Production method of modified resin

Abstract

To provide a method for producing a modified resin stably in a short period of time.SOLUTION: A production method of a modified resin obtains a modified resin from a thermoplastic resin (2) and a side-chain modified material (1) with a molecular weight 2000 or lower. The production method includes steps A to C: the step A of supplying the side-chain modified material (1) to a reaction vessel; the step B of supplying the thermoplastic resin (2) to the reaction vessel after the step A, in a state where the side-chain modified material (1) is flowable; and the step C of modifying a side-chain of the thermoplastic resin (2) after the step B by the side-chain modified material (1).SELECTED DRAWING: None

Description

Technical Field

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

Background Art

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

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0004] By the way, in a 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 stably producing a modified resin in a short time.

Means for Solving the Problems

[0006] [1] A method for producing a modified resin, comprising 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 including the following steps A to C. Step A: A step of supplying a side-chain modifying material (1) to a reactor Step B: After Step A, in a state where the side-chain modifying material (1) can flow, a step of supplying a thermoplastic resin (2) to the reactor Process C: A process of modifying the side chains of the thermoplastic resin (2) with the side chain modifying material (1) after Process B [2] Process C is the method described in [1], which is carried out under reduced pressure. [3] Process C is the method described in [1] or [2], which includes a process of discharging the reaction by-products generated in Process 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 supply amount of the side chain modifying material (1) and the thermoplastic resin (2) 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, based on 100 parts by mass of the total supply amount of the side chain modifying material (1) and the thermoplastic resin (2), the supply amount of the side chain modifying material (1) is 30 parts by mass or more and 70 parts by mass or less, and the supply amount of the thermoplastic resin (2) is 30 parts by mass or more and 70 parts by mass or less. [7] The method according to any one of [1] to [6], wherein after Process 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 Process C includes a process of reacting the thermoplastic resin (2) and 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 is a large blade.

[10] The method according to any one of [1] to [9], wherein the thermoplastic resin (2) has an ester bond in the 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 modifying material (1) has one hydroxy group in the molecule.

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

[12] , wherein the modification in Process C is carried out by an ester exchange reaction.

[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).

Chemical formula

Advantages of the Invention

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

Brief Description of the Drawings

[0008]

Figure 1

Modes for Carrying Out the Invention

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

[0010] In this specification, a numerical range indicated by "~" indicates a range including the numerical values described before and after "~" as the minimum value and the maximum value, respectively. In the numerical ranges described stepwise in this specification, the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of another numerically described range. Further, in the numerical ranges described in this specification, the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the examples.

[0011] In this specification, the materials exemplified below may be used alone or in combination of two or more within the range corresponding to the conditions, unless otherwise specified. The content of each component means the total amount of the plurality of substances corresponding to each component when there are a plurality of substances corresponding to each component, unless otherwise specified.

[0012] (Method for producing modified resin) The method for producing a modified resin according to this embodiment is a method for producing a modified resin, which obtains 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 the side chain modifying material (1) to a reactor Step B: After step A, in a state where the side chain modifying material (1) can flow, a step of supplying the thermoplastic resin (2) to the reactor Step C: After step B, a step of modifying the side chain of the thermoplastic resin (2) with the side chain modifying material (1)

[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, when increasing the reaction rate, the batch type is preferably used. However, the residence time distribution in the continuous polymerization reactor can be adjusted by appropriately designing and installing the connection mode of the containers and the stirring blades, and a balance of productivity can be achieved while suppressing a decrease in the reaction rate.

[0015] [Thermoplastic resin (2)] Examples of the thermoplastic resin (2) include resins that soften upon heating and have plasticity, such as polyethylene (PE), ethylene copolymers, polypropylene (PP), propylene copolymers, vinyl chloride homopolymer (PVC), polystyrene homopolymer (PS), cyclic olefin copolymer (COC), acrylonitrile-styrene copolymer (AS), acrylonitrile-butadiene-styrene copolymer (ABS), polymethyl methacrylate (PMMA), polyacrylate methyl (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).

[0016] From the perspective of the moldability and shape retention of the resulting modified resin, the thermoplastic resin (2) may, for example, have 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) can be a polymer having a structural unit (C) represented by the following formula (2).

Chemical formula

[0018] In formula (2), R represents a hydrogen atom or a methyl group, L 1 represents a single bond, —CO—O—, —O—CO—, or —O—, L 4 represents an alkylene group having 1 to 8 carbon atoms, L 5 represents a hydrogen atom, an epoxy group, —CH(OH)—CH2OH, a carboxy group, a hydroxy group, an amino group, or an alkylamino group having 1 to 4 carbon atoms. Note that L 1Each of the horizontally-written chemical formulas corresponds such that its left side corresponds to the upper side of formula (2) and its right side corresponds to the lower side of formula (2).

[0019] From the viewpoint of being easy to control the side-chain modification reaction, the thermoplastic resin (2) may have, for example, an ester bond in the side chain.

[0020] Examples of the thermoplastic resin (2) having an ester bond in the side chain include polymers having the structural unit (C) represented by the above formula (2), and in formula (2), L 1 is —CO—O—.

[0021] In formula (2), examples of the alkylene group having 1 to 8 carbon atoms as L 4 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-heptylene group, an n-octylene group, and a 2-ethyl-n-hexylene group.

[0022] In formula (2), examples of the alkylamino group having 1 to 4 carbon atoms as L 5 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, a structural unit derived from sec-butyl methacrylate, a structural unit derived from tert-butyl methacrylate, a structural unit derived from vinyl formate, a structural unit derived from vinyl acetate, a structural unit derived from vinyl propionate, a structural unit derived from vinyl (n-butyrate), a structural unit derived from vinyl (isobutyrate), a structural unit derived from methyl vinyl ether, a structural unit derived from ethyl vinyl ether, a structural unit derived from n-propyl vinyl ether, a structural unit derived from isopropyl vinyl ether, a structural unit derived from n-butyl vinyl ether, a structural unit derived from isobutyl vinyl ether, a structural unit derived from sec-butyl vinyl ether, a structural unit derived from tert-butyl vinyl ether, a structural unit derived from glycidyl acrylate, a structural unit derived from glycidyl methacrylate, a structural unit derived from 2,3-dihydroxypropyl acrylate, a structural unit derived from 2,3-dihydroxypropyl methacrylate, a structural unit derived from 3-(dimethylamino)propyl acrylate, and a structural unit derived from 3-(dimethylamino)propyl methacrylate.

[0024] The thermoplastic resin (2) may have two or more of the above-described structural units (C). For example, it may be 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-butyrate) 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-ethyl acrylate copolymers, ethylene-n-propyl acrylate copolymers, ethylene-n-butyl acrylate copolymers, ethylene-methyl methacrylate copolymers, ethylene-ethyl methacrylate copolymers, ethylene-n-propyl methacrylate copolymers, ethylene-n-butyl methacrylate copolymers, ethylene-vinyl formate copolymers, ethylene-vinyl acetate copolymers, ethylene-vinyl propionate copolymers, ethylene-vinyl (n-butyrate) copolymers, ethylene-methyl vinyl ether copolymers, ethylene-ethyl vinyl ether copolymers, ethylene-n-propyl vinyl ether copolymers, ethylene-n-butyl vinyl ether copolymers, ethylene-maleic anhydride copolymers, ethylene-glycidyl acrylate copolymers, ethylene-glycidyl methacrylate copolymers, ethylene-3-(dimethylamino)propyl acrylate copolymers, and ethylene-3-(dimethylamino)propyl methacrylate copolymers. The thermoplastic resin (2) is preferably an ethylene 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-carboxylic acid vinyl 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 constitutional unit (A) is 0% or more and 99% or less, and the total number of the constitutional unit (C) is 1% or more and 100% or less, based on 100% of the total number of the constitutional unit (A) and the constitutional unit (C). More preferably, it is a polymer in which the number of the constitutional unit (A) is 70% or more and 99% or less, and the total number of the constitutional unit (C) is 1% or more and 30% or less.

[0027] The melt flow rate (MFR) of the thermoplastic resin (2) measured at a temperature of 190 °C and a load of 21 N in accordance with JIS K7210 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 still 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 an alcohol, an amine, an alkyl halide, a carboxylic acid, a carboxylic acid amide, a carboxylic acid halide, a carbamic acid, an alkyl urea, and an isocyanate having a molecular weight of 2000 or less.

[0029] The side chain-modified material (1) can, in one example, be at least one compound selected from the group consisting of an alcohol having an alkyl group with 14 to 30 carbon atoms, an amine having an alkyl group with 14 to 30 carbon atoms, an alkyl halide having an alkyl group with 14 to 30 carbon atoms, a carboxylic acid having an alkyl group with 14 to 30 carbon atoms, a carboxylic acid amide having an alkyl group with 14 to 30 carbon atoms, a carboxylic acid halide having an alkyl group with 14 to 30 carbon atoms, a carbamic acid having an alkyl group with 14 to 30 carbon atoms, an alkyl urea having an alkyl group with 14 to 30 carbon atoms, and an isocyanate having an alkyl group with 14 to 30 carbon atoms (hereinafter also referred to as "compound (α)").

[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 straight-chain alkyl group with 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-henicosyl 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 with 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 with 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 with 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 with 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-henicosyl 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 with 14 to 30 carbon atoms include isotetradecyl iodide, isopentadecyl iodide, isohexadecyl iodide, isooctadecyl iodide, isononadecyl iodide, isoeicosyl iodide, isononacosyl iodide, and isotriacontyl iodide.

[0037] Examples of the carboxylic acid having a linear alkyl group with 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-henicosanoic 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 with 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 carboxamide having a linear alkyl group with 14 to 30 carbon atoms include n-tetradecanamide, n-pentadecanamide, n-hexadecanamide, n-heptadecanamide, n-octadecanamide, n-nonadecanamide, n-eicosanamide, n-heneicosanamide, n-docosanamide, n-tricosanamide, n-tetracosanamide, n-pentacosamide, n-hexacosamide, n-heptacosamide, n-octacosamide, n-nonacosamide, and n-triacontanamide.

[0040] Examples of the carboxamide having a branched alkyl group with 14 to 30 carbon atoms include isotetradecanamide, isopentadecanamide, isohexadecanamide, isoheptadecanamide, isooctadecanamide, isononadecanamide, isoeicosanamide, isoheneicosanamide, isodocosamide, isotricosamide, isotetracosamide, isopentacosamide, isohexacosamide, isoheptacosamide, isooctacosamide, isononacosamide, and isotriacontanamide.

[0041] Examples of the carboxylic acid halide having a linear alkyl group with 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 with 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 with 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 with 14 to 30 carbon atoms include isotetradecyl carbamic acid, isopentadecyl carbamic acid, isohexadecyl carbamic acid, isoheptadecyl carbamic acid, isooctadecyl carbamic acid, isononadecyl carbamic acid, isoeicosyl carbamic acid, isoheneicosyl carbamic acid, isodocosyl carbamic acid, isotricosyl carbamic acid, isotetracosyl carbamic acid, isopentacosyl carbamic acid, isohexacosyl carbamic acid, isoheptacosyl carbamic acid, isooctacosyl carbamic acid, isononacosyl carbamic acid, and isotriacontyl carbamic acid.

[0045] Examples of the alkyl urea having a linear alkyl group with 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 with 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 with 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 with 14 to 30 carbon atoms include isotetradecyl isocyanate, isopentadecyl isocyanate, isohexadecyl 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] From the viewpoint that the side - chain modifying material (1) is easy to handle industrially and there are many substances that are easy to use as side - chain modifying materials, it may have one hydroxy group in the molecule.

[0050] Examples of the side-chain modified material (1) having one hydroxy group in the molecule include monohydric alcohols such as 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, n-triacontyl 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, isotriacontyl alcohol, etc.

[0051] [Step A] In Step A, the side-chain modified material (1) is supplied to the reactor.

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

[0053] The nominal volume of the reactor can be, for example, 0.1 m 3 or more and 50 m 3 or less, or 0.5 m 3 or more and 30 m 3 or less, or 1.0 m 3 or more and 20 m 3 or less.

[0054] The reactor preferably has a stirring blade.

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

[0056] From the perspective of being able to handle the high-viscosity region, the stirring blade can be, for example, a large blade. Also, from the perspective of being able to handle a wide viscosity range, it can be a wide blade. Examples of wide blades include the stirring blade "Full Zone" (trade name) manufactured by Kobe Steel Environmental Solutions Co., Ltd., "Super-Mix MR203" and "Super-Mix MR205" manufactured by Satake Chemical Machinery Co., Ltd., "Hi-F Mixer" (all trade names) manufactured by Soken Techniques Co., Ltd., and "MAXBLEND" (trade name) manufactured by Sumitomo Heavy Industries Process Equipment Co., Ltd.

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

[0058] The side-chain modified material (1) in a state where it can flow can be, for example, the side-chain modified material (1) in a molten state or a state dissolved in a solvent. The molten state or the state dissolved in a solvent includes a state where there are solids partially remaining undissolved in the liquid and the solids remaining undissolved in the liquid can be stirred.

[0059] When supplying the solid side-chain modified material (1), before step B, the side-chain modified material (1) in the reactor can be heated, for example, to a state where it can flow.

[0060] [Step B] In step B, with the side-chain modified material (1) in a state where it can flow, the thermoplastic resin (2) is supplied to the reactor.

[0061] The total supply amount of the side-chain modified material (1) and the thermoplastic resin (2) is preferably 90% by mass or more, more preferably 95% by mass or more, and still more preferably 98% by mass or more, based on the total mass of the components supplied to the reactor, from the viewpoint of improving productivity. The total supply amount of the side-chain modified material (1) and the thermoplastic resin (2) 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 supply amount of the side-chain modified material (1) 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, based on 100 parts by mass of the total supply amount of the side-chain modified material (1) and the thermoplastic resin (2).

[0063] The supply amount of the thermoplastic resin (2) 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, based on 100 parts by mass of the total supply amount of the side-chain modified material (1) and the thermoplastic resin (2).

[0064] Preferably, based on 100 parts by mass of the total supply amount of the side-chain modified material (1) and the thermoplastic resin (2), the supply amount of the side-chain modified material (1) is 30 parts by mass or more and 70 parts by mass or less, and the supply amount of the thermoplastic resin (2) is 30 parts by mass or more and 70 parts by mass or less.

[0065] The supply amount of the side-chain modified material (1) with respect 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] The filling ratios of the side-chain modified material (1) and the thermoplastic resin (2) are preferably 80% or less of the nominal volume of the reactor from the viewpoint of operation stability by liquid level control. This filling ratio 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 ratio 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 process, the above filling ratio can be calculated by the following formula. (Filling ratio of raw materials) [%] = 100 × (Total volume of raw materials) [m 3 / (Nominal volume of reactor) [m 3 [In the formula, 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 value obtained by adding the volume of the side-chain modified material (1) [m 3 and the volume of the thermoplastic resin (2) [m 3 . The volume of each raw material [m 3 is calculated by dividing the usage amount [kg] of each raw material by the density [kg / m 3 in the range of 20°C to 25°C.] In the case of a continuous process, the above filling ratio can be calculated by the following formula. (Filling ratio of raw materials) [%] = 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 (e.g., liquid state).

[0069] When supplying the solid thermoplastic resin (2), it is preferable to heat the reactor after supply 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 above modification can be carried out, for example, by an addition reaction, a substitution reaction, a redox reaction, etc. From the viewpoint of small reaction heat and easy reaction control, the modification is preferably carried out by a transesterification reaction which is a kind of substitution reaction.

[0071] Step C is preferably carried out under reduced pressure. When foaming occurs, for example, the pressure can be gradually reduced. In Step C, the pressure in the reactor 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 of Step C may be, for example, 40°C or more and 250°C or less, 100°C or more and 200°C or less, or 130°C or more and 180°C or less.

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

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

[0075] From the viewpoint of promoting the reaction, Step C may include a step of discharging the reaction by-products generated in Step C. This step can be, for example, a step of discharging the reaction by-products distilled off under reduced pressure from the reactor out 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 addition amount of the catalyst 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, based on 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 and before extracting the components in the reactor, additives (such as antioxidants and reaction terminators), other functional material components (such as low molecular weight heat storage materials), etc. can also be supplied to the reactor.

[0081] [Modified resin]

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

[0083] [Chemical formula]

[0084] 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 represents a single bond, —CH2—, —CH2—CH2—, —CH2—CH2—CH2—, —CH2—CH(OH)—CH2—, or —CH2—CH(CH2OH)—, L3 represents a single bond, ―CO―O―, ―O―CO―, ―O―, ―CO―NH―, ―NH―CO―, ―CO―NH―CO―, ―NH―CO―NH―, ―NH―, or ―N(CH3)―, L 6 represents an alkyl group having 14 to 30 carbon atoms, L 1 L 2 and L 3 In the description of the chemical structure of each of the horizontal chemical formulas, 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) can be produced, for example, by modifying the side chain (-L 1 -L 4 -L 5 ) of the polymer having the structural unit (C).

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

[0087] Examples of the linear alkyl group having 14 to 30 carbon atoms include n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-eicosyl group, n-henicosyl group, n-docosyl group, n-tricosyl group, n-tetracosyl group, n-pentacosyl group, n-hexacosyl group, n-heptacosyl group, n-octacosyl group, n-nonacosyl group, and 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 structural units derived from n-hexadecene, structural units derived from n-octadecene, structural units derived from n-eicosene, structural units derived from n-docosene, structural units derived from n-tetracosene, structural units derived from n-hexacosene, structural units derived from n-octacosene, structural units derived from n-triacontene, structural units derived from n-dotriacontene, structural units derived from n-tetradecyl acrylate, structural units derived from n-pentadecyl acrylate, structural units derived from n-hexadecyl acrylate, structural units derived from n-heptadecyl acrylate, structural units derived from n-octadecyl acrylate, structural units derived from n-nonadecyl acrylate, structural units derived from n-eicosyl acrylate, structural units derived from n-henicosyl acrylate, structural units derived from n-docosyl acrylate, structural units derived from n-tricosyl acrylate, structural units derived from n-tetracosyl acrylate, structural units derived from n-pentacosyl acrylate, structural units derived from n-hexacosyl acrylate, structural units derived from n-heptacosyl acrylate, structural units derived from n-octacosyl acrylate, structural units derived from n-nonacosyl acrylate, structural units derived from n-triacontyl acrylate, structural units derived from n-tetradecyl methacrylate, structural units derived from n-pentadecyl methacrylate, structural units derived from n-hexadecyl methacrylate, structural units derived from n-heptadecyl methacrylate, structural units derived from n-octadecyl methacrylate, structural units derived from n-nonadecyl methacrylate, structural units derived from n-eicosyl methacrylate, structural units derived from n-henicosyl methacrylate, structural units derived from n-docosyl methacrylate, structural units derived from n-tricosyl methacrylate, structural units derived from n-tetracosyl methacrylate, structural units derived from n-pentacosyl methacrylate, structural units derived from n-hexacosyl methacrylate, structural units derived from n-heptacosyl methacrylate, structural units derived from n-octacosyl methacrylate, structural units derived from n-nonacosyl methacrylate,Constituent units derived from n - triacontyl methacrylate, constituent units derived from n - vinyl tetradecylate, constituent units derived from n - vinyl hexadecylate, constituent units derived from n - vinyl octadecylate, constituent units derived from n - vinyl eicosylate, constituent units derived from n - vinyl docosylate, constituent units derived from n - tetradecyl vinyl ether, constituent units derived from n - hexadecyl vinyl ether, constituent units derived from n - octadecyl vinyl ether, constituent units derived from n - eicosyl vinyl ether, and constituent units derived from n - docosyl vinyl ether may be mentioned.

[0090] The modified resin may have two or more of the above - mentioned constituent units (B). For example, it may be a polymer having a constituent unit derived from n - eicosyl acrylate and a constituent unit derived from n - octadecyl acrylate.

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

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

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

[0094] The modified resin may have two or more of the above - mentioned constituent units (C). For example, it may be a polymer having a constituent unit derived from methyl acrylate, a constituent unit derived from ethyl acrylate, and a constituent unit derived from glycidyl methacrylate.

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

[0096] Examples of the polymer having a constituent unit (B) represented by the formula (1) include The polymer composed of the constitutional unit (B), The polymer having the constitutional unit (B) and the constitutional unit (A), The polymer having the constitutional unit (B) and the constitutional unit (C), and The polymer having the constitutional unit (B), the constitutional unit (A), and the constitutional unit (C) may be mentioned.

[0097] Examples of the polymer composed of the constitutional unit (B) include R is a hydrogen atom, and L 1 、L 2 、and L 3 are single bonds, and L 6 is an alkyl group having 14 to 30 carbon atoms, a polymer composed of the constitutional unit (B) represented by the formula (1), and R is a hydrogen atom or a methyl group, and L 1 is -CO-O-, and L 2 and L 3 are single bonds, and L 6 is an alkyl group having 14 to 30 carbon atoms, a polymer composed of the constitutional unit (B) represented by the formula (1) may be mentioned.

[0098] Examples of the polymer having the constitutional unit (B) and the constitutional unit (A) include R is a hydrogen atom, and L 1 、L 2 、and L 3 are single bonds, and L 6 is an alkyl group having 14 to 30 carbon atoms, having the constitutional unit (B) represented by the formula (1) and the constitutional unit (A), and the total number of the constitutional unit (A) and the constitutional unit (B) is 90% or more with respect to 100% of the total number of all constitutional units contained in the polymer, and R is a hydrogen atom or a methyl group, and L 1 is -CO-O-, and L 2 and L 3 are single bonds, and L 6A polymer having a structural unit (B) represented by the formula (1) in which the alkyl group has 14 to 30 carbon atoms and a structural unit (A), and may further have the structural unit (C), wherein the total number of all structural units contained in the polymer is 100%, and the total number of the structural unit (A) and the structural unit (B) is 90% or more.

[0099] From the viewpoint of increasing ΔH, the modified resin may be a polymer in which the number of the structural unit (B) is more than 50% and 80% or less with respect to 100% of the total number of the structural unit (B) and the structural unit (A).

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

[0101] Examples of the polymer having the structural unit (B) and the structural unit (C) include 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 a structural unit (B) represented by the formula (1) in which the alkyl group has 14 to 30 carbon atoms, and 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 is a hydrogen atom, and a polymer having a structural unit (C) represented by the formula (2). In this case, a polymer in which the number of the structural unit (B) is 80% or more with respect to 100% of the total number of the structural unit (B) and the structural unit (C) contained in the polymer is preferable.

[0102] In the above-mentioned modified resin, based on 100% of the total number of the structural unit (A), the structural unit (B), and the structural unit (C), the number of the structural unit (A) is, for example, 0% or more and 99% or less, the total number of the structural unit (B) and the structural unit (C) is, for example, 1% or more and 100% or less, based on 100% of the total number of the structural unit (B) and the structural unit (C), the number of the structural unit (B) is, for example, 1% or more and 100% or less, and the number of the structural unit (C) can be, for example, 0% or more and 99% or less.

[0103] In the above-mentioned modified resin, from the viewpoint of shape retention when formed into a molded body, based on 100% of the total number of the structural unit (A), the structural unit (B), and the structural unit (C), the number of the structural unit (A) is preferably 70% or more and 99% or less, more preferably 80% or more and 97.5% or less, and still more preferably 83% or more and 92.5% or less. In the above-mentioned modified resin, from the viewpoint of shape retention when formed into a molded body, based on 100% of the total number of the structural unit (A), the structural unit (B), and the structural unit (C), the total number of the structural unit (B) and the structural unit (C) is preferably 1% or more and 30% or less, more preferably 2.5% or more and 20% or less, and still more preferably 7.5% or more and 17% or less.

[0104] In the above-mentioned modified resin, the number of the structural unit (B) can be, for example, 1% or more and 100% based on 100% of the total number of the structural unit (B) and the structural unit (C). From the viewpoint of heat storage performance, this number may be, for example, 60% or more and 100%, or 80% or more and 100%.

[0105] In the above-mentioned modified resin, the number of the structural unit (C) can be, for example, 0% or more and 99% based on 100% of the total number of the structural unit (B) and the structural unit (C). From the viewpoint of heat storage performance, this number may be, for example, 0% or more and 40%, or 0% or more and 20%.

[0106] The number of the constitutional unit (A), the number of the constitutional unit (B), and the number of the constitutional unit (C) are measured by a well-known method 13 from the carbon nuclear magnetic resonance spectrum (hereinafter referred to as 13 the 13C-NMR spectrum) or 1 from the proton nuclear magnetic resonance spectrum (hereinafter referred to as 1 the 1H-NMR spectrum), which can be determined from the integral values of the signals attributed to each constitutional unit.

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

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

[0109] Number of constitutional unit (A) = 100 - number of constitutional unit (C) Number of constitutional unit (C) = 100×(AC / 2 + CC) / (AA + AC + CC) Since the constitutional unit (B) in the modified resin is formed by the reaction of the constitutional unit (C) contained in the thermoplastic resin (2) with the compound (α), the conversion rate of the constitutional unit (C) by the reaction is determined by the following method.

[0110] The conversion rate is obtained by substituting the integral value of the signal attributed to the specific carbon contained in the side chain of the constitutional unit (C) of the thermoplastic resin (2) (hereinafter referred to as integral value Y) and the integral value of the signal attributed to the specific carbon contained in the side chain of the constitutional 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 the thermoplastic resin (2) and the compound (α), since the constitutional unit (A) contained in the thermoplastic resin (2) does not change, the number of constitutional units (A) contained in the modified resin is assumed to be the same as the number of constitutional units (A) contained in the thermoplastic resin (2). The number of constitutional units (B) contained in the modified resin is obtained as the product of the number of constitutional units (C) contained in the thermoplastic resin (2) and the conversion rate. The number of constitutional units (C) contained in the modified resin is obtained as the difference between the number of constitutional units (C) contained in the thermoplastic resin (2) and the number of constitutional units (B) contained in the modified resin.

[0112] The method of the present embodiment described above is a method for producing a modified resin by obtaining 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. According to such a method, a modified resin can be stably produced in a short time. Step A: A step of supplying the side chain modifying material (1) to the reactor Step B: After step A, in a state where the side chain modifying material (1) can flow, a step of supplying the thermoplastic resin (2) to the reactor Step C: After step B, a step of modifying the side chain 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. Thereby, the production time of the modified resin can be further shortened.

[0114] In the above method, step C can include a step of discharging the reaction by-products generated in step C. Thereby, the operation stability can be further improved, and the production time of the modified resin can be further shortened.

[0115] In the above method, the filling rates of the side-chain modified material (1) and the thermoplastic resin (2) can be 80% or less of the nominal volume of the reactor. Thereby, the operation stability can be further improved, and the production time of the modified resin can be further shortened.

[0116] In the above method, the total supply amount of the side-chain modified material (1) and the thermoplastic resin (2) can be 90% by mass or more based on the total mass of the components supplied to the reactor. Thereby, the productivity can be further improved.

[0117] In the above method, with respect to 100 parts by mass of the total supply amount of the side-chain modified material (1) and the thermoplastic resin (2), the supply amount of the side-chain modified material (1) can be 30 parts by mass or more and 70 parts by mass or less, and the supply amount of the thermoplastic resin (2) can be 30 parts by mass or more and 70 parts by mass or less. Thereby, the production time of the modified resin can be further shortened.

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

[0119] In the above method, step C can include a step of reacting the thermoplastic resin (2) and the side-chain modified material (1) at a temperature of 180°C or lower. Thereby, while suppressing the deterioration of the thermoplastic resin (2) and the scattering of the side-chain modified material (1) outside the reactor, the production time of the modified resin can be further shortened.

[0120] In the above method, the reactor is equipped with a stirrer, and the stirrer can be a large blade. Thereby, the operation stability is further improved.

[0121] In the above method, the thermoplastic resin (2) can have an ester bond in the side chain. Thereby, it is easy to control the side-chain modification, and the modified resin can be easily produced.

[0122] In the above method, the thermoplastic resin (2) can have a structural unit derived from ethylene. Thereby, a modified resin excellent in moldability and shape retention when formed can be easily produced.

[0123] In the above method, the side-chain modifying material (1) can have one hydroxy group in the molecule. Thereby, a modified resin that is easy to handle industrially can be easily produced.

[0124] In the above method, the modification in step C can be carried out by a transesterification reaction. Thereby, side-chain modification can be easily controlled, and a modified resin can be easily produced.

[0125] In the above method, the modified resin can be a polymer containing a structural unit (B) represented by the following formula (1). Such a modified resin is excellent in heat storage performance. [Chemical formula] (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 represents a single bond, —CH2—, —CH2—CH2—, —CH2—CH2—CH2—, —CH2—CH(OH)—CH2—, or —CH2—CH(CH2OH)—, L 3 represents a single bond, —CO—O—, —O—CO—, —O—, —CO—NH—, —NH—CO—, —CO—NH—CO—, —NH—CO—NH—, —NH—, or —N(CH3)—, L 6 represents an alkyl group having 14 or more and 30 or less carbon atoms, L 1 L 2 and L 3 In the description of the chemical structure of each of the horizontally written chemical formulas, the left side thereof corresponds to the upper side of formula (1), and the right side thereof corresponds to the lower side of formula (1).) [Examples]

[0126] Hereinafter, the present invention will be described in more detail by way of Examples and Comparative Examples, but the present invention is not limited to the Examples.

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

[0128] <Carbon nuclear magnetic resonance ( 13 C-NMR) measurement conditions> Apparatus: AVANCE III 600HD manufactured by Bruker BioSpin Corporation Measurement probe: 10 mm cryoprobe Measurement solvent: Mixture 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 integrations: 256 times Pulse width: 45 degrees Pulse repetition time: 4 seconds Measurement standard: Tetramethylsilane

[0129] From the measurement results, integration values in the ranges of a1, b1, c1, d1, and e1 were obtained, and the numbers of dyads (AA, AC, CC) of structural unit (A) and structural unit (C) were calculated from 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 unit (A)-unit (A) dyad, AC is a unit (A)-unit (C) dyad, and CC is a unit (C)-unit (C) dyad.

[0130] Next, the amounts (number [%] and mass [mass%]) of unit (A) and unit (C) were determined from the following formulas. Number of unit (A) = 100 - Number of unit (C) Number of unit (C) = 100×(AC / 2 + CC) / (AA + AC + CC) Mass% of unit (A) = (Number of unit (A) × Molecular weight of unit (A)) / (Number of unit (A) × Molecular weight of unit (A) + Number of unit (C) × Molecular weight of unit (C)) Mass% of unit (C) = (Number of unit (C) × Molecular weight of unit (C)) / (Number of unit (A) × Molecular weight of unit (A) + Number of unit (C) × Molecular weight of unit (C))

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

[0132] Under the same conditions as the above carbon nuclear magnetic resonance ( 13 C-NMR) measurement conditions, the NMR spectrum of the modified resin was measured. From the measurement results, the integral value of the signal (range f1) attributed to the specific carbon contained in the side chain of the unit (C) and the integral value of the signal (range g1) attributed to the specific carbon contained in the side chain of the 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 [mass%]) of structural unit (A) derived from ethylene, structural unit (B) represented by formula (1), and structural unit (C) derived from methyl acrylate contained in the modified resin> In the reaction of the thermoplastic resin (2) with the compound (α), since the structural unit (A) contained in the thermoplastic resin (2) does not change, the number of structural units (A) contained in the modified resin was made the same as the number of structural units (A) contained in the thermoplastic resin (2). The number of structural units (B) contained in the modified resin was determined 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 determined 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), structural unit (B), and structural unit (C) contained in the modified resin were calculated from the following formulas, respectively. Mass% of structural unit (A) = (number of structural units (A) × molecular weight of structural unit (A)) / (number of structural units (A) × molecular weight of structural unit (A) + number of structural units (B) × molecular weight of structural unit (B) + number of structural units (C) × molecular weight of structural unit (C)) Mass% of structural unit (B) = (number of structural units (B) × molecular weight of structural unit (B)) / (number of structural units (A) × molecular weight of structural unit (A) + number of structural units (B) × molecular weight of structural unit (B) + number of structural units (C) × molecular weight of structural unit (C)) Mass% of structural unit (C) = (number of structural units (C) × molecular weight of structural unit (C)) / (number of structural units (A) × molecular weight of structural unit (A) + number of structural units (B) × molecular weight of structural unit (B) + number of structural units (C) × molecular weight of structural unit (C))

[0135] [III] Content (mass%) of unreacted compound having a C14 - 30 alkyl group (side chain modifying material (1)) The products obtained in the examples and comparative examples are mixtures of a modified resin and a compound having an unreacted C14-30 alkyl group. The content of the compound having an 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 the value when the total mass of the modified resin and the unreacted compound is 100% by mass.

[0136] [GC Measurement Conditions] Apparatus: GC-2030 manufactured by Shimadzu Corporation Column: DB-1 (30 m, 0.25 mm φ, 1.0 μm) Column temperature: Held at 60 °C for 5 minutes, then heated to 280 °C at 25 °C / min, held at 280 °C for 10 minutes, and then heated to 300 °C at 10 °C / min. Vaporization chamber / 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) Calibration curve preparation [Preparation of internal standard solution] To 40 g of anisole, 0.2 g of 1,4-dioxane and 0.2 g of octadecane were added and dissolved to prepare an internal standard solution. Octadecane was used as the internal standard substance for 1-hexadecanol and 1-octadecanol. [Preparation of standard solution for calibration curve] Solutions (1) to (4) for preparing the standard solution were prepared according to the following procedure. 0.1 g each of the analytes (1-hexadecanol and 1-octadecanol) and 9.8 g of 1,2-dichlorobenzene were mixed 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 calibration standard solutions.

[0138] [GC measurement] The standard solution for preparing the calibration curve was measured under the GC measurement conditions in the previous section, and a calibration curve was created with the vertical axis being the GC area ratio of the analyte to the internal standard substance and the horizontal axis being the mass ratio of the analyte to the internal standard substance, and the slope a of the calibration curve was determined.

[0139] (2) Measurement of the content of the analyte (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 in the previous section, and the content PS of the analyte in the sample was determined according to the following formula. PS: Content of the analyte in the sample (mass%) WS: Mass of the sample (mg) WIS: Mass of the internal standard substance (IS) (mg) AS: Peak area count number of the analyte AIS: Peak area count number of the internal standard substance (IS) a: Slope of the calibration curve of the analyte [Equation]

[0141] [IV] Filling rate of raw materials The filling rate of the raw materials [%] was calculated by the following formula. 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 sum of the volume of the side-chain modified material (1) [m 3 and the volume of the thermoplastic resin (2) [m 3 . The volume of each raw material [m 3 was calculated by dividing the usage amount of each raw material [kg] by the density [kg / m 3 in the range of 20°C to 25°C. (Filling rate of raw materials) [%] = 100 × (Total volume of raw materials) [m 3 / (Nominal volume of the reactor) [m 3

[0142] <Thermoplastic resin (2)> The following ethylene-methyl acrylate copolymer is produced, for example, in an autoclave reactor at a reaction temperature of 195°C and a reaction pressure of 160 MPa using tert-butyl peroxy pivalate as a radical polymerization initiator by copolymerizing ethylene and methyl acrylate. 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 data not available (density of A-1, 968 kg / m 3 , was used for the filling rate calculation)

[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 Pipe> D-1: 2-Propanol [manufactured by Fujifilm Wako Pure Chemical Corporation]

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

[0147] The manufacturing equipment 100 has a reaction kettle 10 with a nominal volume of 1.25 m 3 and equipped with a Max Blend 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 reaction kettle 10 and the vacuum pump 3. The reaction kettle 10, the cooling trap 2, and the vacuum pump 3 are connected by pipes heated to a temperature above the melting point of the side-chain modification material.

[0148] [Procedure] 109 kg of B-1 and 225 kg of B-2 were charged into a nitrogen-purged reaction kettle, and while stirring under the conditions of a jacket temperature of 175 °C or lower and a minimum pressure of 2 Torr, melting and drying of B-1 and B-2 were carried out. After 0.5 hours, it was visually confirmed that B-1 and B-2 were melted. Subsequently, the pressure was restored to atmospheric pressure with nitrogen. While B-1 and B-2 were in a molten state, after 358 kg of A-1 was charged, melting, mixing, and drying of the raw materials were carried out while stirring under the conditions of a jacket temperature of 175 °C or lower and a minimum pressure of 0.6 Torr until the sample temperature reached 130 °C or higher. At the time point 1 hour after mixing, the raw materials were completely melted, and the raw material temperature was 134 °C. The actual raw material mixing time was 0.5 hours for the dissolution of B-1 and B-2 and 1 hour for the subsequent mixing with A-1, for a total of 1.5 hours.

[0149] Subsequently, the pressure was restored to atmospheric pressure with nitrogen. After 2.13 kg of C-1 was pressured in, 0.72 kg of dehydrated D-1 was pressured in for washing the remaining amount of C-1 in the catalyst supply pipe. Then, 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 a pressure-reducing reaction was carried out until the total amount of B-1 and B-2 by GC measurement was less than 1.5% by mass. The sample temperature at the start of the pressure-reducing reaction was 134 °C, and the highest temperature during the reaction was 149 °C. The pressure was gradually reduced while paying attention to the liquid level rise 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 the pressure-reducing reaction. In addition, at the timing of 2 hours of the pressure-reducing reaction, an operation was carried out to discharge the substances accumulated in the cooling trap 2 for reaction by-products out of the system through the pipe L21.

[0150] Subsequently, the inside of the reaction kettle was set to a pressure higher than atmospheric pressure with nitrogen, and the sample was withdrawn in a veil shape from the lower part of the reaction kettle. The number of constituent units of the obtained ethylene-octadecyl acrylate-hexadecyl acrylate-methyl acrylate was as follows. Constituent unit (A): 84.1 mol% Constituent unit (B): 13.2 mol% Constituent unit (C): 2.7 mol%

[0151] When the second batch of production was carried out continuously, the total amount of B-1 and B-2 at the 4th hour of the reduced-pressure reaction was 1.2% by mass, and the reduced-pressure reaction time was the same as that of the first batch.

[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 charged into a nitrogen-purged reaction kettle, and melting and drying of B-1 and B-2 were carried out while stirring under the conditions of a jacket temperature of 175 °C or lower and a minimum pressure of 3 Torr. After 0.9 hours, it was visually confirmed that B-1 and B-2 were melted. Subsequently, the pressure was restored to atmospheric pressure with nitrogen. With B-1 and B-2 in a melted state, 359 kg of A-1 was charged, and then melting, mixing, and drying of the raw materials were carried out while stirring under the conditions of a jacket temperature of 175 °C or lower and a minimum pressure of 3 Torr until the sample temperature reached 130 °C or higher. At the time point 1.5 hours after 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 the dissolution of 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. After injecting 2.12 kg of C-1, 0.72 kg of dehydrated D-1 was injected for cleaning the remaining amount of C-1 in the catalyst supply pipe. Then, 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 a pressure reduction reaction was carried out until the total amount of B-1 and B-2 by GC measurement was less than 1.5% by mass. The sample temperature at the start of the pressure reduction reaction was 133°C, and the maximum temperature during the reaction was 150°C. The pressure was gradually reduced while paying attention to the liquid level rise 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 pressure reduction reaction. Note that at the timing of 2 hours into the pressure reduction reaction, the pressure reduction reaction was continued without discharging the substances accumulated in the cooling trap 2 for the reaction by-products to the outside of the system. The accumulated substances boiled at a low pressure and were discharged to the side of the vacuum pump 3. At that time, a small amount of B-1 and B-2 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, inhibiting the pressure drop during the pressure reduction reaction.

[0155] Subsequently, the inside of the reaction kettle was made into a high-pressure state higher than atmospheric pressure with nitrogen, and the product was withdrawn in a veil shape from the lower part of the reaction kettle. The number of constituent units of the obtained ethylene-octadecyl acrylate-hexadecyl acrylate-methyl acrylate was as follows. Constituent unit (A): 84.1 mol% Constituent unit (B): 13.1 mol% Constituent unit (C): 2.8 mol%

[0156] When the second batch of production was continuously carried out, the pressure did not drop during the pressure reduction reaction (poor pressure adjustment). The total amount of B-1 and B-2 at 4 hours into the pressure reduction reaction 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 put into a nitrogen-substituted 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 by visual inspection that B-1 had melted. Next, the pressure was returned to atmospheric pressure with nitrogen, and in the state in which B-1 was melted, 483 kg of A-1 was put in, and the raw materials were melted and 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 more. 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 mixing with A-1.

[0159] Next, the pressure was returned to atmospheric pressure with nitrogen, and when they tried to inject the specified amount of 2.88 kg of C-1, when 1.98 kg was injected, the liquid level rose due to foaming, making it difficult to reduce the pressure. After injecting 0.96 kg of dehydrated D-1 to wash the remaining C-1 in the catalyst supply piping, it took 4.5 hours to go from the pressurized state to normal pressure. 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 started. 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 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. The amount of B-1 was confirmed to be 1.0 mass % after 9.5 hours of reduced pressure reaction. The time required from adding the catalyst to the end 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-substituted reaction kettle, and while stirring under the conditions of a jacket temperature of 175°C or lower and a minimum pressure of 1 Torr, the raw materials were melt-mixed and dried until the sample temperature reached 130°C or higher. After the charging of A-2 and B-1, the stirring load was large and stirring was difficult for about 1 hour. At the time 7 hours after the raw material charging, the raw materials were completely melted and the raw material temperature was 130°C. Subsequently, the pressure was restored to atmospheric pressure with nitrogen, and 1.01 kg of C-2 was charged from the upper part of the reaction kettle to start the decompression 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 decompression reaction was carried out until the amount of B-1 by GC measurement was less than 1.5% by mass. At the 8th hour of the decompression reaction, 1.01 kg of C-2 was additionally added. The sample temperature at the start of the decompression reaction was 130°C, and the highest temperature during the reaction was 136°C. The pressure was gradually reduced while paying attention to the liquid level rise due to foaming, and the minimum pressure during the reaction was 3 Torr. It was confirmed that the amount of B-1 was 1.0% by mass at 12 hours of the decompression reaction.

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

[0164] [Table 1]

[0165] In the table, the description of "(1)→(2)" indicates that after the side chain-modified material (1) was brought into a flowable state, the thermoplastic resin (2) was added. "(1)+(2)" indicates that the side chain-modified material (1) and the thermoplastic resin (2) were mixed without performing the operation of bringing them into a flowable state.

[0166] It can be seen that the method according to the example can stably produce a modified resin in a short time as compared with the method according to the comparative example. [Explanation of Reference Signs]

[0167] 1... Heat exchanger, 2... Cooling trap, 3... Vacuum pump, 10... Reactor, 100... Manufacturing equipment, L10, L20, L21, L22... Pipes.

Claims

1. A method for producing a modified resin by 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 includes the following steps A to C. Step A: A step of supplying the side-chain modifying material (1) to a reactor Step B: After step A, in a state where the side-chain modifying material (1) can flow, a step of supplying the thermoplastic resin (2) to the reactor Step C: After step B, a step of modifying the side chain of the thermoplastic resin (2) with the side-chain modifying material (1)

2. The method according to claim 1, wherein step C is performed under reduced pressure.

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

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

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

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

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 includes a step of reacting the thermoplastic resin (2) and the side-chain modifying material (1) at a temperature of 180°C or lower.

9. The reactor is equipped with a stirrer, The stirrer is a large blade. The method according to claim 1 or 2.

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

11. The thermoplastic resin (2) has a structural unit derived from ethylene. The method according to claim 1 or 2.

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

13. The modification in step C is performed by a transesterification reaction. The method according to claim 1 or 2.

14. The modified resin is a polymer containing a structural unit (B) represented by the following formula (1). The method according to claim 1 or 2. 【Chemical 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)—, and represents L ３ represents a single bond, —CO—O—, —O—CO—, —O—, —CO—NH—, —NH—CO—, —CO—NH—CO—, —NH—CO—NH—, —NH—, or —N(CH ３ )—, and L ６ represents an alkyl group having 14 to 30 carbon atoms, L １ , L ２ , and L ３ In the description of the chemical structures of each of the horizontal chemical formulas, the left side thereof corresponds to the upper side of formula (1), and the right side thereof corresponds to the lower side of formula (1).

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