Resin composition, method for producing same, and method for modifying polymer

Abstract

The present invention addresses the problem of providing a resin composition in which a polymer having a carbonyl group and / or a carboxyl group is modified so as to change the physical properties thereof. The problem is solved by a resin composition which is obtained by melt-kneading a component A that is a polymer having a carbonyl group and / or a carboxyl group and a component B that is a terminally modified vinyl polymer having one or more amino groups at an end of the molecule.

Description

Resin composition, method for producing the same, and method for modifying polymer

[0001] The present invention relates to a resin composition and a method for producing the same. The present invention also relates to a method for modifying a polymer.

[0002] Techniques for using other polymers as modifiers for polymers are known in the art. For example, Patent Document 1 discloses modifying polyethylene with a composition containing polyethylene, polyamide, and a compatibilizer.

[0003] Japanese Patent Application Publication No. 2022-114420

[0004] In addition to the method using the composition disclosed in Patent Document 1, there is still room for further development in the method of modifying a polymer using a polymer.

[0005] An object of one aspect of the present invention is to provide a resin composition having altered physical properties by modifying a polymer having a carbonyl group and / or a carboxyl group.

[0006] A resin composition according to one embodiment of the present invention is prepared by melt-kneading the following components A and B: Component A: a polymer having a carbonyl group and / or a carboxyl group; Component B: a terminal-modified vinyl polymer having one or more amino groups at the molecular terminal.

[0007] According to one aspect of the present invention, there is provided a resin composition in which the physical properties are changed by modifying a polymer having a carbonyl group and / or a carboxyl group.

[0008] However, the present invention is not limited to the following embodiments and various modifications may be made within the scope of the claims. Embodiments that combine technical means described in different embodiments are also included in the technical scope of the present invention.

[0009] Unless otherwise specified in this specification, "A to B" representing a numerical range means "A or more and B or less." In this specification, "(meth)acrylic" means "acrylic and / or methacrylic."

[0010] [1. Components of Resin Composition] A resin composition according to one aspect of the present invention is prepared by melt-kneading component A: a polymer having a carbonyl group and / or a carboxyl group, and component B: a terminal-modified vinyl polymer having one or more amino groups at the molecular terminal. A resin composition according to another aspect of the present invention contains component A: a polymer having a carbonyl group and / or a carboxyl group, and component B: a terminal-modified vinyl polymer having one or more amino groups at the molecular terminal. In one embodiment, the latter resin composition is a precursor of the former resin composition.

[0011] The resin composition may contain other components in addition to Component A and Component B. Only one type of Component A, Component B, and other components may be contained, or two or more types of each may be contained.

[0012] 1.1. Component A: Polymer Having Carbonyl Groups and / or Carboxyl Groups Component A is a polymer having carbonyl groups and / or carboxyl groups. In one embodiment, component A has carbonyl groups and / or carboxyl groups in the main chain (such as polyamide). In one embodiment, component A has carbonyl groups and / or carboxyl groups as side chains (such as poly(meth)acrylic acid). In one embodiment, component A has carbonyl groups and / or carboxyl groups in both the main chain and side chains.

[0013] Examples of component A include polyamides, polyesters, polyimides, polycarbonates, polyurethanes, polyureas, polyketones, poly(meth)acrylic acid, poly(meth)acrylates, carboxymethyl cellulose, and styrene-maleic anhydride copolymers. In one embodiment, component A is one or more selected from the group consisting of polyamides, polyesters, polyimides, and polycarbonates.

[0014] Examples of the monomer that constitutes component A include diamines, dicarboxylic acids, aminocarboxylic acids, and lactams.

[0015] A diamine is a compound having two amino groups in one molecule. Examples of diamines include aromatic diamines, aliphatic diamines, and polyether diamines.

[0016] Aliphatic diamines are diamines having a linear, branched, or cyclic hydrocarbon structure in the molecule. Specific examples of aliphatic diamines include 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 1,13-diaminotridecane, 1,14-diaminotetradecane, 1,15-diaminopentadecane, 1,16-diaminohexadecane, 1,17-diaminoheptadecane, 1,18-diaminooctadecane, 1,19-diaminononadecane, 1,20-diaminoeicosane, cyclohexanediamine, and bis-(4-aminocyclohexyl)methane.

[0017] The aromatic diamine is a diamine having an aromatic ring structure in the molecule. Specific examples of aromatic diamines include 4,4'-diaminodiphenyl ether (ODA), 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP), p-phenylenediamine (PDA), 4,4'-diaminodiphenylmethane, benzidine, 3,3'-dichlorobenzidine, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 1,5-diaminonaphthalene, 4,4'-diaminodiphenyldiethylsilane, 4,4'-diaminodiphenylsilane, 4,4'-diminodiphenylethylphosphine oxide, 4,4'-diaminodiphenyl N-methylamine, 4,4'-diaminodiphenyl N-phenylamine, 1,3-diaminobenzene, and 1,2-diaminobenzene.

[0018] Polyetherdiamines are diamines having a polyether structure in the molecule. Specific examples of polyetherdiamines include amino-modified polyoxyalkylenes (such as polyoxyethylene, 1,2-polyoxypropylene, 1,3-polyoxypropylene, and copolymers thereof).

[0019] A dicarboxylic acid is a compound having two carboxylic acids in one molecule. Examples of dicarboxylic acids include aromatic dicarboxylic acids and aliphatic dicarboxylic acids.

[0020] Aliphatic dicarboxylic acids are dicarboxylic acids having a linear, branched, or cyclic hydrocarbon structure in the molecule. Specific examples of aliphatic dicarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brassicic acid, tetradecanedioic acid, pentadecanedioic acid, and octadecanedioic acid.

[0021] An aromatic dicarboxylic acid is a dicarboxylic acid having an aromatic ring structure in the molecule. Specific examples of aromatic dicarboxylic acids include terephthalic acid, phthalic acid, isophthalic acid, naphthalenedicarboxylic acid, and 2,6-naphthalenedicarboxylic acid.

[0022] An aminocarboxylic acid is a compound having both an amino group and a carboxylic acid in one molecule. Examples of aminocarboxylic acids include 12-aminododecanoic acid, 6-aminocaproic acid, 11-aminoundecanoic acid, para-aminomethylbenzoic acid, 4-aminocyclohexanecarboxylic acid, glycine, and alanine.

[0023] Lactams are compounds that contain a cyclic amide within the molecule. Examples of lactams include ε-caprolactam, ε-aminolaurolactam, ω-enantholactam, ω-undecanelactam, ω-dodecanelactam, α-pyrrolidone, and α-piperidone.

[0024] [1.2. Component B: Terminally modified vinyl polymer having one or more amino groups at molecular terminals] Component B is a terminally modified vinyl polymer having one or more amino groups at molecular terminals. In one embodiment, component B has one terminal having one or more amino groups. In one embodiment, component B has two or more terminals having one or more amino groups. In one embodiment, the terminal having an amino group contains one amino group. In one embodiment, the terminal having an amino group contains two or more amino groups.

[0025] [1.2.1. Terminals Having Amino Groups] Component B has one or more terminals having one or more amino groups. The number of terminals having amino groups may be one, two, three, four, five, or more per molecule. When one molecule of component B has multiple terminals having amino groups, the structures of the terminals may be the same or different. In one embodiment, component B is a linear polymer. In this case, component B has two terminals, one or both of which have an amino group.

[0026] The number of amino groups contained in the amino group-containing terminal may be 1, 2, 3 or more. When there are multiple amino group-containing terminals in one molecule of component B, the number of amino groups contained in each terminal may be the same or different.

[0027] In one embodiment, Component B has a molecular terminal structure represented by the following general formula (1).

[0028] In formula (1), R １ -O-, -O(CO)-, -NH-, -N(CH ３ )- or -N(CH ２ CH ３ )-. Among them, R １ is preferably —O(CO)— or —NH—.

[0029] In formula (1), R ２is a single bond or a divalent or trivalent group having 1 to 8 carbon atoms, which may have a heteroatom. ２ The number of carbon atoms is preferably 1 to 6.

[0030] R ２ Examples of heteroatoms that may be contained include an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a silicon atom, and a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom).

[0031] R ２ may have a linear structure, a branched structure, or a cyclic structure. ２ When R is a cyclic structure, ２ may have a heterocyclic structure.

[0032] In one embodiment, R ２ is a divalent or trivalent alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, aryl, or heteroaryl.

[0033] In this specification, divalent alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, aryl or heteroaryl refers to a group obtained by removing one hydrogen atom from a normally monovalent alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, aryl or heteroaryl. That is, divalent alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, aryl or heteroaryl has two bonding positions with other atoms. In addition, divalent alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, aryl or heteroaryl is also referred to as alkylene, heteroalkylene, cycloalkylene, heterocycloalkylene, arylene or heteroarylene.

[0034] As used herein, a trivalent alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, aryl, or heteroaryl refers to a group in which two hydrogen atoms have been removed from a normally monovalent alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, aryl, or heteroaryl. That is, the trivalent alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, aryl, or heteroaryl has three bonding positions to other atoms.

[0035] In general formula (1), R ３ is a single bond or a divalent group having 1 to 8 carbon atoms, which may have a heteroatom.

[0036] R ３ The number of carbon atoms in R is 0 to 8, preferably 0 to 6, more preferably 0 to 4, and even more preferably 0 to 2. ３ The number of carbon atoms in R is 0. ３ is a single bond or consists of only heteroatoms.

[0037] R ３ Examples of heteroatoms that may be contained include an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a silicon atom, and a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom).

[0038] R ３ may have a linear structure, a branched structure, or a cyclic structure. ３ When R is a cyclic structure, ３ may have a heterocyclic structure.

[0039] In one embodiment, R ３ is a divalent alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, aryl, or heteroaryl.

[0040] In general formula (1), R ４ and R ５ are each independently hydrogen, a methyl group, or an ethyl group. Among these, R ４ and R ５is preferably hydrogen. ４ or R ５ At least one of R is preferably hydrogen. ４ and R ５ More preferably, all of are hydrogen.

[0041] In a preferred embodiment of the present invention, in general formula (1), R ２ has 1 to 6 carbon atoms, and R ３ has 0 to 2 carbon atoms, and R ４ and R ５ are both hydrogen.

[0042] In general formula (1), n ​​is 1 or 2. In the terminal structure represented by general formula (1), when n=1, one structure represented by the following general formula (1′) is present, and when n=2, two structures are present. -R ３ -N(R ４ ) R ５ (1')

[0043] When n is 2, the terminal structure represented by general formula (1) is R ３ , R ４ and R ５ Each of the structures has two structures in parentheses containing:

[0044] When n is 2, two R ３ , R ４ and R ５ The structures represented by general formula (1′) may be the same or different from each other. That is, when n is 2, the two structures represented by general formula (1′) present in each terminal structure represented by general formula (1) may be the same or different from each other.

[0045] Specific examples of the terminal structure represented by general formula (1) include structures represented by the following formulas (i) to (iii).

[0046] [1.2.2. Main Chain of Component B] Component B is a terminally modified vinyl polymer. Therefore, the main chain of component B is primarily composed of structural units derived from vinyl monomers. When the total structural units contained in the main chain of component B is taken as 100 mol%, the structural units derived from vinyl monomers may be 50 mol%, 60 mol% or more, 70 mol% or more, 80 mol% or more, 90 mol% or more, or 100 mol%.

[0047] The vinyl monomer from which the structural units constituting the main chain of Component B are derived is not particularly limited as long as it has a vinyl group. Examples of the vinyl monomer include (meth)acrylic monomers, styrene monomers, maleimide monomers, chlorine-containing vinyl monomers, fluorine-containing vinyl monomers, silicon-containing vinyl monomers, nitrile group-containing vinyl monomers, amide group-containing vinyl monomers, vinyl esters, alkenes, and conjugated dienes.

[0048] Examples of the (meth)acrylic monomer include (meth)acrylic acid, (meth)acrylic acid salts, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, phenyl (meth)acrylate, toluyl (meth)acrylate, benzyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, Examples of such compounds include 2-hydroxypropyl acrylate, stearyl (meth)acrylate, glycidyl (meth)acrylate, 2-aminoethyl (meth)acrylate, γ-((meth)acryloyloxypropyl)trimethoxysilane, ethylene oxide adducts of (meth)acrylic acid, trifluoromethylmethyl (meth)acrylate, 2-trifluoromethylethyl (meth)acrylate, perfluoroethylethyl (meth)acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth)acrylate, 2-perfluoroethyl (meth)acrylate, perfluoromethyl (meth)acrylate, diperfluoromethylmethyl (meth)acrylate, perfluoromethylperfluoroethylmethyl (meth)acrylate, 2-perfluorohexylethyl (meth)acrylate, 2-perfluorodecylethyl (meth)acrylate, and 2-perfluorohexadecylethyl (meth)acrylate.

[0049] Examples of styrene monomers include styrene, vinyltoluene, α-methylstyrene, chlorostyrene, styrenesulfonic acid and styrenesulfonates.

[0050] Examples of the maleimide monomer include maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide and cyclohexylmaleimide.

[0051] Examples of chlorine-containing vinyl monomers include vinyl chloride, vinylidene chloride and allyl chloride.

[0052] Examples of the fluorine-containing vinyl monomer include perfluoroethylene, perfluoropropylene, and vinylidene fluoride.

[0053] Examples of silicon-containing vinyl monomers include vinyltrimethoxysilane and vinyltriethoxysilane.

[0054] Examples of the nitrile group-containing vinyl monomer include acrylonitrile and methacrylonitrile.

[0055] Examples of the amide group-containing vinyl monomer include acrylamide and methacrylamide.

[0056] Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, and vinyl cinnamate.

[0057] Examples of alkenes include ethylene, propylene, butylene and isobutylene.

[0058] Examples of conjugated dienes include butadiene and isoprene.

[0059] Other examples of vinyl monomers include maleic anhydride, maleic acid, monoalkyl esters of maleic acid, dialkyl esters of maleic acid, fumaric acid, monoalkyl esters of fumaric acid, dialkyl esters of fumaric acid, and allyl alcohol.

[0060] The main chain of component B may be derived from only one type of vinyl monomer, or may be derived from two or more types of vinyl monomers.

[0061] Since modification of the polymer terminals is relatively easy, the main chain of component B preferably contains as a main component at least one selected from the group consisting of poly(meth)acrylate, polystyrene, and polyisobutylene.

[0062] As used herein, the phrase "the main chain of component B is composed primarily of structural unit X" means that, assuming that all structural units contained in the main chain are 100 mol%, the proportion of structural unit X is 50 mol% or more. The proportion of structural unit X can be 60 mol% or more, 70 mol% or more, 80 mol% or more, 90 mol% or more, or 100 mol%.

[0063] Two or more types of structural unit X １ , X ２ ...X ｎ In the case where component B contains the structural unit X, the phrase "the main chain of component B is mainly composed of structural unit X" means that, assuming that all structural units contained in the main chain are 100 mol %, １ , X ２ ...X ｎ It is intended that the total proportion of the structural units X be 50 mol % or more. １ , X ２ ...X ｎ The total proportion of may be 60 mol % or more, 70 mol % or more, 80 mol % or more, 90 mol % or more, or 100 mol %.

[0064] The main chain of Component B may contain, in addition to the structural units derived from vinyl monomers, structural units derived from monomers other than vinyl monomers.

[0065] The backbone of component B may be a linear polymer, a branched polymer, or a star polymer.

[0066] In one embodiment, the main chain of component B is a linear polymer, and one or both ends of the linear polymer have an amino group.

[0067] [1.2.3. Physical Properties of Component B] The lower limit of the weight average molecular weight of Component B is preferably 550 or more, more preferably 1,200 or more, and even more preferably 2,400 or more. The upper limit of the weight average molecular weight of Component B is preferably 1,100,000 or less, more preferably 200,000 or less, and even more preferably 50,000 or less. The weight average molecular weight is measured by size exclusion chromatography. If the weight average molecular weight is within the above range, the number of amino groups introduced to the terminals of the vinyl polymer can be easily controlled.

[0068] The lower limit of the number average molecular weight of Component B is preferably 500 or more, more preferably 1,000 or more, and even more preferably 2,000 or more. The upper limit of the number average molecular weight of Component B is preferably 600,000 or less, more preferably 100,000 or less, and even more preferably 30,000 or less. The weight average molecular weight is measured by size exclusion chromatography. If the number average molecular weight is within the above range, the number of amino groups introduced into the terminals of the vinyl polymer can be easily controlled.

[0069] The molecular weight distribution of component B is preferably 1.8 or less, more preferably 1.7 or less, more preferably 1.6 or less, even more preferably 1.5 or less, even more preferably 1.4 or less, and particularly preferably 1.3 or less. Theoretically, the lower limit of the molecular weight distribution is 1. The molecular weight distribution is a value given by the weight average molecular weight (Mw) ÷ the number average molecular weight (Mn). If the molecular weight distribution is within the above range, the number of amino groups introduced to the terminals of the vinyl polymer can be easily controlled.

[0070] The weight average molecular weight (Mw) and number average molecular weight (Mn) of Component B are values ​​measured by size exclusion chromatography and calculated in terms of polystyrene. Specific examples of methods for measuring the weight average molecular weight (Mw) and number average molecular weight (Mn) of Component B are described in the Examples.

[0071] [1.2.4. Production Method of Component B] (Method for Forming an End Having an Amino Group) Component B can be produced, for example, by introducing a structure having an amino group into the end of a vinyl polymer to form an end having an amino group. Specific examples of such production methods include methods (1) to (3).

[0072] Method (1): A method comprising a step of reacting a halogen group located at the terminal of a vinyl polymer with a compound represented by the following general formula (2a): In formula (2a), X is —OH, —COOH, —NH ２ , -N(CH ３ )H or -N(CH ２ CH ３ ) H, or a salt thereof; R ２ is a trivalent group having 1 to 8 carbon atoms, which may have a heteroatom; R ３ is a single bond or a divalent group having 1 to 8 carbon atoms, which may have a heteroatom; R ４ and R ５ are each independently hydrogen, a methyl group, or an ethyl group; n is 1 or 2; when n=2 in formula (1) and formula (2a), there are two R ３ , R ４ and R ５ may be the same or different; When there are two or more terminal structures represented by general formula (1), the terminal structures may be the same or different.

[0073] Method (2): A method comprising the steps of reacting a halogen group located at the terminal of a vinyl polymer with a compound represented by the following general formula (2b), and reducing the resulting reaction product: In formula (2b), X is —OH, —COOH, —NH ２ , -N(CH ３ )H or -N(CH ２ CH ３ ) H, or a salt thereof; R ２ is a trivalent group having 1 to 8 carbon atoms, which may have a heteroatom; R ３ is a single bond or a divalent group having 1 to 8 carbon atoms, which may have a heteroatom; R ４ and R ５are each independently hydrogen, a methyl group, or an ethyl group; n is 1 or 2; when n=2 in formula (1) and formula (2b), there are two R ３ , R ４ and R ５ may be the same or different; When there are two or more terminal structures represented by general formula (1), the terminal structures may be the same or different.

[0074] Method (3): A method comprising a step of reacting a functional group (such as a hydroxyl group or a carboxyl group) other than a halogen group located at the terminal of a vinyl polymer with a compound of the following general formula (2c): In formula (2c), X' is -OH, -NH ２ , -N(CH ３ )H, —N(CH ２ CH ３ ) H, —COOH, —COZ or —Z (Z is a halogen atom); R ２ is a trivalent group having 1 to 8 carbon atoms, which may have a heteroatom; R ３ is a single bond or a divalent group having 1 to 8 carbon atoms, which may have a heteroatom; R ４ and R ５ are each independently hydrogen, a methyl group, or an ethyl group; n is 1 or 2; when n=2 in formula (2c), there are two R ３ , R ４ and R ５ The structures of may be the same or different.

[0075] In formula (2a) and formula (2b), examples of salts for X include alkali metal salts (potassium, sodium, etc.) and alkaline earth metal salts (calcium, magnesium, etc.). In formula (2c), examples of halogens represented by Z include fluorine, chlorine, bromine, and iodine.

[0076] Methods (1) to (3) are explained in more detail below, although component B can also be produced by methods other than these.

[0077] Method (1) In method (1), a halogen group located at the end of a vinyl polymer is reacted with a compound represented by general formula (2a) to form an amino group-containing end.

[0078] An example of a method for reacting a halogen group located at the terminal of a vinyl polymer with a compound represented by general formula (2a) is as follows: 1. Dissolve a vinyl polymer having a halogen group at its terminal and a compound represented by general formula (2a) in a solvent. 2. Heat the solution (with stirring, if necessary).

[0079] Since the above reaction is a nucleophilic substitution reaction, the solvent used is preferably a polar solvent, examples of which include N,N-dimethylacetamide, tetrahydrofuran, dioxane, diethyl ether, acetone, dimethyl sulfoxide, dimethylformamide, hexamethylphosphoric triamide, and acetonitrile.

[0080] The lower limit of the heating temperature of the solution may be 30° C. or higher, 50° C. or higher, or 70° C. or higher. The upper limit of the heating temperature of the solution may be 120° C. or lower, 100° C. or lower, or 90° C. or lower.

[0081] The heating time of the solution is usually set to a time sufficient for all halogen groups in the vinyl polymer to be substituted with the compound represented by general formula (2a), and may be, for example, 30 minutes to 6 hours.

[0082] The terminal structure formed by the method (1) corresponds to the terminal structure represented by the general formula (1). Specifically, R １ is the partial structure of X in general formula (2) (R １ R in general formula (1) is a structure in which a hydrogen atom or a metal atom constituting a salt is eliminated from R ２ , R ３ , R ４ and R ５ have the same structure as those in the general formula (2). Therefore, R in the compound represented by the general formula (2a) １ ~R ５ For more detailed aspects of the above, the description of general formula (1) is cited as appropriate.

[0083] Specific examples of the compound represented by general formula (2a) include compounds represented by the following formulas (iv) to (vi): In one embodiment, the compound represented by general formula (2a) is one or more compounds selected from the group consisting of compounds represented by formulas (iv) to (vi).

[0084] Method (2) In method (2), a halogen group located at the end of a vinyl polymer is reacted with a compound represented by general formula (2b), and the nitro group is further reduced to form a terminal having an amino group.

[0085] An example of a method for reacting a halogen group located at the terminal of a vinyl polymer with a compound represented by general formula (2b) is as follows: 1. Dissolve a vinyl polymer having a halogen group at its terminal and a compound represented by general formula (2b) in a solvent. 2. Heat the solution (with stirring as necessary). 3. Reduce the nitro group to convert it to an amino group.

[0086] Since the above reaction is a nucleophilic substitution reaction, the solvent used is preferably a polar solvent, examples of which include N,N-dimethylacetamide, tetrahydrofuran, dioxane, diethyl ether, acetone, dimethyl sulfoxide, dimethylformamide, hexamethylphosphoric triamide, and acetonitrile.

[0087] The lower limit of the heating temperature of the solution may be 30° C. or higher, 50° C. or higher, or 70° C. or higher. The upper limit of the heating temperature of the solution may be 120° C. or lower, 100° C. or lower, or 90° C. or lower.

[0088] The heating time of the solution is usually set to a time sufficient for all halogen groups in the vinyl polymer to be substituted with the compound represented by general formula (2b), and may be, for example, 30 minutes to 6 hours.

[0089] When reducing the nitro group, a reducing agent can be appropriately used, examples of which include ammonium chloride, hydrogen, hydrazine, lithium aluminum hydride, and sodium borohydride.

[0090] The terminal structure formed by the method (2) corresponds to the terminal structure represented by the general formula (1). Specifically, R １ is the partial structure of X in general formula (2) (R １ R in general formula (1) is a structure in which a hydrogen atom or a metal atom constituting a salt is eliminated from R ２ and R ３ have the same structure as those in the general formula (2). Therefore, R in the compound represented by the general formula (2b) １ ~R ３ For more detailed aspects of the formula (1), the description of the formula (1) is appropriately cited. ４ and R ５ are the products of reduction of the nitro group, so both are hydrogen.

[0091] Specific examples of the compound represented by general formula (2b) include compounds represented by the following formula (vii):

[0092] Method (3) In method (3), a functional group other than a halogen group located at the end of a vinyl polymer is reacted with a compound of general formula (2c) to form an end having an amino group.

[0093] The terminal structure formed by the method (3) corresponds to the terminal structure represented by the general formula (1). Specifically, R １ is the partial structure of X′ in general formula (2) (R １ R in general formula (1) is a structure in which a hydrogen atom, a hydroxyl group, Z, or the like has been removed. ２ , R ３ , R ４ and R ５ have the same structure as those in the general formula (2). Therefore, R in the compound represented by the general formula (2b) ２ , R ３ , R ４ and R ５ For more detailed aspects of the above, the description of general formula (1) is cited as appropriate.

[0094] (Main Chain Polymerization Method) The polymerization method for the vinyl polymer that forms the main chain of Component B is not particularly limited. For example, known polymerization methods such as living cationic polymerization and living radical polymerization can be used. More specific examples include the polymerization methods described in JP-A-2005-232419, JP-A-2006-291073, and JP-A-2016-88944. By using such methods, it is possible to polymerize a vinyl polymer having a terminal halogen group.

[0095] Hereinafter, a specific embodiment of the vinyl polymer preparation process will be described in detail, taking a living radical polymerization method as an example.

[0096] Examples of vinyl monomers that are raw materials for vinyl polymers include the monomers described in Section [1.2.2].

[0097] Specific examples of living radical polymerization include the following: - Polymerization methods using chain transfer agents (such as polysulfides) - Polymerization methods using radical scavengers (such as organic tellurium compounds, cobalt porphyrin complexes, and nitroxide compounds) - Atom transfer radical polymerization using organic halides as initiators and transition metal complexes as catalysts - Reversible transfer catalyst polymerization using organic halides as initiators and organic molecules with nitrogen, oxygen, or other central atoms as catalysts

[0098] Among the above, the atom transfer radical polymerization method is preferred because it is easy to control the molecular weight and molecular weight distribution.

[0099] In living radical polymerization, for example, the number of halogen terminal groups in the vinyl polymer obtained by polymerization can be adjusted by appropriately selecting the type of polymerization initiator. Specifically, when an initiator with one polymerization initiation point is used, a linear vinyl polymer having a halogen group at one end can be prepared. When an initiator with two polymerization initiation points is used, a linear vinyl polymer having a halogen group at both ends can be produced. When an initiator with three or more polymerization initiation points is used, a star-shaped vinyl polymer having a halogen group at three or more ends can be produced.

[0100] Examples of initiators having one polymerization initiation point include ethyl 2-bromoisobutyrate, ethyl bromoacetate, methyl bromoacetate, (1-bromoethyl)benzene, allyl bromide, methyl 2-bromopropionate, methyl chloroacetate, methyl 2-chloropropionate, and (1-chloroethyl)benzene. Examples of initiators having two polymerization initiation points include diethyl 2,5-dibromoadipate, dimethyl 2,5-dibromoadipate, and diethyl 2,5-dibromoadipate. Examples of initiators having three or more polymerization initiation points include 1,1,1-tris(2-bromoisobutyryloxymethyl)ethane, tetrakis(2-bromoisobutyryloxymethyl)methane, and dipentaerythritol hexakis(2-bromoisobutyrate).

[0101] As described above, in methods (1) and (2), the halogen terminals of the vinyl polymer are converted to terminals having an amino group. Therefore, by adjusting the number of halogen terminals contained in the vinyl polymer, the number of terminals having an amino group contained in component B can be adjusted.

[0102] In living radical polymerization, in addition to an initiator, a polymerization catalyst, a polydentate amine (ligand), a base, a reducing agent, a solvent, etc. The type and amount of each of these components can be appropriately selected by those skilled in the art.

[0103] In the method (3), a vinyl polymer not having a halogen terminal is used as the raw material to produce the component B. Examples of the polymerization method for such a vinyl polymer include a polymerization method using mercaptans having a hydroxyl group or a carboxyl group (mercaptoethanol, mercaptoacetic acid, etc.) (see, for example, JP-A-1-203412).

[0104] Vinyl polymers obtained by the polymerization method using mercaptans as described above may have a sulfur atom-containing structure derived from the mercaptans near their terminals. When such vinyl monomers are used as raw materials to form terminals having amino groups, sulfur atom-containing structures derived from the mercaptans are further positioned between one or more amino groups at the terminals and the main chain structure consisting of the vinyl monomer. Terminally modified vinyl polymers having such structures are also included in the category of Component B.

[0105] [1.3. Other Components] The resin composition may contain various additives as components other than Component A and Component B. Examples of additives include phosphorus compounds (e.g., phosphoric acid, pyrophosphoric acid, polyphosphoric acid, phosphorous acid, hypophosphorous acid, or alkali metal or alkaline earth metal salts thereof), heat resistance agents, ultraviolet absorbers, light stabilizers, antioxidants, antistatic agents, lubricants, slip agents, crystal nucleating agents, tackifiers, mold release agents, plasticizers, pigments, dyes, flame retardants, reinforcing materials, inorganic fillers and microfibers, and X-ray opaque agents.

[0106] [2. Composition of Resin Composition] In the resin composition, the upper limit of the content ratio (weight ratio) of Component A / Component B may be 99.99 / 0.01 or less, 99.95 / 0.05 or less, or 99.9 / 0.1 or less. In the resin composition, the lower limit of the content ratio (weight ratio) of Component A / Component B may be 70 / 30 or more, 80 / 20 or more, 90 / 10 or more, or 94 / 6 or more.

[0107] In one embodiment, component A is a polyamide, and component B is a linear poly(meth)acrylate, with component B having an amino group at one end. Such a resin composition may provide, for example, one or more of the following modifying effects: - Improved toughness (increased breaking strain) - Improved moldability (decreased melt viscosity) - Improved heat resistance (increased deflection temperature under load)

[0108] In one embodiment, component A is a polyamide, and component B is a linear poly(meth)acrylate, with component B having amino groups at both ends. Such a resin composition may provide, for example, one or more of the following modifying effects: - Improved strength (increased tensile modulus) - Improved impact resistance (increased Charpy impact strength) - Improved moldability (reduced melt viscosity)

[0109] [3. Method for Producing Resin Composition] A method for producing a resin composition according to one embodiment of the present invention includes a step of melt-kneading Component A and Component B. Specific embodiments of Component A and Component B are as described in Section [1].

[0110] The resin composition can be melt-kneaded using known devices, such as extruders (single-screw extruders, twin-screw extruders, etc.), batch kneaders (laboplastomills, pressure kneaders, Banbury mixers, etc.), and roll mills (two-roll mills, three-roll mills, etc.).

[0111] The lower limit of the melt-kneading temperature is preferably 180° C. or higher, more preferably 200° C. or higher, and even more preferably 240° C. or higher. The upper limit of the melt-kneading temperature is preferably 400° C. or lower, more preferably 350° C. or lower, and even more preferably 300° C. or lower.

[0112] The lower limit of the melt-kneading time may be 1 minute or more, or 3 minutes or more, and the upper limit of the melt-kneading time may be 24 hours or less, 12 hours or less, 6 hours or less, or 1 hour or less.

[0113] In melt-kneading component A and component B, component B may be added to molten component A, component A may be added to molten component B, or component A and component B may be melted simultaneously.

[0114] The resin composition obtained by melt-kneading may be molded to obtain a molded article, for example by extrusion molding, blow molding, injection molding, compression molding, or calendar molding.

[0115] [4. Method for Modifying a Polymer] A method for modifying a polymer according to one embodiment of the present invention includes a step of melt-kneading component A and component B. Specific embodiments of component A and component B are as described in Section [1]. Specific embodiments of the melt-kneading are as described in Section [2].

[0116] The mechanism by which this modification method produces a modification effect is presumed to be as follows (however, this explanation is provided to aid in understanding the invention and is not intended to limit the scope of the invention): By melt-kneading components A and B, the carbonyl and / or carboxyl groups contained in component A interact with the amino groups contained in component B. As a result, the structures or movements that the polymer chains of component A and component B can take are restricted or changed. These microscopic changes manifest as macroscopic changes in the physical properties of the resin composition.

[0117] The properties of component A modified by the modification method can be adjusted by appropriately combining component A and component B.

[0118] In one embodiment, component A is a polyamide, and component B is a linear poly(meth)acrylate, with component B having an amino group at one end. Such a combination of components A and B may provide, for example, one or more of the following modifying effects: - Improved toughness (increased breaking strain) - Improved moldability (decreased melt viscosity) - Improved heat resistance (increased deflection temperature under load)

[0119] In one embodiment, component A is a polyamide, and component B is a linear poly(meth)acrylate, with component B having amino groups at both ends. Such a combination of components A and B may provide, for example, one or more of the following modifying effects: - Improved strength (increased tensile modulus) - Improved impact resistance (increased Charpy impact strength) - Improved moldability (reduced melt viscosity)

[0120] [5. Summary] The present invention includes the following aspects. <1> A resin composition obtained by melt-kneading the following components A and B: Component A: a polymer having a carbonyl group and / or a carboxyl group; Component B: a terminal-modified vinyl polymer having one or more amino groups at the molecular terminal. <2> The resin composition according to <1>, in which the component A is one or more selected from polyamide, polyester, polyimide, and polycarbonate. <3> The resin composition according to <1> or <2>, in which the molecular terminal structure of the component B is a structure represented by the following general formula (1): In formula (1), R １ -O-, -O(CO)-, -NH-, -N(CH ３ )- or -N(CH ２ CH ３ )- and R ２ and R ３ are each independently a single bond or a divalent or trivalent group having 1 to 8 carbon atoms, which may have a heteroatom; R ４ and R ５ are each independently hydrogen, a methyl group, or an ethyl group; n is 1 or 2; when n is 2, there are two R ３ , R ４ and R ５ When there are two or more terminal structures represented by general formula (1), the terminal structures may be the same or different. ２ and R ３ <5> The resin composition according to <3>, wherein R is each independently a divalent or trivalent alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, aryl, or heteroaryl. ２ has 1 to 6 carbon atoms, and R ３ has 0 to 2 carbon atoms, and R ４ and R ５and are both hydrogen. <6> The resin composition according to any one of <1> to <5>, wherein Component B is a linear polymer, and the linear polymer has one or more amino groups at one or both ends. <7> The resin composition according to any one of <1> to <6>, wherein the main chain of Component B is primarily composed of one or more compounds selected from the group consisting of poly(meth)acrylate, polystyrene, and polyisobutylene. <8> The resin composition according to any one of <1> to <7>, wherein Component B has a polystyrene-equivalent number average molecular weight of 500 to 600,000 and a molecular weight distribution of 1.8 or less, as measured by size exclusion chromatography. <9> A method for producing a resin composition, comprising the step of melt-kneading the following Components A and B: Component A: a polymer having a carbonyl group and / or a carboxyl group; Component B: a terminal-modified vinyl polymer having one or more amino groups at molecular ends. <10> The manufacturing method according to <9>, wherein the melt-kneading temperature is 180°C or higher. <11> The manufacturing method of a resin composition according to <9> or <10>, wherein the component A is one or more selected from polyamide, polyester, polyimide, and polycarbonate. <12> A method for modifying a polymer, comprising a step of melt-kneading the following components A and B: Component A: a polymer having a carbonyl group and / or a carboxyl group; Component B: a terminal-modified vinyl polymer having one or more amino groups at a molecular terminal. <13> The method according to <12>, wherein the melt-kneading temperature is 180°C or higher. <14> The method according to <12> or <13>, wherein the component A is one or more selected from polyamide, polyester, polyimide, and polycarbonate. <15> A resin composition comprising the following components A and B: Component A: a polymer having a carbonyl group and / or a carboxyl group; Component B: a terminal-modified vinyl polymer having one or more amino groups at a molecular terminal.

[0121] [Measurement Method] [Polymerization Conversion Rate of Component B] The conversion rate of vinyl monomers to polymers in the production process of Component B was measured by gas chromatography. The measurement conditions were as follows: Measuring instrument: GC-2000 (Shimadzu Corporation) Column: GC column HP-1 (Agilent J&W) Standard: toluene

[0122] [Analysis of Functional Groups Contained in Component B] The functional groups contained in Component B (and the vinyl polymer that is the raw material for Component B) were analyzed by １ Qualitative and quantitative analysis was performed by H NMR under the following measurement conditions: Measurement equipment: 400 MHz NMR (Bruker) Analysis sample: A solution prepared by dissolving 30 mg of component B in 0.8 g of deuterated chloroform.

[0123] [Weight-average molecular weight (Mw) and number-average molecular weight (Mn) of component B] The weight-average molecular weight and number-average molecular weight of component B (and the vinyl polymer that is the raw material for component B) were measured by size exclusion chromatography. The measurement conditions were as follows: Measurement equipment: HLC-8420GPC (Tosoh Corporation) Column: TOSOH TSKgel Super HM-L (Tosoh Corporation) Standard: Polystyrene Eluent: Chloroform with 1.5 wt% triethylamine added Analytical sample: Solution prepared by dissolving 3 mg of component B in 3 mL of eluent

[0124] [Amount of Terminal Bromine in Vinyl Polymer] The amount of terminal bromine in the vinyl polymer used as the raw material for Component B was quantified by the following procedure. 1. A large excess of dimethylacetamide and potassium acrylate was added to the vinyl polymer. The resulting solution was stirred at 50°C for 30 minutes. This substituted the terminal bromine in the vinyl polymer with acrylic acid groups. 2. An excess of ethyl acetate and water was added to the system. From the resulting mixture, only the organic phase was collected. 3. The organic phase was concentrated to obtain a vinyl polymer whose terminals were modified with acrylic acid groups. 4. The vinyl polymer obtained in step 3 was dissolved in deuterated chloroform. The resulting solution was used as an analytical sample. １The polymer was analyzed by H NMR. 5. The signal appearing in the range of 4.8 to 5.2 ppm was detected as the H signal at the site where the acrylic acid group was bonded. The amount of terminal bromine originally contained in the vinyl polymer was calculated from the integral value of the signal.

[0125] [Tensile Test] A tensile test was performed according to the following procedure to measure the yield stress (MPa), yield strain (%), break strain (%), and tensile modulus (MPa). 1. The resin composition was press-molded into a 0.5 mm thick sheet. 2. A dumbbell No. 3 piece was cut out. This piece was aged overnight or more in a constant temperature and humidity chamber at 23°C and 50% RH to prepare a test specimen. 3. A tensile test was performed in accordance with JIS K 6251:2017. The tensile speed was 200 mm / min. The test was performed three times for each type of test specimen, and the average of the three measurements was used as the measured value. However, if a test specimen containing air bubbles inside broke at the air bubbles, the results of that test were excluded from the calculation of the average value.

[0126] [Melt Viscosity] The viscosity of the resin composition in the molten state was measured using a capillary rheometer. The measurement conditions were as follows: Measurement equipment: Capillograph 1D (Toyo Seiki Seisakusho, Ltd.) Measurement temperature: 250°C (preheating for 5 minutes) Shear rate during measurement: 1220 s －１ Orifice: Radius 0.5 mm, length 10 mm

[0127] [Deflection temperature under load] The deflection temperature under load was measured in accordance with JIS K 7191. The measurement conditions were as follows: Test load: 0.45 MPa Heating rate: 120°C / h (preheating for 5 minutes) Specified deflection: 0.340 mm Test piece: width 10.00 mm, thickness 4.00 mm

[0128] [Charpy Impact Test] The notched Charpy impact strength was measured in accordance with JIS K 7111. The measurement conditions were as follows: Hammer capacity: 0.5 J; Distance: 0.2300 m; Hammer lifting angle α': 141.0°; Specified deflection: 0.340 mm

[0129] [Production Example 1: Production of Vinyl Polymer] [Production Example 1-1: Vinyl Polymer 1] Vinyl polymer 1 was synthesized according to the following procedure. Vinyl polymer 1 is a linear polybutyl acrylate in which one end of the molecular chain is bromine-terminated. 1. 160 g of methanol, 320 g of butyl acrylate, 55.3 g of ethyl 2-bromoisobutyrate (a monoinitiation initiator), 4.3 g of triethylamine, 0.16 g of cupric bromide, and 0.16 g of tris[2-(dimethylamino)ethyl]amine were charged into a flask. 2. Nitrogen was bubbled through the flask. This removed oxygen from the flask. 3. The temperature inside the flask was raised to 45°C. 4. In a separate container, 49 g of methanol, 0.25 g of ascorbic acid, and 0.29 g of triethylamine were mixed. In this way, a methanol solution was obtained. Nitrogen was bubbled through the methanol solution. 5. The methanol solution was added dropwise to the flask at a rate of 5.1 mL / hour. 6. 0.5 hours after the start of the addition of the methanol solution, 480 g of butyl acrylate was added dropwise to the flask. Nitrogen had been bubbled through the butyl acrylate beforehand. The butyl acrylate was added dropwise over 1.5 hours. 7. Seven hours after the start of the addition of the methanol solution, it was confirmed that the conversion rate of butyl acrylate had reached 95% or more. The addition of the methanol solution was then stopped. 8. The reaction solution in the flask was concentrated under vacuum at 100°C for 1 hour. 9. 800 g of butyl acetate, 8 g of Kyoward 500 (Kyowa Chemical Industry Co., Ltd.), 8 g of Kyoward 700 (Kyowa Chemical Industry Co., Ltd.), and 8 g of Radiolite 900 (Showa Chemical Industry Co., Ltd.) were added to the flask. The mixture was then stirred at 80°C for 1 hour. 10. The solid content was filtered off, and the obtained filtrate was concentrated under vacuum at 100° C. for 2 hours, thereby obtaining a vinyl polymer 1.

[0130] The number average molecular weight of vinyl polymer 1 was 2,570. The molecular weight distribution of vinyl polymer 1 was 1.30. Vinyl polymer 1 had an average of 0.86 bromine terminals per molecule.

[0131] [Production Example 1-2: Vinyl Polymer 2] Vinyl Polymer 2 was synthesized according to the following procedure. Vinyl Polymer 2 is a linear polybutyl acrylate with both bromine ends in the molecular chain. 1. 160 g of methanol, 320 g of butyl acrylate, 50 g of diethyl 2,5-dibromoadipate (a dual-initiation initiator), 1.4 g of triethylamine, 0.15 g of cupric bromide, and 0.16 g of tris[2-(dimethylamino)ethyl]amine were charged into a flask. 2. Nitrogen was bubbled through the flask. This removed oxygen from the flask. 3. The temperature inside the flask was raised to 45°C. 4. 24 g of methanol, 0.12 g of ascorbic acid, and 0.14 g of triethylamine were mixed in a separate container. A methanol solution was thus obtained. Nitrogen was bubbled through the methanol solution. 5. The methanol solution was added dropwise to the flask. The dropping rate was 2.4 mL / hour. 6. 0.5 hours after the start of the methanol solution dropping, 480 g of butyl acrylate was dropped into the flask. Nitrogen had been bubbled through the butyl acrylate beforehand. The butyl acrylate was dropped over 1.5 hours. 7. 4 hours after the start of the methanol solution dropping, it was confirmed that the conversion of butyl acrylate had reached 95% or more. The dropping of the methanol solution was then stopped. 8. The reaction solution in the flask was concentrated under vacuum at 100°C for 1 hour. 9. 800 g of butyl acetate, 8 g of Kyoward 500 (Kyowa Chemical Industry Co., Ltd.), 8 g of Kyoward 700 (Kyowa Chemical Industry Co., Ltd.), and 8 g of Radiolite 900 (Showa Chemical Industry Co., Ltd.) were added to the flask. The mixture was then stirred at 80°C for 1 hour. 10. The filtrate obtained by filtering off the solids was concentrated under vacuum at 100°C for 2 hours. In this way, vinyl polymer 2 was obtained.

[0132] The number average molecular weight of vinyl polymer 2 was 6,050. The molecular weight distribution of vinyl polymer 2 was 1.10. Vinyl polymer 2 had an average of 1.6 bromine terminals per molecule.

[0133] [Production Example 1-3: Vinyl Polymer 3] Vinyl Polymer 3 was synthesized according to the following procedure. Vinyl Polymer 3 is a linear polybutyl acrylate with both bromine terminals on the molecular chain. 1. 160 g of methanol, 320 g of butyl acrylate, 9.4 g of diethyl 2,5-dibromoadipate (a dual-initiation initiator), 0.3 g of triethylamine, 0.07 g of cupric bromide, and 0.07 g of tris[2-(dimethylamino)ethyl]amine were charged into a flask. 2. Nitrogen was bubbled through the flask. This removed oxygen from the flask. 3. The temperature inside the flask was raised to 45°C. 4. 9 g of methanol, 0.23 g of ascorbic acid, and 0.26 g of triethylamine were mixed in a separate container. This resulted in a methanol solution. Nitrogen was bubbled through the methanol solution. 5. The methanol solution was added dropwise to the flask. The dropping rate was 5.0 mL / hour. 6. 0.5 hours after the start of the methanol solution dropping, 480 g of butyl acrylate was dropped into the flask. Nitrogen had been bubbled through the butyl acrylate beforehand. The butyl acrylate was dropped over 1.5 hours. 7. 3 hours after the start of the methanol solution dropping, it was confirmed that the conversion of butyl acrylate had reached 95% or more. The dropping of the methanol solution was then stopped. 8. The reaction solution in the flask was concentrated under vacuum at 100°C for 1 hour. 9. 800 g of butyl acetate, 8 g of Kyoward 500 (Kyowa Chemical Industry Co., Ltd.), 8 g of Kyoward 700 (Kyowa Chemical Industry Co., Ltd.), and 8 g of Radiolite 900 (Showa Chemical Industry Co., Ltd.) were added to the flask. The mixture was then stirred at 80°C for 1 hour. 10. The filtrate obtained by filtering off the solids was concentrated under vacuum at 100°C for 2 hours. In this way, vinyl polymer 3 was obtained.

[0134] The number average molecular weight of vinyl polymer 3 was 28,800. The molecular weight distribution of vinyl polymer 3 was 1.10. Vinyl polymer 3 had an average of 1.5 bromine terminals per molecule.

[0135] [Production Example 2: Introduction of Amino Groups] [Production Example 2-1: Terminally Modified Vinyl Polymer 1] Terminally modified vinyl polymer 1 was synthesized according to the following procedure. Terminally modified vinyl polymer 1 is a linear polybutyl acrylate in which two amino groups have been introduced at one end of the molecular chain. 1. 150 g of vinyl polymer 1 and 150 g of N,N-dimethylacetamide were charged into a flask and stirred until homogeneous. 2. While continuing to stir, 13.5 g of potassium carbonate and 16.4 g of diaminobenzoic acid were added. 3. The contents of the flask were heated and stirred at 80°C for 4 hours. 4. The resulting solution was concentrated under vacuum at 80°C for 1 hour. 5. The solution was diluted with 150 g of toluene. The solution was then passed through a Kiriyama funnel pre-coated with filter paper and Radiolite R300 to obtain a clear filtrate. 6. The resulting filtrate was concentrated under vacuum at 100°C for 2 hours. As a result, a terminally modified vinyl polymer 1 was obtained.

[0136] Terminally modified vinyl polymer 1 has a molecular structure in which the bromine terminals of vinyl polymer 1 have been substituted with diaminobenzoic acid. The number average molecular weight of terminally modified vinyl polymer 1 was 2,628. The molecular weight distribution of terminally modified vinyl polymer 1 was 1.19. Terminally modified vinyl polymer 1 had an average of 0.93 diamino terminals per molecule. NMR spectrum confirmed that the bromine terminals of terminally modified vinyl polymer 1 had been substituted with diaminobenzoic acid ester.

[0137] [Production Example 2-2: Terminal-Modified Vinyl Polymer 2] Terminal-modified vinyl polymer 2 was synthesized according to the following procedure. Terminal-modified vinyl polymer 2 is a linear polybutyl acrylate in which two amino groups have been introduced at both ends of the molecular chain. 1. 100 g of vinyl polymer 2 and 100 g of N,N-dimethylacetamide were placed in a flask and stirred until homogeneous. 2. While continuing to stir, 9.1 g of potassium carbonate and 11.2 g of diaminobenzoic acid were added. 3. The contents of the flask were heated and stirred at 80°C for 5 hours. 4. 200 g of 1-butanol and 100 g of water were added to the flask, stirred at room temperature, and allowed to stand. After phase separation, only the organic phase was extracted. This operation was repeated three times. 5. The resulting organic phase was concentrated under vacuum at 80°C for 1 hour. This yielded terminal-modified vinyl polymer 2.

[0138] Terminally modified vinyl polymer 2 has a molecular structure in which the bromine terminals of vinyl polymer 2 have been substituted with diaminobenzoic acid. The number average molecular weight of terminally modified vinyl polymer 2 was 5,070. The molecular weight distribution of terminally modified vinyl polymer 2 was 1.18. Terminally modified vinyl polymer 2 had an average of 1.6 diamino terminals per molecule. NMR spectrum confirmed that the bromine terminals of terminally modified vinyl polymer 2 had been substituted with diaminobenzoic acid ester.

[0139] [Production Example 2-3: Terminal-Modified Vinyl Polymer 3] Terminal-modified vinyl polymer 3 was synthesized according to the following procedure. Terminal-modified vinyl polymer 3 is a linear polybutyl acrylate in which two amino groups have been introduced at both ends of the molecular chain. 1. 100 g of vinyl polymer 3 and 100 g of N,N-dimethylacetamide were placed in a flask and stirred until homogeneous. 2. While continuing to stir, 1.9 g of potassium carbonate and 2.3 g of diaminobenzoic acid were added. 3. The contents of the flask were heated and stirred at 80°C for 9 hours. 4. 200 g of 1-butanol and 100 g of water were added to the flask, stirred at room temperature, and allowed to stand. After phase separation, only the organic phase was extracted. This operation was repeated three times. 5. The resulting organic phase was concentrated under vacuum at 80°C for 1 hour. This yielded terminal-modified vinyl polymer 3.

[0140] Terminally modified vinyl polymer 3 has a molecular structure in which the bromine terminal of vinyl polymer 3 has been substituted with diaminobenzoic acid. The number average molecular weight of terminally modified vinyl polymer 3 was 27,770. The molecular weight distribution of terminally modified vinyl polymer 3 was 1.11. Terminally modified vinyl polymer 3 had an average of 1.5 diamino terminals per molecule. NMR spectrum confirmed that the bromine terminal of terminally modified vinyl polymer 3 had been substituted with diaminobenzoic acid ester.

[0141] Examples 1-1 to 1-5 Resin compositions were prepared using nylon 6 (UBE Corporation) as component A and terminally modified vinyl polymer 1 as component B. The specific procedures are as follows: 1. Component A was melted by kneading at 250°C and 50 rpm. A Laboplastomill 4C150-01 (Toyo Seiki Seisaku-sho, Ltd.) was used for kneading. 2. Component B and an antioxidant (SUMILIZER GA-80, Sumitomo Chemical Co., Ltd.) listed in Table 1 were added, and the mixture was heated and kneaded at 250°C and 50 rpm for 10 minutes to obtain a resin composition. 3. The obtained resin composition was compression molded at 250°C and 5 MPa. This resulted in molded bodies having a thickness of 2 mm or 0.5 mm.

[0142] Comparative Examples 1-1 and 1-2 Molded bodies were obtained in the same manner as in Examples, except that component B was not added.

[0143] [Results] The results are shown in Table 1.

[0144] As can be seen from Table 1, the molded articles of Examples 1-1 and 1-2 had higher breaking strains than the molded article of Comparative Example 1-1. Other physical properties were generally comparable between the two. Furthermore, the molded articles of Examples 1-3 to 1-5 had higher breaking strains than the molded article of Comparative Example 1-2. This suggests that kneading a terminal-modified vinyl polymer having an amino group at one end increases the breaking strain of the polymer (i.e., improves the toughness of the molded article). In particular, as in Examples 1-1 to 1-3, it suggests that when the blending amount of the terminal-modified vinyl polymer falls within a predetermined range (e.g., 0.3 to 2 wt % relative to the total of Components A and B), the toughness of Component A is improved without deteriorating other physical properties.

[0145] Examples 2-1 to 2-4 Resin compositions were prepared using nylon 6 (UBE Corporation) as component A and terminally modified vinyl polymer 2 or terminally modified vinyl polymer 3 as component B. The amount of component B was varied to observe changes in physical properties. The specific procedures are as follows: 1. Component A was melted by kneading at 250°C and 50 rpm. A Labo Plastomill 4C150-01 (Toyo Seiki Seisaku-sho, Ltd.) was used for kneading. 2. Component B listed in Table 1 was added, and the mixture was heated and kneaded at 250°C and 50 rpm for 10 minutes. A resin composition was thus obtained. 3. The resulting resin composition was compression molded at 250°C and 5 MPa. This resulted in molded bodies with a thickness of 2 mm or 0.5 mm.

[0146] Comparative Example 2-1 A molded article was obtained in the same manner as in Examples 2-1 to 2-4, except that Component B was not added.

[0147] [Results] The results are shown in Table 2.

[0148] As can be seen from Table 2, the molded articles of Examples 2-1 to 2-4 had higher tensile moduli than the molded article of Comparative Example 2-1. Other physical properties were roughly equivalent between the two. This suggests that kneading a terminal-modified vinyl polymer having amino groups at both ends increases the tensile modulus of the polymer (i.e., improves the strength of the molded article). In particular, it suggests that the strength of the polymer is improved without deteriorating other physical properties.

[0149] Examples 3-1 to 3-3 Resin compositions were prepared using nylon 6 (UBE Corporation) as component A and one of terminally modified vinyl polymers 1 to 3 as component B. The type of component B was varied to observe changes in physical properties. The specific procedures were as follows: 1. Components A and B listed in Table 3 were dry blended at room temperature. 2. The resulting mixture was heated and kneaded at 250°C and 100 rpm. A 25 mm twin-screw extruder (Technovel Corporation) was used for kneading. 3. The heated and kneaded resin composition was stretched into strands and cut into approximately 3 mm pieces using a pelletizer. 4. The resulting pellets were injection molded using a 100 ton injection molding machine (SI-100IV, Toyo Machinery & Metal Co., Ltd.). This resulted in ISO Type A1 dumbbell test specimens.

[0150] Comparative Example 3-1 A molded product was obtained in the same manner as in Example 3, except that component B was not added.

[0151] [Results] The results are shown in Table 3.

[0152] As can be seen from Table 3, the molded article of Example 3-1 had a higher deflection temperature under load and a lower melt viscosity than the molded article of Comparative Example 3-1. This suggests that by kneading a terminal-modified vinyl polymer having an amino group at one end, the deflection temperature under load of the polymer increases (i.e., the heat resistance of the molded article improves) and the melt viscosity of the polymer decreases (i.e., the moldability of the molten resin improves).

[0153] As can also be seen from Table 3, the molded articles of Examples 3-2 to 3-3 had higher Charpy impact strength and lower melt viscosity than the molded article of Comparative Example 3-1. This suggests that kneading a terminally modified vinyl polymer having amino groups at both ends increases the Charpy impact strength of the polymer (i.e., improves the impact resistance of the molded article) and decreases the melt viscosity of the polymer (i.e., improves the moldability of the molten resin).

[0154] The present invention can be used to modify polymers.

Claims

1. A resin composition obtained by melt-kneading the following components A and B: Component A: A polymer having a carbonyl group and / or a carboxyl group; 3. The resin composition according to claim 1, wherein the molecular terminal structure of the above component B is a structure represented by the following general formula (1): In formula (1), １ R is -O-, -O(CO)-, -NH-, -N(CH ３ )- or -N(CH ２ CH ３ )-; ２ R ３ and R ４ are each independently a single bond or a divalent or trivalent group having 1 to 8 carbon atoms, and may have a hetero atom; ５ R ３ and R ４ are each independently hydrogen, a methyl group or an ethyl group; ５ n is 1 or 2; when n is 2, the structures of two R ３ 's, two R ４ 's and two R ５ 's may be the same or different; when there are two or more terminal structures represented by the general formula (1), the terminal structures may be the same or different from each other.

4. R ２ and R ３ The resin composition according to claim 3, wherein R and R are each independently a divalent or trivalent alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, aryl or heteroaryl.

5. R ２ has 1 to 6 carbon atoms, and R ３ has 0 to 2 carbon atoms, and R ４ and R ５ are both hydrogen, the resin composition according to claim 3. Component B: A terminal-modified vinyl-based polymer having one or more amino groups at its molecular terminals.

2. The resin composition according to claim 1, wherein the above component A is one or more selected from polyamide, polyester, polyimide, and polycarbonate.

6. The resin composition according to claim 1, wherein the above component B is a linear polymer, and the linear polymer has one or more amino groups at one or both of its terminals.

7. The resin composition according to claim 1, wherein the main chain of the above component B is mainly composed of one or more selected from the group consisting of poly(meth)acrylate, polystyrene, and polyisobutylene.

8. The resin composition according to claim 1, wherein when measured by size exclusion chromatography, the polystyrene-equivalent number average molecular weight of the above component B is 500 to 600,000, and the molecular weight distribution is 1.8 or less.

9. A method for producing a resin composition, comprising a step of melt-kneading the following components A and B: Component A: A polymer having a carbonyl group and / or a carboxyl group; Component B: A terminal-modified vinyl-based polymer having one or more amino groups at its molecular terminals.

10. The production method according to claim 9, wherein the temperature of the above melt-kneading is 180°C or higher.

11. The method for producing a resin composition according to claim 9, wherein the above component A is one or more selected from polyamide, polyester, polyimide, and polycarbonate.

12. A method for modifying a polymer, comprising a step of melt-kneading the following components A and B: Component A: A polymer having a carbonyl group and / or a carboxyl group; Component B: A terminal-modified vinyl-based polymer having one or more amino groups at its molecular terminals.

13. The method according to claim 12, wherein the temperature of the above melt-kneading is 180°C or higher.

14. The method according to claim 12, wherein the above component A is one or more selected from polyamide, polyester, polyimide, and polycarbonate.

15. A resin composition containing the following components A and B: Component A: A polymer having a carbonyl group and / or a carboxyl group; Component B: A terminal-modified vinyl-based polymer having one or more amino groups at its molecular terminals.

Images