents a hydrogen atom, an epoxy group, —CH(OH)—CH ２ OH, a carboxy group, a hydroxy group, an amino group, or an alkylamino group having 1 to 4 carbon atoms. １ In each of the horizontally written chemical formulas, the left side corresponds to the upper side of formula (2), and the right side corresponds to the lower side of formula (2).

[0019] The thermoplastic resin (2) may have, for example, an ester bond in the side chain, from the viewpoint of facilitating control of the side chain modification reaction.

[0020] The thermoplastic resin (2) having an ester bond in the side chain may be, for example, a resin having a structural unit (C) represented by the above formula (2), in which L １ is —CO—O—.

[0021] In formula (2), L ４ Examples of the alkylene group having 1 to 8 carbon atoms as the alkylene group 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.

[0022] In formula (2), L ５ Examples of the alkylamino group having 1 to 4 carbon atoms as the alkylamino group include a methylamino group, an ethylamino group, a propylamino group, a butylamino group, a dimethylamino group, and a diethylamino group.

[0023] Examples of the structural unit (C) include a structural unit derived from propylene, a structural unit derived from butene, a structural unit derived from 1-pentene, a structural unit derived from 1-hexene, a structural unit derived from 1-heptene, a structural unit derived from 1-octene, a structural unit derived from acrylic acid, a structural unit derived from methacrylic acid, a structural unit derived from vinyl alcohol, a structural unit derived from methyl acrylate, a structural unit derived from ethyl acrylate, a structural unit derived from n-propyl acrylate, a structural unit derived from isopropyl acrylate, a structural unit derived from n-butyl acrylate, a structural unit derived from isobutyl acrylate, a structural unit derived from sec-butyl acrylate, a structural unit derived from tert-butyl acrylate, a structural unit derived from methyl methacrylate, a structural unit derived from ethyl methacrylate, a structural unit derived from n-propyl methacrylate, a structural unit derived from isopropyl methacrylate, a structural unit derived from n-butyl methacrylate, a structural unit derived from isobutyl methacrylate, and a structural unit derived from sec-butyl methacrylate. structural units derived from tert-butyl methacrylate, structural units derived from vinyl formate, structural units derived from vinyl acetate, structural units derived from vinyl propionate, structural units derived from vinyl(n-butylate), structural units derived from vinyl(isobutyrate), structural units derived from methyl vinyl ether, structural units derived from ethyl vinyl ether, structural units derived from n-propyl vinyl ether, structural units derived from isopropyl vinyl ether, structural units derived from n-butyl vinyl ether, structural units derived from isobutyl vinyl ether, structural units derived from sec-butyl vinyl ether, structural units derived from tert-butyl vinyl ether, structural units derived from glycidyl acrylate, structural units derived from glycidyl methacrylate, structural units derived from 2,3-dihydroxypropyl acrylate, structural units derived from 2,3-dihydroxypropyl methacrylate, structural units derived from 3-(dimethylamino)propyl acrylate, and structural units derived from 3-(dimethylamino)propyl methacrylate.

[0024] The thermoplastic resin (2) may have two or more types of the structural unit (C), and may be, for example, a polymer having a structural unit derived from methyl acrylate, a structural unit derived from ethyl acrylate, and a structural unit derived from glycidyl methacrylate.

[0025] Specific examples of the thermoplastic resin (2) 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, and ethylene-methyl acrylate copolymers. , 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. The thermoplastic resin (2) is preferably an ethylene-based copolymer.Examples of the ethylene copolymer include an ethylene-unsaturated carboxylic acid copolymer, an ethylene-vinyl alcohol copolymer, an ethylene-unsaturated carboxylic acid ester copolymer, an ethylene-vinyl carboxylate copolymer, and an ethylene-alkyl vinyl ether copolymer. Examples of the ethylene-unsaturated carboxylic acid copolymer include an ethylene-acrylic acid copolymer, an ethylene-methacrylic acid copolymer, and an ethylene-maleic anhydride copolymer.

[0026] The thermoplastic resin (2) is preferably a polymer in which the number of the structural units (A) is 0% or more and 99% or less, and the total number of the structural units (C) is 1% or more and 100% or less, relative to 100% as the total number of the structural units (A) and the structural units (C); more preferably, the number of the structural units (A) is 70% or more and 99% or less, and the total number of the structural units (C) is 1% or more and 30% or less.

[0027] The melt flow rate (MFR) of the thermoplastic resin (2), measured in accordance with JIS K7210 at a temperature of 190°C and a load of 21 N, is preferably 0.1 g / 10 min or more and 500 g / 10 min or less, more preferably 1 g / 10 min or more and 300 g / 10 min or less, and even more preferably 5 g / 10 min or more and 100 g / 10 min or less.

[0028] [Side Chain Modifying Material (1)] Examples of the side chain modifying material (1) include alcohols, amines, alkyl halides, carboxylic acids, carboxylic acid amides, carboxylic acid halides, carbamic acids, alkyl ureas, and isocyanates, all of which have a molecular weight of 2000 or less.

[0029] The side chain modifying material (1), for example, may be at least one compound (hereinafter also referred to as "compound (α)") selected from the group consisting of alcohols having an alkyl group containing 14 to 30 carbon atoms, amines having an alkyl group containing 14 to 30 carbon atoms, alkyl halides having an alkyl group containing 14 to 30 carbon atoms, carboxylic acids having an alkyl group containing 14 to 30 carbon atoms, carboxylic acid amides having an alkyl group containing 14 to 30 carbon atoms, carboxylic acid halides having an alkyl group containing 14 to 30 carbon atoms, carbamic acids having an alkyl group containing 14 to 30 carbon atoms, alkyl ureas having an alkyl group containing 14 to 30 carbon atoms, and isocyanates having an alkyl group containing 14 to 30 carbon atoms.

[0030] The alkyl group may be, for example, a straight-chain alkyl group or a branched alkyl group.

[0031] Examples of the alcohol having a linear alkyl group having from 14 to 30 carbon atoms 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.

[0032] Examples of the alcohol having a branched alkyl group having from 14 to 30 carbon atoms 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.

[0033] Examples of the amine having a linear alkyl group having from 14 to 30 carbon atoms 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.

[0034] Examples of the amine having a branched alkyl group having from 14 to 30 carbon atoms include isotetradecylamine, isopentadecylamine, isohexadecylamine, isoheptadecylamine, isooctadecylamine, isononadecylamine, isoeicosylamine, isoheneicosylamine, isodocosylamine, isotricosylamine, isotetracosylamine, isopentacosylamine, isohexacosylamine, isoheptacosylamine, isooctacosylamine, isononacosylamine, and isotriacontylamine.

[0035] Examples of the alkyl halide having a linear alkyl group having from 14 to 30 carbon atoms 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.

[0036] Examples of the alkyl halide having a branched alkyl group having from 14 to 30 carbon atoms 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.

[0037] Examples of the carboxylic acid having a linear alkyl group having from 14 to 30 carbon atoms 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.

[0038] Examples of the carboxylic acid having a branched alkyl group having from 14 to 30 carbon atoms 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.

[0039] Examples of the carboxylic acid amide having a linear alkyl group having from 14 to 30 carbon atoms 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.

[0040] Examples of the carboxylic acid amide having a branched alkyl group having from 14 to 30 carbon atoms 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.

[0041] Examples of the carboxylic acid halide having a linear alkyl group having from 14 to 30 carbon atoms 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.

[0042] Examples of the carboxylic acid halide having a branched alkyl group having from 14 to 30 carbon atoms 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.

[0043] Examples of the carbamic acid having a linear alkyl group having from 14 to 30 carbon atoms 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.

[0044] Examples of the carbamic acid having a branched alkyl group having from 14 to 30 carbon atoms 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.

[0045] Examples of the alkyl urea having a linear alkyl group having from 14 to 30 carbon atoms 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.

[0046] Examples of the alkyl urea having a branched alkyl group having from 14 to 30 carbon atoms 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.

[0047] Examples of the isocyanate having a linear alkyl group having 14 to 30 carbon atoms 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.

[0048] Examples of the isocyanate having a branched alkyl group having 14 to 30 carbon atoms 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.

[0049] The side chain modifying material (1) may have one hydroxy group in the molecule, from the viewpoint that it is easy to handle industrially and there are many substances that can be easily used as a side chain modifying material.

[0050] Examples of the side chain modified material (1) having one hydroxy group in the molecule 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-triacosyl alcohol. Examples of monohydric alcohols include butyl alcohol, 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.

[0051] [Step A] In step A, the side chain-modifying material (1) is fed into a reactor.

[0052] The reactor is a reactor in which the side chains of the thermoplastic resin (2) are modified with the side chain modifying material (1). The reactor can be, for example, a tank-type reactor (such as a reaction kettle).

[0053] The nominal volume of the reactor is, for example, 0.1 m ３ More than 50m ３ It may be less than 0.5 m ３ More than 30m ３ It may be 1.0 m or less, ３ More than 20m ３ It may be the following:

[0054] The reactor is preferably equipped with a stirring blade.

[0055] Examples of stirring blades include large blades such as ribbon blades, anchor blades, and wide blades, and small blades such as paddle blades, turbine blades, propeller blades, and Pfaudler blades.

[0056] The stirring blade can be, for example, a large blade from the viewpoint of being able to handle high viscosity ranges. Furthermore, it can be a wide blade from the viewpoint of being able to handle a wide viscosity range. Examples of wide blades include the stirring blade "FULLZONE" (product name) manufactured by Kobelco Environmental Solutions Co., Ltd., "Super-Mix MR203" and "Super-Mix MR205" manufactured by Satake Chemical Machinery Mfg. Co., Ltd., "Hi-F Mixer" (all product names) manufactured by Soken Technics Co., Ltd., and "MAXBLEND" (product name) manufactured by Sumitomo Heavy Industries Process Equipment Co., Ltd.

[0057] The side chain-modifying material (1) can be supplied in a solid state or in a flowable state (for example, a liquid state).

[0058] The flowable side-chain-modified material (1) may be, for example, a molten or dissolved side-chain-modified material (1) in a solvent. The molten or dissolved state includes a state in which a solid remains partially dissolved in the liquid and is stirrable.

[0059] When the side chain modifying material (1) is supplied in a solid state, before step B, the side chain modifying material (1) in the reactor can be heated, for example, to make it flowable.

[0060] [Step B] In step B, the thermoplastic resin (2) is supplied to the reactor while the side-chain-modifying material (1) is in a flowable state.

[0061] From the viewpoint of improving productivity, the total amount of the side chain modifying material (1) and the thermoplastic resin (2) supplied to the reactor is preferably 90% by mass or more, more preferably 95% by mass or more, and even more preferably 98% by mass or more, based on the total mass of the components supplied to the reactor. The total amount of the side chain modifying material (1) and the thermoplastic resin (2) supplied to the reactor may be, for example, 100% by mass or less, 99.8% by mass or less, or 99.6% by mass or less, based on the total mass of the components supplied to the reactor.

[0062] The amount of the side chain modifying material (1) supplied may be, for example, 30 parts by mass or more and 70 parts by mass or less, 35 parts by mass or more and 60 parts by mass or less, 40 parts by mass or more and 65 parts by mass or less, 40 parts by mass or more and 55 parts by mass or less, or 45 parts by mass or more and 60 parts by mass or less, relative to 100 parts by mass of the total amount of the side chain modifying material (1) and the thermoplastic resin (2) supplied.

[0063] The amount of the thermoplastic resin (2) supplied may be, for example, 30 parts by mass or more and 70 parts by mass or less, 35 parts by mass or more and 60 parts by mass or less, 40 parts by mass or more and 65 parts by mass or less, 40 parts by mass or more and 55 parts by mass or less, or 45 parts by mass or more and 60 parts by mass or less, relative to 100 parts by mass of the total amount of the side chain modifying material (1) and the thermoplastic resin (2) supplied.

[0064] Preferably, the amount of the side chain modifying material (1) supplied is 30 parts by mass or more and 70 parts by mass or less, and the amount of the thermoplastic resin (2) supplied is 30 parts by mass or more and 70 parts by mass or less, relative to 100 parts by mass in total of the side chain modifying material (1) and the thermoplastic resin (2).

[0065] The amount of the side chain modifying material (1) supplied relative to 100 parts by mass of the thermoplastic resin (2) may be, for example, 42 parts by mass or more and 234 parts by mass or less, 53 parts by mass or more and 150 parts by mass or less, or 66 parts by mass or more and 123 parts by mass or less.

[0066] From the viewpoint of operational stability through liquid level control, the filling rate of the side chain modifying material (1) and the thermoplastic resin (2) is preferably 80% or less of the nominal volume of the reactor. This filling rate may be 90% or less, 70% or less, or 65% or less of the nominal volume of the reactor. From the viewpoint of productivity, this filling rate may be 30% or more, 40% or more, or 50% or more of the nominal volume of the reactor.

[0067] In the case of a batch type, the above-mentioned filling rate can be calculated by the following formula: (Filling rate of raw materials) [%] = 100 × (Total volume of raw materials) [m ３ ] / (nominal volume of reactor) [m ３] [wherein the raw materials are the side chain modified material (1) and the thermoplastic resin (2), and the total volume of the raw materials [m ３ ] is the volume [m ３ ] and the volume [m ３ ] and the volume of each raw material [m ３ ] is the ratio of the amount of each raw material used [kg] to the density [kg / m ３ In the case of a continuous reactor, the packing rate can be calculated by the following formula: (Filling rate of raw material) [%] = 100 × (Total volume of raw materials present in the reactor) [m ３ ]) / (nominal volume of reactor) [m ３ ]

[0068] The thermoplastic resin (2) may be supplied, for example, in a solid state or in a flowable state (for example, in a liquid state).

[0069] When the thermoplastic resin (2) is fed in a solid state, it is preferable to heat the reactor after feeding to melt or dissolve the thermoplastic resin (2).

[0070] [Step C] In step C, the side chains of the thermoplastic resin (2) are modified with the side chain modifying material (1). The modification can be carried out by, for example, an addition reaction, a substitution reaction, or an oxidation-reduction reaction. The modification is preferably carried out by a transesterification reaction, which is a type of substitution reaction, because the reaction heat is small and the reaction is easy to control.

[0071] Step C is preferably carried out under reduced pressure. When foaming occurs, the pressure can be gradually reduced, for example. The pressure in the reactor in step C may be, for example, 500 Torr or less, 200 Torr or less, or 100 Torr or less. From the viewpoint of promoting the equilibrium reaction, this pressure may be, for example, 10 Torr or less. This pressure may be, for example, 3 Torr or more, 1 Torr or more, or 0.5 Torr or more.

[0072] The temperature in step C may be, for example, 40°C or higher and 250°C or lower, 100°C or higher and 200°C or lower, or 130°C or higher and 180°C or lower.

[0073] Step C preferably includes a step of reacting the thermoplastic resin (2) with the side-chain modifying material (1) at a temperature of 180°C or lower.

[0074] Step C may be carried out in the presence of a solvent, such as hexane, heptane, octane, nonane, decane, toluene, and xylene.

[0075] From the viewpoint of promoting the reaction, step C may include a step of discharging reaction by-products produced in step C. This step may be, for example, a step of discharging reaction by-products distilled off under reduced pressure from the reactor to the outside of the reaction system.

[0076] Step C may be carried out in the presence of a catalyst.

[0077] Examples of the 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.

[0078] The amount of the catalyst added may be, for example, 0.01 parts by mass or more and 50 parts by mass or less, or 0.01 parts by mass or more and 5 parts by mass or less, relative to 100 parts by mass of the total amount of the thermoplastic resin (2) and the side chain modifying material (1).

[0079] After step C, the components in the reactor are discharged, for example, from the bottom of the reactor.

[0080] After step C, before the components in the reactor are extracted, additives (antioxidants, reaction terminators, etc.), other functional material components (low-molecular-weight heat storage materials, etc.), etc. may be supplied to the reactor.

[0081] [Modified resin]

[0082] In one example, the modified resin may be a polymer containing a structural unit (B) represented by the following formula (1).

[0083]

[0084] In formula (1), R represents a hydrogen atom or a methyl group; １ represents a single bond, —CO—O—, —O—CO—, or —O—; L ２ 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 ３ is a single bond, -CO-O-, -O-CO-, -O-, -CO-NH-, -NH-CO-, -CO-NH-CO-, -NH-CO-NH-, -NH-, or -N(CH ３ )- represents L ６ represents an alkyl group having 14 to 30 carbon atoms; １ , L ２ , and L ３ 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 (1) and the right side corresponds to the lower side of formula (1).

[0085] The polymer containing the structural unit (B) may be, for example, a polymer having a side chain (-L １ -L ４ -L ５ ) can be prepared by modifying

[0086] In formula (1), L ６ Examples of the alkyl group having 14 to 30 carbon atoms as L include a linear alkyl group having 14 to 30 carbon atoms and a branched alkyl group having 14 to 30 carbon atoms. ６ is preferably a linear alkyl group having from 14 to 30 carbon atoms, more preferably a linear alkyl group having from 14 to 24 carbon atoms, and even more preferably a linear alkyl group having from 16 to 22 carbon atoms.

[0087] Examples of the linear alkyl group having from 14 to 30 carbon atoms 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.

[0088] Examples of the branched alkyl group having 14 to 30 carbon atoms 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.

[0089] Examples of the structural unit (B) include a structural unit derived from n-hexadecene, a structural unit derived from n-octadecene, a structural unit derived from n-eicosene, a structural unit derived from n-docosene, a structural unit derived from n-tetracosene, a structural unit derived from n-hexacosene, a structural unit derived from n-octacosene, a structural unit derived from n-triacontene, a structural unit derived from n-dotriacontene, a structural unit derived from n-tetradecyl acrylate, a structural unit derived from n-pentadecyl acrylate, a structural unit derived from n-hexadecyl acrylate, and a structural unit derived from n-hexadecyl acrylate. A structural unit derived from n-heptadecyl acrylate, a structural unit derived from n-octadecyl acrylate, a structural unit derived from n-nonadecyl acrylate, a structural unit derived from n-eicosyl acrylate, a structural unit derived from n-heneicosyl acrylate, a structural unit derived from n-docosyl acrylate, a structural unit derived from n-tricosyl acrylate, a structural unit derived from n-tetracosyl acrylate, a structural unit derived from n-pentacosyl acrylate, a structural unit derived from n-hexacosyl acrylate, -a structural unit derived from heptacosyl acrylate, a structural unit derived from n-octacosyl acrylate, a structural unit derived from n-nonacosyl acrylate, a structural unit derived from n-triacontyl acrylate, a structural unit derived from n-tetradecyl methacrylate, a structural unit derived from n-pentadecyl methacrylate, a structural unit derived from n-hexadecyl methacrylate, a structural unit derived from n-heptadecyl methacrylate, a structural unit derived from n-octadecyl methacrylate, a structural unit derived from n-nonadecyl methacrylate, a structural unit derived from n-eicosyl methacrylate, a structural unit derived from n-heneicosyl methacrylate, a structural unit derived from n-docosyl methacrylate, a structural unit derived from n-tricosyl methacrylate, a structural unit derived from n-tetracosyl methacrylate, a structural unit derived from n-pentacosyl methacrylate, a structural unit derived from n-hexacosyl methacrylate, a structural unit derived from n-heptacosyl methacrylate, a structural unit derived from n-octacosyl methacrylate, a structural unit derived from n-nonacosyl methacrylate,Examples of such a structural unit include a structural unit derived from n-triacontyl methacrylate, a structural unit derived from n-vinyltetradecylate, a structural unit derived from n-vinylhexadecylate, a structural unit derived from n-vinyloctadecylate, a structural unit derived from n-vinyleicosylate, a structural unit derived from n-vinyldocosylate, a structural unit derived from n-tetradecyl vinyl ether, a structural unit derived from n-hexadecyl vinyl ether, a structural unit derived from n-octadecyl vinyl ether, a structural unit derived from n-eicosyl vinyl ether, and a structural unit derived from n-docosyl vinyl ether.

[0090] The modified resin may have two or more types of the structural unit (B), and may be, for example, a polymer having a structural unit derived from n-eicosyl acrylate and a structural unit derived from n-octadecyl acrylate.

[0091] From the viewpoint of moldability and shape retention when formed into a molded article, the modified resin is preferably a polymer having a structural unit (A) derived from ethylene.

[0092] The modified resin is preferably a polymer having a structural unit (B) represented by formula (1) and a structural unit (A) derived from ethylene.

[0093] The modified resin may have a structural unit (C) represented by the above formula (2).

[0094] The modified resin may have two or more types of the structural unit (C), and may be, for example, a polymer having a structural unit derived from methyl acrylate, a structural unit derived from ethyl acrylate, and a structural unit derived from glycidyl methacrylate.

[0095] The modified resin is preferably a polymer having a structural unit (B) represented by formula (1).

[0096] Examples of polymers having the structural unit (B) represented by formula (1) include: polymers consisting of the structural unit (B); polymers having the structural unit (B) and the structural unit (A); polymers having the structural unit (B) and the structural unit (C); and polymers having the structural unit (B), the structural unit (A), and the structural unit (C).

[0097] The polymer composed of the structural unit (B) may be, for example, a polymer in which R is a hydrogen atom and L １ , L ２ , and L ３ is a single bond, and L ６ a polymer comprising a structural unit (B) represented by formula (1), wherein R is an alkyl group having from 14 to 30 carbon atoms; and １ is —CO—O—, and L ２ and L ３ is a single bond, and L ６ is an alkyl group having from 14 to 30 carbon atoms.

[0098] The polymer having the structural unit (B) and the structural unit (A) may be, for example, a polymer in which R is a hydrogen atom and L １ , L ２ , and L ３ is a single bond, and L ６ a polymer having a structural unit (B) represented by formula (1), wherein R is an alkyl group having from 14 to 30 carbon atoms, and the structural unit (A), wherein the total number of the structural units (A) and the structural units (B) is 90% or more relative to 100% of the total number of all structural units contained in the polymer; and １ is —CO—O—, and L ２ and L ３ is a single bond, and L ６ is an alkyl group having from 14 to 30 carbon atoms, and a structural unit (A), and may further include the structural unit (C), wherein the total number of the structural units (A) and (B) is 90% or more relative to 100% of the total number of all structural units contained in the polymer.

[0099] From the viewpoint of increasing ΔH, the modified resin may be a polymer in which the number of the structural units (B) is more than 50% and not more than 80%, relative to 100% in total number of the structural units (B) and the structural units (A).

[0100] From the viewpoint of moldability, the modified resin may be a polymer in which the number of the structural units (B) is 10% or more and 50% or less, relative to 100% in total of the structural units (B) and the structural units (A).

[0101] The polymer having the structural unit (B) and the structural unit (C) may be, for example, a polymer in which R is a hydrogen atom or a methyl group, and L １ is —CO—O—, and L ２ and L ３ is a single bond, and L ６ is an alkyl group having 14 to 30 carbon atoms; R is a hydrogen atom or a methyl group; and L １ is —CO—O—, and L ４ is a methylene group, and L ５ and a structural unit (C) represented by formula (2) in which R is a hydrogen atom. In this case, the number of structural units (B) is preferably 80% or more relative to 100% of the total number of structural units (B) and (C) contained in the polymer.

[0102] In the modified resin, the number of the structural units (A) is, for example, 0% or more and 99% or less, and the total number of the structural units (B) and (C) is, for example, 100%, relative to the total number of the structural units (A), (B), and (C), respectively. The total number of the structural units (B) and (C) is, for example, 1% or more and 100% or less, and the number of the structural units (C) is, for example, 0% or more and 99% or less, relative to the total number of the structural units (B) and (C), respectively.

[0103] In the modified resin, the number of the structural units (A) is, from the viewpoint of shape retention when molded into a molded article, preferably 70% to 99% of the total number of the structural units (A), the structural units (B), and the structural units (C), 100%, more preferably 80% to 97.5%, and even more preferably 83% to 92.5%. In the modified resin, the total number of the structural units (B) and the structural units (C), from the viewpoint of shape retention when molded into a molded article, is, from the viewpoint of shape retention when molded into a molded article, preferably 1% to 30% of the total number of the structural units (A), the structural units (B), and the structural units (C), 100%, more preferably 2.5% to 20%, and even more preferably 7.5% to 17%.

[0104] In the modified resin, the number of the structural units (B) can be, for example, 1% or more and 100% or less, relative to the total number of the structural units (B) and the structural units (C), which is 100%. From the viewpoint of heat storage performance, this number may be, for example, 60% or more and 100% or less, or 80% or more and 100% or less.

[0105] In the modified resin, the number of the structural units (C) can be, for example, 0% to 99% relative to the total number of the structural units (B) and (C), which is 100%. From the viewpoint of heat storage performance, this number may be, for example, 0% to 40% or 0% to 20%.

[0106] The number of the structural units (A), the number of the structural units (B), and the number of the structural units (C) were measured by a well-known method. １３ C nuclear magnetic resonance spectrum (hereinafter, １３ C-NMR spectrum) or １ H nuclear magnetic resonance spectrum (hereinafter, １ The 1H-NMR spectrum can be obtained from the integral values ​​of the signals assigned to each structural unit.

[0107] When the modified resin is produced by a method of reacting a polymer having the structural unit (C) represented by the above formula (2) and which may have a structural unit (A) derived from ethylene with at least one compound (α), the number of the structural units (A), the number of the structural units (B), and the number of the structural units (C) can be determined, for example, by the following method.

[0108] When the thermoplastic resin (2) contains a structural unit (A) derived from ethylene, first, the number of the structural unit (A) and the structural unit (C) contained in the thermoplastic resin (2) is determined. １３ When determining from a C-NMR spectrum, for example, the number of dyads (AA, AC, CC) of the structural unit (A) and the structural unit (C) is determined from the spectrum and substituted into the following formula to determine the number of the structural unit (A) and the structural unit (C): Here, AA is a structural unit (A)-structural unit (A) dyad, AC is a structural unit (A)-structural unit (C) dyad, and CC is a structural unit (C)-structural unit (C) dyad.

[0109] Number of structural units (A)=100−number of structural units (C) Number of structural units (C)=100×(AC / 2+CC) / (AA+AC+CC) The structural unit (C) contained in the thermoplastic resin (2) reacts with the compound (α) to form the structural unit (B) in the modified resin, and the conversion rate of the structural unit (C) due to the reaction is determined by the following method.

[0110] The conversion rate is calculated by substituting the integral value of the signal attributed to a specific carbon contained in the side chain of the structural unit (C) of the thermoplastic resin (2) (hereinafter referred to as integral value Y) and the integral value of the signal attributed to a specific carbon contained in the side chain of the structural unit (B) of the modified resin (hereinafter referred to as integral value Z) into the following formula.

[0111] Conversion rate = Z / (Y + Z) In the reaction between thermoplastic resin (2) and compound (α), the structural unit (A) contained in thermoplastic resin (2) does not change, so the number of structural units (A) contained in the modified resin and the number of structural units (A) contained in thermoplastic resin (2) are assumed to be the same. The number of structural units (B) contained in the modified resin is calculated as the product of the number of structural units (C) contained in thermoplastic resin (2) and the conversion rate. The number of structural units (C) contained in the modified resin is calculated as the difference between the number of structural units (C) contained in thermoplastic resin (2) and the number of structural units (B) contained in the modified resin.

[0112] The method of this embodiment described above is a method for producing a modified resin from a thermoplastic resin (2) and a side-chain modifying material (1) having a molecular weight of 2000 or less, and includes the following steps A to C. This method allows for stable production of a modified resin in a short time. Step A: Supplying the side-chain modifying material (1) to a reactor; Step B: After step A, supplying the thermoplastic resin (2) to the reactor while the side-chain modifying material (1) is in a flowable state; and Step C: After step B, modifying the side chains of the thermoplastic resin (2) with the side-chain modifying material (1).

[0113] In the above method, step C can be carried out under reduced pressure, which can further shorten the production time of the modified resin.

[0114] In the above method, step C may include a step of discharging reaction by-products produced in step C. This can further improve operational stability and further shorten the production time of the modified resin.

[0115] In the above method, the filling rate of the side chain modifying material (1) and the thermoplastic resin (2) can be 80% or less of the nominal volume of the reactor, which can further improve operational stability and further shorten the production time of the modified resin.

[0116] In the above method, the total amount of the side chain modifying material (1) and the thermoplastic resin (2) supplied to the reactor may be 90% by mass or more, based on the total mass of the components supplied to the reactor, thereby further improving productivity.

[0117] In the above method, the amount of the side chain modifying material (1) supplied may be 30 parts by mass or more and 70 parts by mass or less, and the amount of the thermoplastic resin (2) supplied may be 30 parts by mass or more and 70 parts by mass or less, relative to 100 parts by mass of the total amount of the side chain modifying material (1) and the thermoplastic resin (2). This can further shorten the production time of the modified resin.

[0118] In the above method, it is preferable to discharge the components in the reactor from the bottom of the reactor after step C. This allows the obtained modified resin to be efficiently recovered.

[0119] In the above method, step C may include a step of reacting the thermoplastic resin (2) with the side-chain modifying material (1) at a temperature of 180° C. or less, thereby further shortening the production time of the modified resin while suppressing deterioration of the thermoplastic resin (2) and scattering of the side-chain modifying material (1) outside the reactor.

[0120] In the above method, the reactor may be equipped with a stirrer, and the stirrer may have large blades, thereby further improving operational stability.

[0121] In the above method, the thermoplastic resin (2) may have an ester bond in the side chain, which makes it easier to control the side chain modification and to easily produce the modified resin.

[0122] In the above method, the thermoplastic resin (2) may have a structural unit derived from ethylene, which makes it possible to easily produce a modified resin that is excellent in moldability and shape retention when formed into a molded article.

[0123] In the above method, the side chain-modified material (1) can have one hydroxy group in the molecule, which makes it possible to easily produce a modified resin that is easy to handle industrially.

[0124] In the above method, the modification in step C can be carried out by transesterification, which makes it easy to control the side chain modification and to easily produce the modified resin.

[0125] In the above method, the modified resin may be a polymer containing a structural unit (B) represented by the following formula (1): Such a modified resin has excellent heat storage performance. (In formula (1), R represents a hydrogen atom or a methyl group; L １ represents a single bond, —CO—O—, —O—CO—, or —O—; L ２ 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 ３ is a single bond, -CO-O-, -O-CO-, -O-, -CO-NH-, -NH-CO-, -CO-NH-CO-, -NH-CO-NH-, -NH-, or -N(CH ３ )- represents L ６ represents an alkyl group having 14 to 30 carbon atoms; １ , L ２ , and L ３ 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 (1) and the right side corresponds to the lower side of formula (1).

[0126] 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.

[0127] [I] Amounts (number [%] and mass [% by mass]) of the structural unit (A) derived from ethylene and the structural unit (C) derived from methyl acrylate contained in thermoplastic resin (2) (ethylene-methyl acrylate copolymer) Nuclear magnetic resonance spectra (hereinafter referred to as NMR spectra) were measured using a nuclear magnetic resonance spectrometer (NMR) under the measurement conditions shown below.

[0128] <Carbon nuclear magnetic resonance ( １３C-NMR) Measurement Conditions> Apparatus: AVANCE III 600HD manufactured by Bruker Biospin Co., Ltd. Measurement probe: 10 mm cryoprobe Measurement solvent: mixed solution of 1,2-dichlorobenzene / 1,1,2,2-tetrachloroethane-d2 = 85 / 15 (volume ratio) 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

[0129] From the measurement results, the integral values ​​in the ranges of a1, b1, c1, d1, and e1 were determined, and the number of dyads (AA, AC, CC) of the structural unit (A) and the structural unit (C) was calculated using the following formula: a1: 29.0-31.0 ppm b1: 32.5-33.2 ppm c1: 42.0-42.3 ppm d1: 43.5-44.5 ppm e1: 45.5-46.5 ppm AA = a1 / 4 + b1 / 2 AC = e1 CC = c1 + d1 Here, AA is a structural unit (A)-structural unit (A) dyad, AC is a structural unit (A)-structural unit (C) dyad, and CC is a structural unit (C)-structural unit (C) dyad.

[0130] Next, the amounts (number [%] and mass [% by mass]) of the structural units (A) and the structural units (C) were determined from the following formulas: Number of structural units (A) = 100 - number of structural units (C) Number of structural units (C) = 100 x (AC / 2 + CC) / (AA + AC + CC) Mass % of structural units (A) = (number of structural units (A) x molecular weight of structural units (A)) / (number of structural units (A) x molecular weight of structural units (A) + number of structural units (C) x molecular weight of structural units (C)) Mass % of structural units (C) = (number of structural units (C) x molecular weight of structural units (C)) / (number of structural units (A) x molecular weight of structural units (A) + number of structural units (C) x molecular weight of structural units (C))

[0131] [II] Amounts (number [%] and mass [% by mass]) of the ethylene-derived structural unit (A), the structural unit (B) represented by formula (1), and the methyl acrylate-derived structural unit (C) contained in the modified resin <Conversion rate XB of the methyl acrylate-derived structural unit (C) to the structural unit (B) represented by formula (1)> (unit: %) Since the structural unit (C) contained in the thermoplastic resin (2) reacts with the compound (α) to form the structural unit (B) of the modified resin, the conversion rate XB of the structural unit (C) to the structural unit (B) was determined by the following method.

[0132] The above carbon nuclear magnetic resonance ( １３ The NMR spectrum of the modified resin was measured under the same conditions as those for the C-NMR measurement, and from the measurement results, the integral value of the signal (range f1) attributed to a specific carbon contained in the side chain of the structural unit (C) and the integral value of the signal (range g1) attributed to a specific carbon contained in the side chain of the structural unit (B) were determined, and the conversion rate XB was calculated from the following formula: f1: 50.5-51.2 ppm g1: 63.9-64.8 ppm Conversion rate (XB) = 100 × g1 / (f1 + g1)

[0133] <Amounts (number [%] and mass [% by mass]) of the ethylene-derived structural unit (A), the structural unit (B) represented by formula (1), and the methyl acrylate-derived structural unit (C) contained in the modified resin> In the reaction between the thermoplastic resin (2) and the compound (α), the structural unit (A) contained in the thermoplastic resin (2) does not change, so the number of structural units (A) contained in the modified resin and the number of structural units (A) contained in the thermoplastic resin (2) were assumed to be the same. The number of structural units (B) contained in the modified resin was calculated as the product of the number of structural units (C) contained in the thermoplastic resin (2) and the conversion rate XB. The number of structural units (C) contained in the modified resin was calculated as the difference between the number of structural units (C) contained in the thermoplastic resin (2) and the number of structural units (B) contained in the modified resin.

[0134] The contents (mass%) of the structural unit (A), the structural unit (B), and the structural unit (C) contained in the modified resin were each calculated using the following formula. Mass % of structural units (A) = (number of structural units (A) × molecular weight of structural units (A)) / (number of structural units (A) × molecular weight of structural units (A) + number of structural units (B) × molecular weight of structural units (B) + number of structural units (C) × molecular weight of structural units (C)) Mass % of structural units (B) = (number of structural units (B) × molecular weight of structural units (B)) / (number of structural units (A) × molecular weight of structural units (A) + number of structural units (B) × molecular weight of structural units (B) + number of structural units (C) × molecular weight of structural units (C)) Mass % of structural units (C) = (number of structural units (C) × molecular weight of structural units (C)) / (number of structural units (A) × molecular weight of structural units (A) + number of structural units (B) × molecular weight of structural units (B) + number of structural units (C) × molecular weight of structural units (C))

[0135] [III] Content (% by mass) of compound having unreacted C14-30 alkyl group (side chain modified material (1)) The products obtained in the examples and comparative examples are mixtures of modified resin and compound having unreacted C14-30 alkyl group. The content of compound having unreacted C14-30 alkyl group contained in the product was measured by the following method using gas chromatography (GC). The content of the unreacted compound is a value when the total mass of the modified resin and unreacted compound is taken as 100% by mass.

[0136] [GC measurement conditions] Apparatus: Shimadzu GC-2030 Column: DB-1 (30 m, 0.25 mmφ, 1.0 μm) Column temperature: After holding at 60°C for 5 minutes, increase the temperature to 280°C at 25°C / min, hold at 280°C for 10 minutes, and then increase the temperature to 300°C at 10°C / min. Vaporizer / detector temperature: 300°C / 300°C (FID) Carrier gas: Helium Pressure: 150 kPa Total flow rate: 107.6 mL / min Column flow rate: 2.05 mL / min Purge flow rate: 3.0 mL / min Linear velocity: 42.8 cm / sec Injection method / split ratio: Split injection / 1:50 Injection volume: 1 μL

[0137] (1) Preparation of Calibration Curve [Preparation of Internal Standard Solution] 0.2 g of 1,4-dioxane and 0.2 g of octadecane were added to 40 g of anisole and dissolved to prepare an internal standard solution. Octadecane was used as the internal standard for 1-hexadecanol and 1-octadecanol. [Preparation of Standard Solution for Calibration Curve] Solutions (1) to (4) for preparing the standard solutions were prepared according to the following procedure. 0.1 g each of the measurement objects (1-hexadecanol and 1-octadecanol) was mixed with 9.8 g of 1,2-dichlorobenzene to prepare solution (4). Solution (4) was diluted 8-fold, 4-fold, or 2-fold with 1,2-dichlorobenzene to prepare solutions (1) to (3), respectively. Then, 0.1 g of each solution for preparing the standard solution, 0.5 g of the internal standard solution, and 16 g of 1,2-dichlorobenzene were mixed to prepare four levels of standard solutions for the calibration curve.

[0138] [GC Measurement] The standard solution for preparing a calibration curve was measured under the GC measurement conditions described above, and a calibration curve was prepared with the GC area ratio of the object to be measured and the internal standard substance on the vertical axis and the mass ratio of the object to be measured and the internal standard substance on the horizontal axis, and the slope a of the calibration curve was determined.

[0139] (2) Measurement of the content of the substance to be measured (a compound having an unreacted C14-30 alkyl group) in the sample (product) [Solution preparation] 0.1 g of the sample and 0.5 g of the internal standard solution were added to 16 g of 1,2-dichlorobenzene, and the sample was completely dissolved at 80°C to obtain a sample solution.

[0140] [GC Measurement] 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

[0141] [IV] Filling rate of raw materials The filling rate [%] of raw materials was calculated using the following formula. The raw materials were the side chain modified material (1) and the thermoplastic resin (2), and the total volume [m ３ ] is the volume [m ３] and the volume [m ３ ] and the volume of each raw material [m ３ ] is the ratio of the amount of each raw material used [kg] to the density [kg / m ３ (Filling rate of raw material) [%] = 100 × (total volume of raw material) [m ３ ] / (nominal volume of reactor) [m ３ ]

[0142] <Thermoplastic resin (2)> The following ethylene-methyl acrylate copolymer is produced, for example, by copolymerizing ethylene and methyl acrylate in an autoclave reactor at a reaction temperature of 195°C and a reaction pressure of 160 MPa using tert-butyl peroxypivalate as a radical polymerization initiator. A-1: ​​Ethylene-methyl acrylate copolymer [manufactured by Sumitomo Chemical Co., Ltd.] Methyl acrylate content: 36.7 mass%, 15.9 mol% MFR: 34 g / 10 min (190°C, 2.16 kgf) Density: 968 kg / m ３ A-2: Ethylene-methyl acrylate copolymer [manufactured by Sumitomo Chemical Co., Ltd.] Methyl acrylate content: 31.4 mass%, 13.0 mol% MFR: 38 g / 10 min (190°C, 2.16 kgf) Density: No data (the density of A-1, 968 kg / m, was used to calculate the filling rate) ３ (Using

[0143] <Side Chain Modified Material (1)> B-1: 1-Hexadecanol [manufactured by GODREJ] Density 818 kg / m ３ B-2: 1-octadecanol [manufactured by Godrej] Density 812 kg / m ３

[0144] <Catalyst> C-1: tetraisopropyl orthotitanate [manufactured by Nippon Soda Co., Ltd.] C-2: tetraoctadecyl orthotitanate [manufactured by Matsumoto Fine Chemical Co., Ltd.]

[0145] <Cleaning solvent for catalyst supply piping> D-1: 2-propanol [manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.]

[0146] <Production of Modified Resin (Heat Storage Polymer)> Example 1: Using the production equipment 100 shown in FIG. 1, side chain modification of thermoplastic resin (2) was carried out according to the following procedure.

[0147] The manufacturing facility 100 has a nominal volume of 1.25 m ３ The reactor 10 is equipped with a Maxblend impeller (manufactured by Sumitomo Heavy Industries Process Equipment Co., Ltd., product name: MAXBLEND), a vacuum pump 3, and a cooling trap 2 for reaction by-products between the reactor 10 and the vacuum pump 3. The reactor 10, the cooling trap 2, and the vacuum pump 3 are connected by piping heated to a temperature equal to or higher than the melting point of the side-chain-modified material.

[0148] [Procedure] 109 kg of B-1 and 225 kg of B-2 were loaded into a nitrogen-purged reactor, and B-1 and B-2 were melted and dried while stirring under conditions of a jacket temperature of 175°C or less and a minimum pressure of 2 Torr. After 0.5 hours, it was visually confirmed that B-1 and B-2 had melted. Subsequently, the pressure was restored to atmospheric pressure with nitrogen, and while B-1 and B-2 were in a molten state, 358 kg of A-1 was loaded, and the raw materials were melted, mixed, and dried while stirring under conditions of a jacket temperature of 175°C or less and a minimum pressure of 0.6 Torr until the sample temperature reached 130°C or higher. After 1 hour of mixing, the raw materials were completely melted, and the raw material temperature was 134°C. The actual raw material mixing time was 1.5 hours, consisting of 0.5 hours for dissolving B-1 and B-2 and 1 hour for subsequent mixing with A-1.

[0149] Subsequently, the pressure was restored to atmospheric pressure with nitrogen, and 2.13 kg of C-1 was injected. Then, 0.72 kg of dehydrated D-1 was injected to wash the remaining amount of C-1 in the catalyst supply pipe. Thereafter, the jacket temperature and the rotation speed of the stirring blade were adjusted so that the internal temperature was 145 ° C or higher and 150 ° C or lower, and the reaction was carried out under reduced pressure until the total amount of B-1 and B-2 measured by GC was less than 1.5% by mass. The sample temperature at the start of the reaction under reduced pressure was 134 ° C, and the maximum temperature during the reaction was 149 ° C. The pressure was gradually reduced while paying attention to the rise in the liquid level due to foaming, and the minimum pressure during the reaction was 0.8 Torr. It was confirmed that the total amount of B-1 and B-2 was 1.1% by mass after 4 hours of reaction under reduced pressure. Incidentally, at the timing of the second hour of the reaction under reduced pressure, an operation was carried out to discharge the substance accumulated in the cooling trap 2 of the reaction by-product from the pipe L21 to the outside of the system.

[0150] Next, the inside of the reactor was pressurized with nitrogen to a pressure higher than atmospheric pressure, and a sample was extracted in the form of a bale from the bottom of the reactor. The number of structural units of the obtained ethylene-octadecyl acrylate-hexadecyl acrylate-methyl acrylate was as follows: structural unit (A): 84.1 mol % structural unit (B): 13.2 mol % structural unit (C): 2.7 mol %

[0151] When the second batch was produced consecutively, the total amount of B-1 and B-2 reached 1.2 mass % after 4 hours of reduced pressure reaction, which was the same as the first batch in reduced pressure reaction time.

[0152] Example 2: Using the same equipment as in Example 1, side chain modification was carried out according to the following procedure.

[0153] [Procedure] 108 kg of B-1 and 224 kg of B-2 were loaded into a nitrogen-purged reactor, and B-1 and B-2 were melted and dried while stirring under conditions of a jacket temperature of 175°C or less and a minimum pressure of 3 Torr. After 0.9 hours, it was visually confirmed that B-1 and B-2 had melted. Subsequently, the pressure was restored to atmospheric pressure with nitrogen, and while B-1 and B-2 were in a molten state, 359 kg of A-1 was loaded, and the raw materials were melted, mixed, and dried while stirring under conditions of a jacket temperature of 175°C or less and a minimum pressure of 3 Torr until the sample temperature reached 130°C or higher. After 1.5 hours of mixing, the raw materials were completely melted, and the raw material temperature was 130°C. The actual raw material mixing time was 0.9 hours for dissolving B-1 and B-2, and 1.5 hours for the subsequent mixing with A-1, for a total of 2.4 hours.

[0154] Subsequently, the pressure was restored to atmospheric pressure with nitrogen, and 2.12 kg of C-1 was injected. Then, 0.72 kg of dehydrated D-1 was injected to wash the remaining amount of C-1 in the catalyst supply piping. Thereafter, the jacket temperature and the rotation speed of the stirring blade were adjusted so that the internal temperature was 145 ° C or higher and 150 ° C or lower, and the reaction was carried out under reduced pressure until the total amount of B-1 and B-2 measured by GC was less than 1.5% by mass. The sample temperature at the start of the reaction under reduced pressure was 133 ° C, and the maximum temperature during the reaction was 150 ° C. The pressure was gradually reduced while paying attention to the rise in the liquid level due to foaming, and the minimum pressure during the reaction was 3 Torr. It was confirmed that the total amount of B-1 and B-2 was 0.9% by mass after 4 hours of the reaction under reduced pressure. It should be noted that, at the timing of the second hour of the reaction under reduced pressure, the reaction under reduced pressure was continued without performing an operation to discharge the substance accumulated in the cooling trap 2 of the reaction by-product out of the system. The accumulated substances boiled at low pressure and were discharged to the vacuum pump 3 side, but at the same time, trace amounts of B-1 and B-2 that had been present in the cooling trap 2 were also carried along and adhered to the strainer of the vacuum pump 3 and inside the vacuum pump 3, preventing the pressure from decreasing during the decompression reaction.

[0155] Next, the inside of the reactor was pressurized with nitrogen to a pressure higher than atmospheric pressure, and the product was extracted in a bale from the bottom of the reactor. The number of structural units of the obtained ethylene-octadecyl acrylate-hexadecyl acrylate-methyl acrylate was as follows: structural unit (A): 84.1 mol % structural unit (B): 13.1 mol % structural unit (C): 2.8 mol %

[0156] When the second batch was produced in succession, the pressure did not decrease during the reduced pressure reaction (poor pressure control). After four hours of reduced pressure reaction, the total amount of B-1 and B-2 was 2.2% by mass, and the reaction was delayed compared to the first batch.

[0157] Example 3: Using the same equipment as in Example 1, side chain modification was carried out according to the following procedure.

[0158] [Procedure] 418 kg of B-1 was charged into a nitrogen-purged reactor, and B-1 was melted and dried while stirring under conditions of a jacket temperature of 175°C or less and a minimum pressure of 2 Torr. After 0.5 hours, it was confirmed visually that B-1 had melted. Subsequently, the pressure was restored to atmospheric pressure with nitrogen, and while B-1 was in a molten state, 483 kg of A-1 was charged, and the raw materials were melted, mixed, and dried while stirring under conditions of a jacket temperature of 175°C or less and a minimum pressure of 2 Torr until the sample temperature reached 130°C or higher. After 2 hours of mixing, the raw materials were completely melted, and the raw material temperature was 132°C. The actual raw material mixing time was 2.5 hours in total, consisting of 0.5 hours for dissolving B-1 and 2 hours for subsequent mixing with A-1.

[0159] Subsequently, the pressure was restored to atmospheric pressure with nitrogen, and when an attempt was made to inject the predetermined amount of 2.88 kg of C-1, a rise in the liquid level due to foaming occurred when 1.98 kg was injected, making it difficult to reduce the pressure. After 0.96 kg of dehydrated D-1 was injected to clean the remaining amount of C-1 in the catalyst supply piping, it took 4.5 hours to change from a pressurized state to a normal pressure state. After normal pressure was reached, an additional 0.90 kg of C-1 and 0.50 kg of D-1 were injected, and the decompression reaction was initiated. The jacket temperature and the rotation speed of the stirring blade were adjusted so that the internal temperature was 145 ° C or higher and 150 ° C or lower, and the decompression reaction was carried out until the amount of B-1 measured by GC was less than 1.5% by mass. The sample temperature at the start of the decompression reaction was 136 ° C, and the maximum temperature during the reaction was 150 ° C. The pressure was gradually reduced while paying attention to the rise in the liquid level due to foaming, and the minimum pressure during the reaction was 0.6 Torr. After 9.5 hours of reaction under reduced pressure, it was confirmed that the amount of B-1 was 1.0 mass %. The time required from the addition of the catalyst to the completion of the reaction was 14 hours in total.

[0160] Next, the inside of the reactor was pressurized with nitrogen to a pressure higher than atmospheric pressure, and the product was extracted in a bale from the bottom of the reactor. The number of structural units of the obtained ethylene-hexadecyl acrylate-methyl acrylate was as follows: structural unit (A): 84.1 mol % structural unit (B): 13.2 mol % structural unit (C): 2.7 mol %

[0161] Comparative Example 1: Using the same equipment as in Example 1, side chain modification was carried out according to the following procedure.

[0162] [Procedure] 243 kg of A-2 and 179 kg of B-1 were continuously charged into a nitrogen-purged reactor, and the raw materials were melt-mixed and dried while stirring under conditions of a jacket temperature of 175°C or less and a minimum pressure of 1 Torr until the sample temperature reached 130°C or higher. After charging A-2 and B-1, the stirring load was large and stirring was difficult for about 1 hour. Seven hours after charging the raw materials, the raw materials were completely melted, and the raw material temperature was 130°C. Next, the pressure was restored to atmospheric pressure with nitrogen, and 1.01 kg of C-2 was charged from the top of the reactor to initiate the reduced-pressure reaction. The jacket temperature and the rotation speed of the stirring blade were adjusted so that the internal temperature was around 135°C, and the reduced-pressure reaction was carried out until the amount of B-1 measured by GC was less than 1.5% by mass. An additional 1.01 kg of C-2 was added 8 hours into the reduced-pressure reaction. The sample temperature at the start of the reduced-pressure reaction was 130°C, and the maximum temperature during the reaction was 136°C. The pressure was gradually reduced while taking care to prevent the liquid level from rising due to foaming, and the minimum pressure during the reaction was 3 Torr. After 12 hours of reaction under reduced pressure, it was confirmed that the amount of B-1 was 1.0 mass %.

[0163] Table 1 shows a summary of the conditions and results of the examples and comparative examples.

[0164]

[0165] In the table, the notation "(1) → (2)" indicates that the thermoplastic resin (2) was added after the side-chain-modifying material (1) was made flowable. "(1) + (2)" indicates that the side-chain-modifying material (1) and the thermoplastic resin (2) were mixed without any operation to make the material flowable.

[0166] It can be seen that the method according to the example can stably produce a modified resin in a short time, compared to the method according to the comparative example.

[0167] 1...heat exchanger, 2...cooling trap, 3...vacuum pump, 10...reaction vessel, 100...manufacturing equipment, L10, L20, L21, L22...piping

Claims

1. A method for producing a modified resin, comprising the steps of: obtaining a modified resin from a thermoplastic resin (2) and a side-chain modifying material (1) having a molecular weight of 2000 or less, the method comprising the steps A to C below. Step A: A step of supplying a side chain modifying material (1) to a reactor. Step B: A step of supplying a thermoplastic resin (2) to the reactor after step A while the side chain modifying material (1) is in a flowable state. Step C: A step of modifying the side chain of the thermoplastic resin (2) with the side chain modifying material (1) after step B.

2. The method of claim 1, wherein step C is carried out under reduced pressure.

3. The method according to claim 1 or 2, wherein step C includes a step of discharging reaction by-products produced in step C.

4. The method according to claim 1 or 2, wherein the filling rate of the side-chain modified material (1) and the thermoplastic resin (2) is 80% or less of the nominal volume of the reactor.

5. The method according to claim 1 or 2, wherein the total amount of the side-chain modifying material (1) and the thermoplastic resin (2) fed is 90% by mass or more based on the total mass of the components fed to the reactor.

6. The method according to claim 5, wherein the amount of the side chain modifying material (1) supplied is 30 parts by mass or more and 70 parts by mass or less, and the amount of the thermoplastic resin (2) supplied is 30 parts by mass or more and 70 parts by mass or less, relative to 100 parts by mass in total of the side chain modifying material (1) and the thermoplastic resin (2).

7. The method according to claim 1 or 2, wherein after step C, the components in the reactor are discharged from the bottom of the reactor.

8. The method according to claim 1 or 2, wherein step C comprises reacting the thermoplastic resin (2) with the side-chain modifying material (1) at a temperature of 180°C or less.

9. The method according to claim 1 or 2, wherein the reactor is equipped with an agitator, the agitator being a large impeller.

10. The method according to claim 1 or 2, wherein the thermoplastic resin (2) has an ester bond in a side chain.

11. The method according to claim 1 or 2, wherein the thermoplastic resin (2) has structural units derived from ethylene.

12. The method according to claim 1 or 2, wherein the side-chain modified material (1) has one hydroxy group in the molecule.

13. The method according to claim 1 or 2, wherein the modification in step C is carried out by transesterification.

14. The method according to claim 1 or 2, wherein the modified resin is a polymer containing a structural unit (B) represented by the following formula (1): (In formula (1), R represents a hydrogen atom or a methyl group; L １ represents a single bond, —CO—O—, —O—CO—, or —O—; L ２ 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 ３ 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 ６ represents an alkyl group having 14 to 30 carbon atoms; １ , L ２ , and L ３ In each of the horizontally written chemical formulas in the description of the chemical structure, the left side corresponds to the upper side of formula (1) and the right side corresponds to the lower side of formula (1).

Images