resin composition

Abstract

The present invention provides a resin composition comprising a nitrogen atom-containing thermoplastic resin and a polymer, wherein the polymer has high heat meltability and excellent hygroscopic properties. [Solution] A resin composition comprising an N-vinyllactam polymer and a nitrogen atom-containing thermoplastic resin, wherein the N-vinyllactam polymer has structural units (a) derived from an N-vinyllactam monomer (A) and structural units (b) derived from an acid (salt) group-containing monomer (B), and the content ratio of structural units (a) is 50% by mass or more and less than 100% by mass, relative to 100% by mass of all structural units.

Description

[Technical Field]

[0001] This invention relates to a resin composition. More specifically, it relates to a resin composition useful for textile products and the like. [Background technology]

[0002] Thermoplastic resins containing nitrogen atoms, such as polyamides and polyurethanes, possess excellent physical and chemical properties, including mechanical properties, dimensional stability, elasticity, and chemical resistance, and are therefore widely used in molded products such as fibers and films. Furthermore, in recent years, various technologies have been developed to improve the physical properties of resins or impart functionality by adding polymers and other materials to them. Regarding techniques for improving the moldability of resins, for example, Patent Document 1 discloses a polyamide resin composition comprising a polyamide, an N-vinyllactam polymer, and a monocarboxylic acid (salt). [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2015-93890 [Overview of the project] [Problems that the invention aims to solve]

[0004] As mentioned above, Patent Document 1 describes a technique for adding an N-vinyllactam polymer to a polyamide resin, but it was insufficient in terms of imparting hygroscopic properties. Furthermore, when imparting functionality using polymers, it is also necessary that the polymer is sufficiently heated and melted within the resin.

[0005] This invention has been made in view of the above-mentioned circumstances, and aims to provide a resin composition comprising a nitrogen atom-containing thermoplastic resin and a polymer, wherein the polymer has high heat meltability and excellent hygroscopic properties. [Means for solving the problem]

[0006] The inventors of the present invention have investigated various techniques for imparting hygroscopic properties to nitrogen atom-containing thermoplastic resins using polymers. They discovered that an N-vinyllactam polymer having structural units derived from N-vinyllactam monomers and structural units derived from acid (salt) group-containing monomers in a predetermined ratio exhibits excellent heat meltability in nitrogen atom-containing thermoplastic resins, and that mixing it with the resin improves hygroscopic properties. This led them to the present invention, as they realized that it could successfully solve the above problem.

[0007] The present invention includes the following resin compositions, etc. [1] A resin composition comprising an N-vinyllactam polymer and a nitrogen atom-containing thermoplastic resin, wherein the N-vinyllactam polymer has structural units (a) derived from an N-vinyllactam monomer (A) and structural units (b) derived from an acid (salt) group-containing monomer (B), and the content of structural units (a) is 50% by mass or more and less than 100% by mass, based on 100% by mass of all structural units. [2] The resin composition according to [1] above, wherein the structural unit (b) includes a structural unit (b1) derived from a salt (B1) of an acid (salt) group-containing monomer, and the content of the structural unit (b1) is 15% by mass or less with respect to 100% by mass of all structural units. [3] The resin composition according to [1] or [2] above, wherein the above acid (salt) group-containing monomer (B) is an unsaturated carboxylic acid monomer and / or an unsaturated sulfonic acid monomer. [4] The resin composition according to any one of [1] to [3] above, wherein the N-vinyl lactam polymer has substituents containing a phosphorus atom in the main chain and / or alkoxy groups at the ends of the main chain. [5] The resin composition according to any one of [1] to [4] above, wherein the nitrogen atom-containing thermoplastic resin is a resin having at least one selected from the group consisting of amide bonds, cyano groups, and urethane bonds. [6] The resin composition according to any one of [1] to [5] above, wherein the nitrogen atom-containing thermoplastic resin is at least one selected from the group consisting of polyamide, AS resin, ABS resin, and urethane resin. [7] The resin composition according to any one of [1] to [6] above, wherein the content of the nitrogen atom-containing thermoplastic resin is 70 to 99.5% by mass with respect to 100% by mass of the resin composition. [8] A hygroscopic or hydrophilic agent for a nitrogen atom-containing thermoplastic resin containing an N-vinyllactam polymer, wherein the N-vinyllactam polymer has structural units (a) derived from an N-vinyllactam monomer (A) and structural units (b) derived from an acid (salt) group-containing monomer (B), and the content of structural units (a) is 50% by mass or more and less than 100% by mass, based on 100% by mass of all structural units. [Effects of the Invention]

[0008] The resin composition of the present invention has the above-described structure, and because the polymer has high heat meltability and excellent hygroscopicity, it can be suitably used in textile products such as clothing. [Modes for carrying out the invention]

[0009] Preferred embodiments of the present invention will be described below in detail, but the present invention is not limited to the following descriptions and can be modified and applied as appropriate without changing the gist of the present invention. Furthermore, embodiments combining two or more of the individual preferred embodiments of the present invention described below also constitute preferred embodiments of the present invention.

[0010] [Resin composition] The resin composition of the present invention comprises an N-vinyllactam polymer having structural units (a) derived from an N-vinyllactam monomer (A) and structural units (b) derived from an acid (salt) group-containing monomer (B), wherein the content of structural unit (a) is 50% by mass or more and less than 100% by mass relative to 100% by mass of all structural units, and a nitrogen atom-containing thermoplastic resin. The above N-vinyl lactam polymer has structural unit (b) in a ratio of 50% by mass or less per 100% by mass of all structural units, and as a result, it can exhibit excellent heat meltability in nitrogen atom-containing thermoplastic resins and efficiently impart hygroscopic properties to the resin. Since the above N-vinyl lactam-based polymer is excellent in heat fusibility in the resin, the resin composition of the present invention can sufficiently suppress filter clogging and molding defects caused by the unmelted N-vinyl lactam-based polymer.

[0011] The content ratio of the nitrogen atom-containing thermoplastic resin in the above resin composition is not particularly limited, but is preferably 70 to 99.5% by mass with respect to 100% by mass of the resin composition. More preferably, it is 75 to 99.0% by mass, still more preferably 80 to 98.5% by mass, and particularly preferably 85 to 98.0% by mass.

[0012] The content ratio of the N-vinyl lactam-based polymer in the above resin composition is not particularly limited, but is preferably 0.5 to 30% by mass with respect to 100% by mass of the resin composition. Thereby, hygroscopicity can be more sufficiently imparted to the nitrogen atom-containing thermoplastic resin. The content ratio of the N-vinyl lactam-based polymer is more preferably 1.0 to 25% by mass, still more preferably 1.5 to 20% by mass, and particularly preferably 2.0 to 15% by mass.

[0013] [[ID=II]] The above resin composition may contain other components other than the nitrogen atom-containing thermoplastic resin and the N-vinyl lactam-based polymer. The content ratio of the other components is not particularly limited, but is preferably 0 to 10% by mass with respect to 100% by mass of the resin composition. More preferably, it is 0 to 7% by mass, still more preferably 0 to 5% by mass, and particularly preferably 0 to 3% by mass.

[0014] Hereinafter, the essential components and optional components contained in the resin composition of the present invention will be further described.

[0015] <N-vinyl lactam-based polymer> The above N-vinyl lactam-based polymer has a structural unit (a) derived from an N-vinyl lactam-based monomer (A) and a structural unit (b) derived from an acid (salt) group-containing monomer (B), and the content ratio of the structural unit (a) is not particularly limited as long as it is 50% by mass or more and less than 100% by mass with respect to 100% by mass of all structural units. The content ratio of the above structural unit (a) is preferably 60 to 99.5% by mass, more preferably 65 to 99.0% by mass, still more preferably 70 to 98.5% by mass, and particularly preferably 80 to 98% by mass. When the content ratio of the above structural unit (a) is within the above range, the dispersibility of the N-vinyl lactam-based polymer in the resin composition can be further improved, and hydrophilicity can be efficiently imparted.

[0016] The content ratio of the above structural unit (b) in the above N-vinyl lactam-based polymer may be greater than 0% and 50% or less based on 100% by mass of all structural units, preferably 0.5 to 40% by mass. More preferably 1 to 35% by mass, still more preferably 1.5 to 30% by mass, and particularly preferably 2 to 20% by mass.

[0017] The above N-vinyl lactam-based polymer preferably has a structural unit (b1) derived from a salt (B1) of an acid (salt) group-containing monomer. That is, the form in which the above structural unit (b) contains the structural unit (b1) derived from the salt (B1) of the acid (salt) group-containing monomer is one of the preferred embodiments of the present invention. The content ratio of the above structural unit (b1) in the above N-vinyl lactam-based polymer is not particularly limited, but it is preferably greater than 0% and 15% or less based on 100% by mass of all structural units. More preferably 1 to 13% by mass, still more preferably 2 to 11% by mass, and particularly preferably 3 to 10% by mass. When the content ratio of (b1) is within the above range, there is a tendency to be particularly excellent in heat melting properties.

[0018] The above N-vinyl lactam-based polymer may have a structural unit (b1) derived from a salt (B) of an acid (salt) group-containing monomer and a structural unit (b2) derived from an acid-type acid group-containing monomer (B2). From the viewpoints of heat melting properties and imparting hygroscopicity, such a form is also one of the preferred embodiments of the present invention.

[0019] In the above N-vinyl lactam polymer, when the content of structural unit (b1) is greater than 0% by mass and 15% by mass or less relative to 100% by mass of all structural units, it is preferable that the proportion of structural unit (b2) is less than 50% by mass. More preferably, the proportion of structural unit (b2) is 0 to 45% by mass, and even more preferably 0 to 40% by mass.

[0020] The above N-vinyllactam polymer may have structural units (e) derived from N-vinyllactam monomers (A) and other monomers (E) other than acid (salt) group-containing monomers (B). The content of the above structural unit (e) in the above N-vinyl lactam polymer is not particularly limited, but is preferably 0 to 10% by mass relative to 100% by mass of the total structural units. More preferably 0 to 5% by mass, even more preferably 0 to 3% by mass, particularly preferably 0 to 1% by mass, and most preferably 0% by mass.

[0021] The above N-vinyl lactam polymer preferably has substituents containing a phosphorus atom (phosphorus atom-containing group) and / or an alkoxy group. This further improves the heat resistance of the resin composition. The above N-vinyl lactam polymer, by having a phosphorus atom-containing group or an alkoxy group within its molecule, can suppress the decomposition of the polymer when heated, thereby further improving the heat resistance of the resin composition. The above N-vinyl lactam polymer is more preferably characterized by a substituent containing a phosphorus atom in the main chain and / or an alkoxy group at the end of the main chain. By polymerizing monomer components in the presence of a chain transfer agent containing a phosphorus atom and / or an alcohol, a phosphorus atom-containing group and / or an alkoxy group at the end of the main chain of the polymer can be introduced. Analysis of phosphorus atom-containing groups in N-vinyl lactam polymers is, for example, 31 This can be done by P-NMR measurement, etc.

[0022] The phosphorus atom-containing group described above is not particularly limited as long as it contains a phosphorus atom, but it is preferably a reducing group. Examples of phosphorus atom-containing groups that have reducing properties include hypophosphorous acid (salt) groups and phosphite (salt) groups. A hypophosphorous acid (salt) group is more preferable. Note that the above-mentioned hypophosphorous(salt) group means a hypophosphorous group or its salt, and the above-mentioned phosphorous(salt) group means a phosphorous group or its salt.

[0023] When the above N-vinyllactam polymer has a phosphorus atom-containing group, the phosphorus atom content in the polymer is preferably 0.1 to 2% by mass, based on sodium hypophosphite, per 100% by mass of the N-vinyllactam polymer. More preferably, it is 0.2 to 1.8% by mass, and even more preferably, 0.3 to 1.6% by mass.

[0024] The alkoxy group mentioned above is not particularly limited and may be any group derived from an alcohol, but is preferably a group derived from a secondary alcohol. The above secondary alcohol is not particularly limited, but secondary alcohols having 3 to 30 carbon atoms, such as 2-propanol (isopropyl alcohol), 2-butanol, 2-pentanol, 3-pentanol, 2-hexanol, 3-hexanol, 2-heptanol, 3-heptanol, 2-octanol, 3-octanol, and glycerin, are preferred. More preferably, it is 2-propanol.

[0025] The above N-vinyl lactam polymer preferably has a weight-average molecular weight of 1,000 to 100,000. More preferably, it is 3,000 to 70,000, even more preferably 5,000 to 50,000, particularly preferably 8,000 to 30,000, and most preferably 9,000 to 28,000. By setting the weight-average molecular weight to 100,000 or less, dispersibility can be further improved, and hygroscopic properties can be efficiently imparted. Furthermore, by setting the weight-average molecular weight to 1,000 or more, water resistance can be improved. The weight-average molecular weight of the N-vinyl lactam polymer can be measured by the method described in the examples.

[0026] ((N-Vinyl lactam monomer (A)) The above N-vinyl lactam monomer (A) is not particularly limited as long as it is a monomer having an N-vinyl lactam structure, but the following formula (1);

[0027] [Chemical formula]

[0028] (In the formula, R 1 , R 2 , R 3 , R 4 are the same or different and each represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may have a substituent. m represents an integer of 0 to 4. n represents an integer of 1 to 3.) It is preferably a structure represented by The number of carbon atoms of the alkyl group in the above R 1 ~R 4 is preferably 1 to 6, more preferably 1 to 4. The alkyl group is more preferably a methyl group or an ethyl group, and particularly preferably a methyl group. The substituents in the above R 1 ~R 4 are not particularly limited, but examples include ethylenically unsaturated hydrocarbon groups; carboxyl groups, sulfonic acid groups and their esters and salts; amino groups, hydroxyl groups and the like. R 1 ~R 3 is preferably a hydrogen atom. R 4 is preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom. m is preferably an integer of 0 to 2, more preferably an integer of 0 to 1, and most preferably 0. n is preferably 1 or 2, more preferably 1.

[0029] Examples of compounds represented by formula (1) above include N-vinylpyrrolidone, N-vinyl-5-methylpyrrolidone, N-vinylpiperidone, N-vinylcaprolactam, and 1-(2-propenyl)-2-pyrrolidone, and one or more of these can be used. As the N-vinyllactam, an unsaturated monomer having a pyrrolidone ring is preferred. More preferably, it is N-vinylpyrrolidone.

[0030] (Acid group-containing monomer (B)) The above-mentioned acid (salt) group-containing monomer (B) may be any compound having an acid group or a salt group and an ethylenically unsaturated hydrocarbon group. Examples of the above-mentioned acid groups include carboxyl groups, carboxylic acid anhydride groups, sulfonic acid groups, phosphoric acid groups, and phenolic hydroxyl groups. Among these, carboxyl groups, carboxylic acid anhydride groups, and sulfonic acid groups are preferred, more preferably carboxyl groups and sulfonic acid groups, and even more preferably carboxyl groups. The above acid group may be in acid form or salt form, but preferably, the acid (salt) group-containing monomer (B) contains a salt (B1) of the acid (salt) group-containing monomer.

[0031] The salts mentioned above are not particularly limited, but examples include metal salts, ammonium salts, and organic amine salts, with metal salts being preferred. Examples of metal salts include alkali metal salts such as lithium salts, sodium salts, and potassium salts; alkaline earth metal salts such as calcium salts and magnesium salts; and transition metal salts. Among these, alkali metal salts are preferred, and sodium salts are more preferred.

[0032] Specifically, the above acid (salt) group-containing monomer (B) includes unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, tigric acid, 3-methylcrotonic acid, 2-methyl-2-pentenoic acid, cinnamic acid, vinylbenzoic acid and their salts; unsaturated dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid and their salts; 3-(meth)allyloxy-2-hydroxypropanesulfonic acid, 2-(meth)allyloxyethylenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, p-styrenesulfonic acid, α-methyl-p-styrenesulfonic acid, vinylsulfonic acid, Examples include vinylsulfamic acid, (meth)allylsulfonic acid, isoprenesulfonic acid, 4-(allyloxy)benzenesulfonic acid, 1-methyl-2-propene-1-sulfonic acid, 1,1-dimethyl-2-propene-1-sulfonic acid, 3-butene-1-sulfonic acid, 1-butene-3-sulfonic acid, 2-acrylamido-1-methylpropanesulfonic acid, 2-acrylamidopropanesulfonic acid, 2-acrylamido-n-butanesulfonic acid, 2-acrylamido-2-phenylpropanesulfonic acid, 2-(meth)acryloyloxy)ethanesulfonic acid, and unsaturated sulfonic acids such as salts thereof.

[0033] The above acid(salt) group-containing monomer (B) is preferably an unsaturated monocarboxylic acid, more preferably a (meth)acrylic acid(salt), even more preferably a (meth)acrylic acid salt, and particularly preferably sodium (meth)acrylate. A form in which the salt (B1) of the acid (salt) group-containing monomer is sodium (meth)acrylate is one of the preferred embodiments of the present invention.

[0034] (Other monomers) N-vinyllactam polymers may have structural units (e) derived from N-vinyllactam monomers (A) and other monomers (E) other than acid (salt) group-containing monomers (B). Other monomers (E) can be copolymerized with N-vinyl lactam monomers and acid (salt) group-containing monomers (B), and are not particularly limited as long as they do not have a lactam structure or acid (salt) group and have an ethylenically unsaturated hydrocarbon group, but include, for example, (meth)acrylic acid esters such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and 2-methoxyethyl (meth)acrylate; and N-monomethyl (meth)acrylamide. Examples include N-substituted (meth)acrylamides such as N-monoethyl(meth)acrylamide and N,N-dimethyl(meth)acrylamide; vinylaryl monomers such as styrene, indene, and vinylaniline; alkenes such as ethylene, propylene, butadiene, isobutylene, and octene; vinylamides such as vinylformamide, vinylacetamide, and vinyloxazolidone; vinylethylene carbonate and its derivatives; and vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, and butyl vinyl ether.

[0035] The method for producing the above-mentioned N-vinyl lactam polymer is not particularly limited and can be produced by polymerizing monomer components. The method for forming the structural unit (b1) in the above N-vinyl lactam polymer is not particularly limited. For example, it may be formed by polymerizing the salt (B1) of the above-mentioned acid (salt) group-containing monomer, or by polymerizing the acid-type acid group-containing monomer (B2) and then neutralizing it. The method for forming the structural unit (b2) in the above N-vinyl lactam polymer is not particularly limited. For example, it may be formed by polymerizing the above-mentioned acid-type acid group-containing monomer (B2), or it may be formed by polymerizing the salt (B1) of the acid (salt) group-containing monomer and then performing ion exchange. Specific examples of monomer components, preferred examples, and preferred proportions are as described above.

[0036] The method for initiating the polymerization of monomer components in the above polymerization process is not particularly limited, but examples include adding a polymerization initiator, irradiating with UV light, applying heat, or irradiating with light in the presence of a photoinitiator. In the polymerization process described above, it is preferable to use a polymerization initiator when carrying out polymerization. Examples of polymerization initiators include peroxides such as hydrogen peroxide and t-butyl hydroperoxide; persulfates such as sodium persulfate, potassium persulfate, and ammonium persulfate; 2,2'-azobis-2-amidinopropane dihydrochloride, dimethyl 2,2'-azobis(2-methylpropionate), 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2-methylpropionamidine) dihydrochloride, 2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine] hydrate, 2,2'-azobis[2-(2-imidazolin-2-yl)propane], 2,2'-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride, 2,2 Suitable polymerization initiators include azo compounds such as '-azobis[2-(2-imidazolin-2-yl)propane] disulfate hydrate, 2,2'-azobis(1-imino-1-pyrrolidino-2-methylpropane) dihydrochloride, 2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine] n hydrate, and 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide]; organic peroxides such as benzoyl peroxide, lauroyl peroxide, peracetic acid, di-t-butyl peroxide, and cumene hydroperoxide; and redox initiators that generate radicals by combining an oxidizing agent and a reducing agent, such as ascorbic acid and hydrogen peroxide, sodium sulfoxylate and t-butyl hydroperoxide, and persulfates and metal salts. Of these polymerization initiators, hydrogen peroxide, persulfates, and azo compounds are preferred, and azo compounds are more preferred. Among the azo compounds, 2,2'-azobis-2-amidinopropane dihydrochloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propane], 2,2'-azobis[2-(2-imidazolin-2-yl)propane] disulfate hydrate, 2,2'-azobis(2-methylpropionamidine) dihydrochloride, and 2,2'-azobis(2-methylbutyronitrile) are even more preferred. These polymerization initiators may be used alone or in the form of a mixture of two or more.

[0037] The amount of polymerization initiator used is preferably 0.1 g or more and 15 g or less per mole of monomer used. More preferably 0.1 g or more and 10 g or less, and even more preferably 0.1 g or more and 5 g or less.

[0038] In the polymerization process described above, a chain transfer agent may be used as needed. Examples of chain transfer agents include thiol-based chain transfer agents such as mercaptoethanol and mercaptopropionic acid; halides such as carbon tetrachloride and methylene chloride; secondary alcohols; hypophosphorous acid(salts) such as hypophosphorous acid and sodium hypophosphorous acid (including their hydrates); phosphorous acid(salts) such as phosphorous acid and sodium phosphite; sulfurous acid(salts) such as sodium sulfite; bisulfite(salts) such as sodium bisulfite; dithionic acid(salts) such as sodium dithionite; pyrosulfite(salts) such as potassium pyrosulfite; and hydrogen peroxide. The secondary alcohols mentioned above can be those described in the section on the introduction of alkoxy groups at the end of the main chain of N-vinyllactam polymers. Preferably, the above chain transfer agent is hypophosphorous acid (salt), bisulfite (salt), hydrogen peroxide, or mercaptopropionic acid, and more preferably hypophosphorous acid (salt). The above chain transfer agent may be used alone or in the form of a mixture of two or more. The amount of chain transfer agent used is preferably 0.1 g or more and 10 g or less per mole of monomer (total monomer) used, and more preferably 0.2 g or more and 5.0 g or less.

[0039] In the polymerization process described above, if a solvent is used, an aqueous solvent is preferred. Examples of aqueous solvents include water, methyl alcohol, ethyl alcohol, isopropyl alcohol (2-propanol), n-butyl alcohol, alcohols such as diethylene glycol, glycols, glycerin, polyethylene glycol, etc., with water being preferred. To improve the solubility of the monomer in the solvent, any suitable organic solvent may be added as needed, provided it does not adversely affect polymerization. Examples of such organic solvents include lower alcohols such as methanol, ethanol, and isopropyl alcohol; lower ketones such as acetone, methyl ethyl ketone, and diethyl ketone; ethers such as dimethyl ether, diethyl ether, and dioxane; and amides such as dimethylformaldehyde. One or more of these solvents may be used. The amount of solvent used is preferably 40 to 300% by mass per 100% by mass of monomer.

[0040] In the polymerization process described above, the polymerization temperature is not particularly limited, but is preferably 20°C to 110°C, more preferably 40°C to 105°C, and even more preferably 50°C to 100°C. Furthermore, the reaction time should be set appropriately according to the reaction temperature, the type (properties) and combination of monomer components, polymerization initiator, and solvent, as well as the amount used, so that the polymerization reaction is completed.

[0041] The pressure within the reaction system during the polymerization process described above may be at normal pressure, under reduced pressure, or under increased pressure. However, in terms of the molecular weight of the resulting polymer, it is preferable to carry out the process at normal pressure or under increased pressure with the reaction system sealed. Furthermore, in terms of equipment such as pressurizing and depressurizing devices, pressure-resistant reaction vessels, and piping, it is preferable to carry out the process at normal pressure. The atmosphere within the reaction system may be an air atmosphere, or it may be an inert atmosphere. For example, the system may be purged with an inert gas such as nitrogen before the start of polymerization.

[0042] The above polymer production method preferably includes a step of maturing the polymer after the polymerization reaction. By performing the maturation step, the amount of residual monomer can be reduced. The temperature in the above maturation step is not particularly limited, but is preferably 50 to 100°C. The maturation time in the above maturation step is not particularly limited, but is preferably 10 minutes to 5 hours. More preferably 20 minutes to 3 hours.

[0043] The above polymer production method may include steps other than the polymerization step and the maturation step. Examples of other steps include a pH adjustment step, a deactivation step for polymerization initiators and chain transfer agents, a dilution step, a drying step, a concentration step, and a purification step.

[0044] <Nitrogen atom-containing thermoplastic resin> The above-mentioned nitrogen atom-containing thermoplastic resin can be any thermoplastic resin having nitrogen atoms in its molecule, which results in excellent compatibility with N-vinyl lactam polymers.

[0045] The above-mentioned nitrogen atom-containing thermoplastic resin is preferably a resin having at least one selected from the group consisting of amide bonds, cyano groups, and urethane bonds. More preferably, it is a resin having amide bonds (polyamide).

[0046] The resins having the above-mentioned amide bond are not particularly limited, but examples include polymers obtained by (co)polycondensation reactions of lactams having 6 to 20 carbon atoms, such as nylon 6, nylon 11, and nylon 12; polymers obtained by copolymerization reactions of diamines having 4 to 20 carbon atoms and dicarboxylic acids, dicarboxylic acid esters, dicarboxylic acid chlorides, etc., having 6 to 20 carbon atoms, such as nylon 66, nylon 46, and nylon 610; and aromatic polyamides (aramids) such as polyphenylene terephthalamide and polymetaphenylene isophthalamide.

[0047] The thermoplastic resin having the cyano group is not particularly limited, but examples include acrylonitrile-styrene resin (AS resin), acrylonitrile-butadiene-styrene resin (ABS resin), poly(meth)acrylonitrile, acrylonitrile-ethylenepropylene-styrene copolymer (AES resin), acrylonitrile-methyl methacrylate copolymer (AMMA), poly(acrylonitrile copolymer), nitrile rubber (NBR), and cyanoester resin. Among these, AS resin and ABS resin are preferred.

[0048] The thermoplastic resin having the above-mentioned urethane bond is not particularly limited and can be obtained, for example, by the reaction of a polyol with an isocyanate such as diisocyanate.

[0049] Examples of the above-mentioned polyols include polyester polyols, polyether polyols, polycarbonate polyols, acrylic polyols, polyurethane polyols, and aromatic polyols (phthalic acid polyols). Specifically, examples include those based on ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, triethylene glycol, etc. These can be used individually or in combination.

[0050] Examples of the above-mentioned isocyanates include diisocyanate compounds such as aromatic diisocyanates, aliphatic diisocyanates, and alicyclic diisocyanates. Specifically, examples include 4,4'-diphenylmethane diisocyanate (MDI), tolylene diisocyanate (TDI), trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), and 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (IPDI).

[0051] A preferred embodiment of the present invention is in which the nitrogen atom-containing thermoplastic resin is at least one selected from the group consisting of polyamide, AS resin, ABS resin, and urethane resin. More preferably, the nitrogen atom-containing thermoplastic resin is a polyamide, and even more preferably a polymer obtained by a (co)polycondensation reaction of lactams having 6 to 20 carbon atoms, and particularly preferably nylon 6.

[0052] (Other ingredients) The resin composition of the present invention may contain other components besides the N-vinyl lactam polymer and nitrogen atom-containing thermoplastic resin. The above-mentioned other components are not particularly limited, but examples include antioxidants, plasticizers, flame retardants, stabilizers, reinforcing agents, near-infrared absorbers, antistatic agents, colorants, fillers, resin modifiers, etc.

[0053] [Method for producing resin compositions] The method for producing the resin composition of the present invention is not particularly limited, and it can be produced by mixing an N-vinyl lactam polymer with a nitrogen atom-containing thermoplastic resin. The present invention also relates to a method for producing a resin composition, which includes a step of mixing an N-vinyl lactam polymer with a nitrogen atom-containing thermoplastic resin.

[0054] The mixing method in the above mixing step is not particularly limited, but a method of kneading the N-vinyllactam polymer into the molten nitrogen atom-containing thermoplastic resin is preferred.

[0055] The temperature in the above mixing step is not particularly limited, but is preferably 150 to 300°C. More preferably 180 to 280°C, and even more preferably 200 to 270°C.

[0056] The mixing time in the above mixing step is not particularly limited, but is preferably 1 to 180 minutes. More preferably 2 to 120 minutes, and even more preferably 3 to 60 minutes.

[0057] The equipment used in the above mixing process is not particularly limited, but examples include mixers, kneaders, kneading extruders, twin-screw extruders, roll kneaders, and other kneading machines.

[0058] The atmosphere in the above mixing process is not particularly limited and may be an air atmosphere, but an inert atmosphere is preferred.

[0059] [Uses of resin compositions] The above-mentioned N-vinyl lactam polymer can impart sufficient hygroscopicity to nitrogen atom-containing thermoplastic resins. Therefore, the resin composition of the present invention can fully exhibit the various properties of nitrogen atom-containing thermoplastic resins, such as mechanical strength, abrasion resistance, flexibility, gloss, dyeability, dimensional stability, and texture, as well as hygroscopicity. The resin composition of the present invention can be suitably used in textile products and the like where hygroscopicity is required.

[0060] [Hygroscopic or hydrophilic agents] Since the above N-vinyllactam polymer can impart sufficient hygroscopicity to nitrogen atom-containing thermoplastic resins, the present invention relates to a hygroscopic or hydrophilic imparting agent for nitrogen atom-containing thermoplastic resins comprising an N-vinyllactam polymer, wherein the N-vinyllactam polymer has structural units (a) derived from an N-vinyllactam monomer (A) and structural units (b) derived from an acid (salt) group-containing monomer (B), and the content of structural unit (a) is 50% by mass or more and less than 100% by mass relative to 100% by mass of all structural units, and is also a hygroscopic or hydrophilic imparting agent. The preferred form of the N-vinyl lactam polymer in the above-mentioned hygroscopic or hydrophilic agent is the same as the N-vinyl lactam polymer in the resin composition of the present invention described above. [Examples]

[0061] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, "parts" means "parts by weight" and "%" means "mass%".

[0062] <Method for measuring weight-average molecular weight> Equipment: Waters Alliance System Detector: RI Column: Tosoh TSK-GEL ALPHA-M (2 pieces) Column temperature: 40℃ Flow rate: 0.6ml / min Calibration curve: TSKgel standard Poly(ethylene oxide) Eluent: A solution prepared by mixing acetonitrile and 0.2M sodium nitrate aqueous solution in a 1:5 ratio.

[0063] <Evaluation of heat meltability> 1.0 g of polymer was weighed into an aluminum cup and left to stand in a drying oven at 250°C for 1 hour under a nitrogen atmosphere. The state was then visually evaluated according to the following criteria. ○: Melts uniformly and well. ×: Unmelted portion exists, defective.

[0064] <Evaluation of hygroscopic properties> Three g of the polymer-containing polyamide resin composition was weighed into a weighing bottle and dried at 105°C for two hours. After measuring the weight of the dried resin composition (dry weight), it was left to stand in a constant temperature and humidity chamber at 30°C and 90% RH for seven days, and then its weight (weight after moisture absorption) was measured again. The moisture absorption rate (i) was calculated using the following formula.

[0065]

number

[0066] The moisture absorption rate (ii) of the polyamide resin composition without polymer kneading was calculated using the same method, and the Δ moisture absorption rate (%) of the polymer-containing polyamide resin composition was calculated using the following formula.

[0067]

number

[0068] <Example 1> Polymerization process: In a 2.5-liter stainless steel reaction vessel equipped with a reflux condenser, agitator (paddle blades), and thermometer, 439.2 g of deionized water and 2.5 g of sodium hypophosphate monohydrate (manufactured by Wako Pure Chemical Industries, Ltd., hereinafter referred to as "SHP·1H2O") were charged, and the mixture was stirred at 200 rpm under a nitrogen atmosphere and heated to 80°C. As an initiator aqueous solution, a solution was prepared by adding 74.9 g of deionized water to 8.3 g of 2,2'-azobis-2-amidinopropane dihydrochloride (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., hereinafter referred to as "V-50"). Nitrogen was introduced at a rate of 50 mL / min, and while maintaining the temperature at 80±2°C, 400 g of N-vinylpyrrolidone (manufactured by Nippon Shokubai Co., Ltd., hereinafter referred to as "NVP") and 56.9 g of 37% by weight sodium acrylate aqueous solution (hereinafter referred to as "37%SA") were added dropwise for 120 minutes each. In addition, 83.2 g of initiator aqueous solution was added dropwise for 130 minutes. After the addition was complete, the temperature was maintained at 80°C for 50 minutes to complete the polymerization reaction and obtain an aqueous solution of polymer (1). The weight-average molecular weight of the aqueous solution of polymer (1) is shown in Table 1. Drying and grinding process: The obtained aqueous solution of polymer (1) was dried under reduced pressure at a temperature of 90°C and a gauge pressure of -0.1 MPa. The resulting dried material was pulverized using a lab mill to obtain polymer (1) powder. The results of the evaluation of the heat meltability of polymer (1) are shown in Table 2. Preparation of polymer-containing polyamide resin compositions: 14.25 parts of nylon 6 (manufactured by Toray Industries, Inc., trade name Amiran CM1017, hereinafter referred to as "PA") as polyamide and 0.75 parts of the polymer (1) powder obtained in the above process were melt-kneaded at 250°C for 5 minutes under a nitrogen stream using a small kneader (X-plore, manufactured by Leo Lab Co., Ltd.). The resulting strands were pulverized to a length of approximately 1-2 mm to obtain the polymer (1)-containing polyamide resin composition of the present invention. The results of the hygroscopicity evaluation of the obtained polymer (1)-containing polyamide resin composition are shown in Table 2.

[0069] <Example 2> Polymerization process: In a 2.5-liter stainless steel reaction vessel equipped with a reflux condenser, agitator (paddle blades), and thermometer, 440.4 g of deionized water and 2.5 g of SHP·1H2O were charged, and the mixture was stirred at 200 rpm under a nitrogen stream to raise the temperature to 80°C. As an initiator aqueous solution, a solution was prepared by adding 79.0 g of deionized water to 8.8 g of V-50. Nitrogen was introduced at a rate of 50 mL / min, and while maintaining the temperature at 80±2°C, 400 g of NVP and 120.1 g of 37% SA were added dropwise continuously for 120 minutes each. In addition, 87.8 g of the initiator aqueous solution was added dropwise continuously for 130 minutes. After the addition was complete, the temperature was maintained at 80°C for 50 minutes to complete the polymerization reaction. Subsequently, 86.1 g of 10 wt% hydrochloric acid aqueous solution was added and stirred to obtain an aqueous solution of polymer (2). The weight-average molecular weight of the aqueous solution of polymer (2) is shown in Table 1. The drying and grinding processes were carried out in the same manner as in Example 1, and the heat meltability and hygroscopicity were evaluated. The results are shown in Table 2.

[0070] <Example 3> Polymerization process: In a 2.5-liter stainless steel reaction vessel equipped with a reflux condenser, agitator (paddle blades), and thermometer, 440.4 g of deionized water and 2.5 g of SHP·1H2O were charged, and the mixture was stirred at 200 rpm under a nitrogen stream to raise the temperature to 80°C. As an initiator aqueous solution, a solution was prepared by adding 63.5 g of deionized water to 7.1 g of V-50. Nitrogen was introduced at a rate of 50 mL / min, and while maintaining the temperature at 80±2°C, 250.0 g of NVP and 289.5 g of 37% SA were added dropwise continuously for 120 minutes each. In addition, 70.6 g of the initiator aqueous solution was added dropwise continuously for 130 minutes. After the addition was complete, the temperature was maintained at 80°C for 50 minutes to complete the polymerization reaction. Subsequently, 41.5 g of 10 wt% hydrochloric acid aqueous solution was added and stirred to obtain an aqueous solution of polymer (3). The weight-average molecular weight of the aqueous solution of polymer (3) is shown in Table 1. The drying and grinding processes were carried out in the same manner as in Example 1, and the heat meltability and hygroscopicity were evaluated. The results are shown in Table 2.

[0071] <Example 4> Polymerization process: In a 2.5-liter stainless steel reaction vessel equipped with a reflux condenser, agitator (paddle blades), and thermometer, 680.8 g of 2-propanol (manufactured by Wako Pure Chemical Industries, Ltd., hereinafter referred to as "IPA") and 105.8 g of NVP were charged and stirred at 200 rpm under a nitrogen stream until the temperature rose to the boiling point. As an initiator aqueous solution, a solution was prepared by adding 90.3 g of IPA to 10.0 g of 2,2'-azobis-(2-methylbutyronitrile) (manufactured by Wako Pure Chemical Industries, Ltd., hereinafter referred to as "V-59"). Nitrogen was introduced at a rate of 50 mL / min, and while maintaining the temperature at the boiling point, 247.0 g of NVP and 151.2 g of 100% by mass acrylic acid (manufactured by Nippon Shokubai, hereinafter referred to as "100% AA") were added dropwise, one at a time, for 120 minutes. Furthermore, 100.3 g of the initiator aqueous solution was added dropwise continuously for 130 minutes. After the addition was complete, the temperature was maintained at the boiling point for 50 minutes to complete the polymerization reaction. Then, 76.5 g of 10 wt% hydrochloric acid aqueous solution was added and stirred to obtain an aqueous solution of polymer (4). The weight-average molecular weight of the aqueous solution of polymer (4) is shown in Table 1. The drying and grinding processes were carried out in the same manner as in Example 1, and the heat meltability and hygroscopicity were evaluated. The results are shown in Table 2.

[0072] <Comparative Example 1> Polymerization process: In a 2.5-liter stainless steel reaction vessel equipped with a reflux condenser, agitator (paddle blades), and thermometer, 420.4 g of deionized water, 2.5 g of SHP·1H2O, and 1.5 g of 5 wt% sodium hydroxide aqueous solution were charged, and the mixture was stirred at 200 rpm under a nitrogen stream, raising the temperature to 90°C. As an initiator aqueous solution, a solution was prepared by adding 17.0 g of deionized water to 3.0 g of V-50. Nitrogen was introduced at 50 mL / min, and while maintaining the temperature at 90±2°C, 555.6 g of NVP aqueous solution (500 g of NVP with 55.6 g of deionized water) was continuously added dropwise for 360 minutes. In addition, 20.0 g of initiator aqueous solution was continuously added dropwise for 390 minutes. After the addition was complete, the temperature was maintained at 90°C for 30 minutes to complete the polymerization reaction, and an aqueous solution of comparative polymer (1) was obtained. Table 1 shows the weight-average molecular weight of the aqueous solution of the comparative polymer (1). The drying and grinding processes were carried out in the same manner as in Example 1, and the heat meltability and hygroscopicity were evaluated. The results are shown in Table 2.

[0073] <Comparative Example 2> Polymerization process: In a 2.5-liter stainless steel reaction vessel equipped with a reflux condenser, agitator (paddle blades), and thermometer, 352.7 g of deionized water and 3.0 g of SHP·1H2O were charged, and the mixture was stirred at 200 rpm under a nitrogen stream to raise the temperature to 80°C. As an initiator aqueous solution, a solution was prepared by adding 88.9 g of deionized water to 9.8 g of V-50. Nitrogen was introduced at a rate of 50 mL / min, and while maintaining the temperature at 80±2°C, 200.0 g of NVP and 810.8 g of 37% SA were added dropwise for 120 minutes each. Additionally, 98.7 g of the initiator aqueous solution was added dropwise for 130 minutes. After the addition was complete, the temperature was maintained at 80°C for 50 minutes to complete the polymerization reaction. Subsequently, 581.6 g of 10 wt% hydrochloric acid aqueous solution was added to obtain an aqueous solution of comparative polymer (2). Table 1 shows the weight-average molecular weight of the aqueous solution of the comparative polymer (2). The process from the drying and grinding stage onward was the same as in Example 1, but only the heat meltability was evaluated, and the results are shown in Table 2.

[0074] <Reference example 1> Preparation of polymer (1)-containing polyester resin composition: 14.25 parts of polyester (manufactured by Unitika Corporation, product name MA-2101M, hereinafter referred to as "PET") and 0.75 parts of polymer (1) powder obtained in Example 1 were melt-kneaded at 280°C for 5 minutes under a nitrogen stream using a small kneader (X-plore, manufactured by Leo Lab Co., Ltd.). The resulting strands were pulverized to a length of approximately 1-2 mm to obtain the polymer (1)-containing polyester resin composition of the present invention. The hygroscopicity of the obtained polymer (1)-containing polyester resin composition was evaluated, and the results are shown in Table 2. When calculating the Δ moisture absorption rate (%), the moisture absorption rate of the polyester resin composition without the polymer was measured and defined as moisture absorption rate (ii).

[0075] [Table 1]

[0076] [Table 2]

Claims

1. A resin composition comprising an N-vinyl lactam polymer and a nitrogen atom-containing thermoplastic resin, The N-vinyllactam polymer has structural units (a) derived from an N-vinyllactam monomer (A) and structural units (b) derived from an acid (salt) group-containing monomer (B), and the content of structural unit (a) is 50% by mass or more and less than 100% by mass, relative to 100% by mass of all structural units, in a resin composition.

2. The resin composition according to claim 1, wherein the structural unit (b) includes a structural unit (b1) derived from a salt (B1) of an acid (salt) group-containing monomer, and the content of the structural unit (b1) is 15% by mass or less with respect to 100% by mass of all structural units.

3. The resin composition according to claim 1 or 2, wherein the acid (salt) group-containing monomer (B) is an unsaturated carboxylic acid monomer and / or an unsaturated sulfonic acid monomer.

4. The resin composition according to claim 1 or 2, wherein the N-vinyl lactam polymer has substituents containing a phosphorus atom in the main chain and / or alkoxy groups at the ends of the main chain.

5. The resin composition according to claim 1 or 2, wherein the nitrogen atom-containing thermoplastic resin is a resin having at least one selected from the group consisting of amide bonds, cyano groups, and urethane bonds.

6. The resin composition according to claim 1 or 2, wherein the nitrogen atom-containing thermoplastic resin is at least one selected from the group consisting of polyamide, AS resin, ABS resin, and urethane resin.

7. The resin composition according to claim 1 or 2, wherein the content of the nitrogen atom-containing thermoplastic resin is 70 to 99.5% by mass with respect to 100% by mass of the resin composition.

8. A hygroscopic or hydrophilic agent for nitrogen atom-containing thermoplastic resins containing an N-vinyllactam polymer, The N-vinyllactam polymer has a structural unit (a) derived from an N-vinyllactam monomer (A) and a structural unit (b) derived from an acid (salt) group-containing monomer (B), and the content of structural unit (a) is 50% by mass or more and less than 100% by mass, relative to 100% by mass of all structural units, and is a hygroscopic or hydrophilic agent.

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