JP7088491B2 - Modified polyrotaxane and its production method and resin composition - Google Patents

Description

The present invention relates to a modified polyrotaxane having a modifying group derived from lactam, a method for producing the same, and a resin composition. Specifically, at least (A) a modified cyclodextrin having a modifying group derived from lactam, (B) a linear molecule penetrating the opening of the cyclodextrin in a skewered manner, and (C) the modified cyclodextrin are removed. A modified polyrotaxane having excellent compatibility with polyamide can be provided by having a structure consisting of a sealing group arranged so as not to be separated.

Polyamide resin has excellent mechanical and thermal properties such as rigidity and toughness, and has properties suitable as engineering plastics. Therefore, mainly for injection molding, various electric / electronic parts, mechanical parts, and Widely used in applications such as automobile parts. As a method for further improving the toughness of the polyamide resin, a technique of blending an olefin-based elastomer or blending a core-shell type compound in which a rubber-like core layer is covered with a glass-like resin shell layer is known.

As a technique for blending an olefin-based elastomer, for example, a continuous phase made of a polyamide resin and a particulate dispersed phase made of a polyolefin modified with α, β-unsaturated carboxylic acid dispersed in the continuous phase are used. A polyamide-based resin composition (see, for example, Patent Document 1) has been proposed.

As a technique for blending a core-shell type compound, for example, a multilayer structure weight having a polyalkyl (meth) acrylate as a core and a first layer made of polyorganosiloxane and a second layer made of polyalkyl (meth) acrylate on the core. An impact-resistant thermoplastic resin composition composed of a composite rubber-based graft copolymer obtained by graft-polymerizing a vinyl-based monomer on the coalesced particles and a thermoplastic resin (see, for example, Patent Document 2) has been proposed. There is. In addition, as a technique for blending a core-shell type compound, a dicarboxylic acid unit containing a terephthalic acid unit and a diamine unit containing a 1,9-nonanediamine unit and / or a 2-methyl-1,8-octanediamine unit are used. A polyamide resin composition comprising the above-mentioned polyamide resin and resin fine particles having a core-shell structure (see, for example, Patent Document 3) has been proposed. When these resin compositions are applied to various applications, particularly automobile structural materials, it is necessary to achieve both rigidity and rigidity. The resin compositions disclosed in Patent Documents 1 to 3 have a problem that the rigidity is lowered, although the impact resistance and the toughness are improved by blending the olefin elastomer and the core-shell type compound.

On the other hand, as a method for improving impact strength and toughness, a resin composition obtained by reacting a polyolefin modified with an unsaturated carboxylic acid anhydride with a polyrotaxane having a functional group (see, for example, Patent Document 4) or A polylactic acid-based resin composition containing a polyrotaxane and a polylactic acid resin in which an opening of a cyclic molecule having a graft chain made of polylactic acid is encapsulated by a linear molecule (see, for example, Patent Document 5) has been proposed. There is.

Japanese Unexamined Patent Publication No. 9-31325 Japanese Unexamined Patent Publication No. 5-339462 Japanese Unexamined Patent Publication No. 2000-186204 Japanese Unexamined Patent Publication No. 2013-209460 Japanese Unexamined Patent Publication No. 2014-84414 International Publication No. 2007/026578

As disclosed in Patent Documents 4 and 5, it is known that the impact strength and toughness of polyolefins and polylactic acids are improved by using polyrotaxane. However, the resin composition described in Patent Document 4 has a problem of insufficient rigidity. The resin composition described in Patent Document 5 has a problem that the toughness of polylactic acid is improved, but the toughness is still insufficient. Further, the polyrotaxanes disclosed in Patent Documents 4 and 5 have low compatibility with polyamides, and it has been difficult to apply these polyrotaxanes to the modification of polyamides.

The present invention has been made in view of the above, and an object of the present invention is to provide a modified polyrotaxane having excellent compatibility with polyamide, a method for producing the same, and a resin composition.

In order to solve the above-mentioned problems and achieve the above-mentioned object, the modified polyrotaxane according to the present invention has (A) a modified cyclodextrin having a modifying group derived from lactam and (B) a cyclodextrin opening in a skewered manner. It is characterized by consisting of at least a penetrating linear molecule and (C) a blocking group arranged so that the modified cyclodextrin does not escape.

The modified polyrotaxane according to one aspect of the present invention is characterized in that, in the above invention, the modified cyclodextrin having a modifying group derived from lactam has a structure represented by the general formula (I).
-NH- (CO- (CH ₂ ) _m -NH) _n -H ... (I)
(M: an integer of 2 to 15 indicating the number of repetitions, n: an integer of 1 to 100 indicating the degree of polymerization)

The modified polyrotaxane according to one aspect of the present invention is characterized in that, in the above invention, the modified cyclodextrin having a modifying group derived from lactam has a structure represented by the general formula (II).
-NH-R-NH- (CO- (CH ₂ ) _m -NH) _n -H ... (II)
(R: hydrocarbon group, m: an integer of 2 to 15 indicating the number of repetitions, n: an integer of 1 to 100 indicating the degree of polymerization)

The modified polyrotaxane according to one aspect of the present invention is characterized in that, in the above invention, the modifying group derived from lactam is a modifying group derived from ε-caprolactam.

The modified polyrotaxane according to one aspect of the present invention is characterized in that, in the above invention, the linear molecule is polyethylene glycol.

The resin composition according to the present invention is characterized by blending at least a polyamide and the modified polyrotaxane according to the above invention.

The method for producing a modified polyrotaxane according to the present invention comprises at least a polyrotaxane consisting of cyclodextrin, a linear molecule penetrating the opening of cyclodextrin in a skewered manner, and a blocking group arranged so that cyclodextrin does not escape. It is characterized in that (a) a step of converting a hydroxyl group on cyclodextrin into a functional group capable of reacting with rotaxane and (b) a step of reacting a functional group on cyclodextrin with lactam are performed in order.

The method for producing a modified polyrotaxane according to one aspect of the present invention is characterized in that, in the above invention, the functional group capable of reacting with the lactam is an amino group.

The method for producing a modified polyrotaxane according to one aspect of the present invention is characterized in that, in the above invention, the lactam is ε-caprolactam.

According to the present invention, it is possible to obtain a modified polyrotaxane having excellent compatibility with polyamide. Further, the resin composition containing the polyamide and the modified polyrotaxane according to the present invention makes it possible to obtain a molded product having an excellent balance between rigidity and toughness.

Hereinafter, embodiments of the present invention will be described. The present invention is not limited to the embodiments described below.

(1) Polyrotaxane The polyrotaxane in the present invention is composed of a linear molecule and a plurality of cyclodextrins, has a structure in which the linear molecule penetrates through the openings of the plurality of cyclodextrins, and both ends of the linear molecule. Has a bulky blocking group to prevent cyclodextrin from desorbing from the linear molecule. In polyrotaxane, cyclodextrin can move freely on the linear molecule, but has a structure that cannot escape from the linear molecule due to the blocking group. That is, the linear molecule and cyclodextrin have a structure that maintains its morphology by a mechanical bond rather than a chemical bond. Since such polyrotaxane has high motility of cyclodextrin, it has an effect of relieving stress from the outside and stress remaining inside.

The above-mentioned linear molecule is not particularly limited as long as it is a compound having a functional group that penetrates the opening of cyclodextrin and can react with a blocking group. Preferred linear molecules include polyalkylene glycols such as polyethylene glycol, polypropylene glycol and polytetramethylene glycol, polybutadiene diols, polyisoprene diols, polyisobutylene diols, poly (acrylonitrile-butadiene) diols, and hydride polybutadiene diols. , Polycarbonate diols, terminal hydroxyl group polyolefins such as polypropylene diols, polycaprolactone diols, polylactic acid, polyethylene adipates, polybutylene adipates, polyethylene terephthalates, polybutylene terephthalates and other polyesters, and terminal silanol-type polydimethylsiloxanes and other terminal functional polys. Terminal carboxyl groups such as siloxanes, terminal amino group polyethylene glycol, terminal amino group polypropylene glycol, terminal amino group polybutadiene, terminal amino group chain polymers, terminal carboxyl group polyethylene glycol, terminal carboxyl group polypropylene glycol, terminal carboxyl group polybutadiene, etc. Examples thereof include chain polymers and polyfunctional chain polymers having three or more functional groups in one molecule and having three or more functionalities. Of these, polyethylene glycol, terminal amino group polyethylene glycol, and terminal carboxyl group polyethylene glycol are more preferable, and terminal carboxyl group polyethylene glycol is particularly preferable, because polyrotaxane can be easily synthesized.

The molecular weight of the above-mentioned linear molecule is preferably 1000 to 500,000, more preferably 10,000 to 300,000, and even more preferably 10,000 to 100,000. When the molecular weight of the linear molecule is in the above range, the solubility of the polyrotaxane containing the modified cyclodextrin as a constituent is increased.

Further, in the present invention, the number of cyclodextrins (engagement amount) to be included in the linear molecule is preferably 0.01 to 0.6, and more preferably, assuming that the maximum inclusion amount is 1. It is 0.1 to 0.5, more preferably 0.2 to 0.4. When the number of cyclodextrins is in the above range, the mobility and solubility of cyclodextrins tend to be compatible with each other. The maximum inclusion amount of cyclodextrin is a theoretical value determined by the molecular chain length of the linear molecule and the cavity height of cyclodextrin.

The blocking group in the present invention may be any group as long as cyclodextrin is not desorbed from the linear molecule, and preferably a bulky group or an ionic group can be mentioned, and the bulky group is particularly bulky. It is preferably a group having a dextrin. Specific examples of such a blocking group include dinitrophenyl groups such as 2,4-dinitrophenyl group and 3,5-dinitrophenyl group, cyclodextrins, adamantans, trityl groups, fluoresceins and pyrenes. And their derivatives or variants can be mentioned.

The weight average molecular weight of the polyrotaxane in the present invention is preferably in the range of 100,000 or more and 1,000,000 or less. When the weight average molecular weight of polyrotaxane is in this range, the compatibility with polyamide tends to be improved. The weight average molecular weight of polyrotaxan here is gel permeation using 1,1,1,3,3,3-hexafluoroisopropanol as a solvent and Chromatography HFIP-806M (2 bottles) + HFIP-LG as a column. Refers to the value in terms of polymethylmethacrylate measured using chromatography.

The above-mentioned polyrotaxane is obtained by mixing cyclodextrin and a linear molecule, penetrating the opening of the cyclodextrin in a skewered manner with the linear molecule, and inclusion the cyclodextrin in the linear molecule to obtain pseudopolyrotaxane. It can be obtained by a step and a step of sealing both ends of the linear molecule of the pseudopolyrotaxane obtained in the previous step with a blocking group to prepare cyclodextrin so as not to escape from the skewed state.

(2) Modified Polyrotaxane The modified polyrotaxane of the present invention is a modified cyclodextrin in which the cyclodextrin in the above-mentioned polyrotaxane has a modifying group derived from lactam.

Here, the modified cyclodextrin having a lactam-derived modifying group may be any as long as it has a lactam-derived modifying group, and preferably has a structure represented by the following general formula (I), and is described below. Those having a structure represented by the general formula (II) are more preferable. From the viewpoint of ease of chemical synthesis, those having these structures can be preferably exemplified.
-NH- (CO- (CH ₂ ) _m -NH) _n -H ... (I)
-NH-R-NH- (CO- (CH ₂ ) _m -NH) _n -H ... (II)
Here, m in the general formulas (I) and (II) is an integer of 2 to 15 indicating the number of repetitions, and it can be preferably exemplified that m = 5 or 11, among which m = 5, that is, that is, It is particularly preferable that the structure is derived from ε-caprolactam. When the number of repetitions m in the general formulas (I) and (II) is such a preferable value, the compatibility between the modified polyrotaxane and the polyamide tends to be improved. Further, n in the general formulas (I) and (II) is a positive integer indicating the degree of polymerization, preferably n = 1 to 100, more preferably 1 to 50, and still more preferably 1 to 1. 20. When the degree of polymerization n is in these ranges, the synthesis of the modified polyrotaxane becomes easy, and the compatibility between the modified polyrotaxane and the polyamide tends to be improved. The degree of polymerization n here can be calculated from the proton ratio of cyclodextrin in the NMR structure analysis and the − (CH ₂ ) _m − group in the general formulas (I) and (II).

R in the general formula (II) is a hydrocarbon group, which is an alkylene group having 2 to 6 carbon atoms, and specific examples thereof include an ethylene group, a propylene group, a butylene group, a pentylene group and a hexylene group, and ethylene. A group and a butylene group are preferable, and an ethylene group is more preferable. The R in the general formula (II) may have a single structure or may be composed of two or more types of R.

Modified cyclodextrins having these lactam-derived modifying groups can be obtained by reacting a functional group on the cyclodextrin with lactam. The modifying group derived from lactam is preferably a polymer of lactam. Further, as the lactam, ε-caprolactam and ω-laurolactam are preferable, and ε-caprolactam is more preferable. Therefore, the modifying group derived from lactam is particularly preferably polycaprolactam, which is a polymer of ε-caprolactam. It is preferable that the modifying group derived from lactam is the above-mentioned modifying group because the compatibility between the modified polyrotaxane and the polyamide tends to be improved.

The functional group on cyclodextrin that reacts with lactam may be any functional group that reacts with lactam, but is preferably an amino group, a carboxyl group, or a hydroxyl group, and more preferably. Is an amino group. Since the functional group on the cyclodextrin is such a suitable functional group, the reactivity with lactam tends to be high.

The weight average molecular weight of the modified polyrotaxane according to the present invention is preferably in the range of 100,000 or more and 1,000,000 or less. When the weight average molecular weight of the modified polyrotaxane is in this range, the compatibility with polyamide tends to be improved. The weight average molecular weight of the modified polyrotaxan here is gel permi using 1,1,1,3,3,3-hexafluoroisopropanol as a solvent and Chromatography HFIP-806M (2 bottles) + HFIP-LG as a column. Refers to the value in terms of polymethylmethacrylate measured using ion chromatography.

The above-mentioned modified polyrotaxane can be used in the above-mentioned (1) polyrotaxane at least in the step of converting a hydroxyl group on cyclodextrin into a functional group capable of reacting with lactam (step (a)) and the following functional group on cyclodextrin. It is obtained by the step of reacting lactam (step (b)). The modified polyrotaxane according to the present invention can also be prepared by using (1) cyclodextrin having a functional group capable of reacting with lactam in advance when preparing the polyrotaxane. In this case, the above-mentioned step (a) can be omitted.

(3) Polyamide The polyamide according to the present invention contains amino acids, lactams, or residues of diamine and dicarboxylic acid as main constituents. Typical examples of the raw materials are amino acids such as 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid and paraaminomethylbenzoic acid, lactam such as ε-caprolactam and ω-laurolactam, tetramethylenediamine and penta. Methylenediamine, hexamethylenediamine, 2-methylpentamethylenediamine, nonamethylenediamine, decamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4- / 2,4,4-trimethylhexamethylenediamine, 5 -A aliphatic diamine such as methylnonamethylenediamine, aromatic diamine such as metaxylylenediamine and paraxylylenediamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 1- Amino-3-aminomethyl-3,5,5-trimethylcyclohexane, bis (4-aminocyclohexyl) methane, bis (3-methyl-4-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane , Bis (aminopropyl) piperazine, alicyclic diamines such as aminoethyl piperazine, aliphatic dicarboxylic acids such as adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, terephthalic acid, isophthalic acid, 2-chloroterephthalic acid. Aromatic dicarboxylic acids such as acids, 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodiumsulfoisophthalic acid, 2,6-naphthalenedicarboxylic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, 1,4-cyclohexane Examples thereof include alicyclic dicarboxylic acids such as dicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, and 1,3-cyclopentanedicarboxylic acid. In the present invention, two or more kinds of polyamide homopolymers or copolymers derived from these raw materials may be blended.

Specific examples of polyamide include polycaproamide (nylon 6), polyhexamethylene adipamide (nylon 66), polytetramethylene adipamide (nylon 46), polytetramethylene sebacamide (nylon 410), and the like. Polypentamethylene adipamide (nylon 56), polypentamethylene sebacamide (nylon 510), polyhexamethylene sebacamide (nylon 610), polyhexamethylene dodecamide (nylon 612), polydecamethylene adipamide (nylon 612) Nylon 106), Polydecamethylene sebacamide (Nylon 1010), Polydecamethylene dodecamide (Nylon 1012), Polyundecaneamide (Nylon 11), Polydodecaneamide (Nylon 12), Polycaproamide / Polyhexamethylene adipa Midcopolymer (nylon 6/66), polycaproamide / polyhexamethylene terephthalamide copolymer (nylon 6 / 6T), polyhexamethylene adipamide / polyhexamethylene terephthalamide copolymer (nylon 66 / 6T), polyhexamethylene hydrangea Pamide / polyhexamethylene isophthalamide copolymer (nylon 66 / 6I), polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer (nylon 6T / 6I), polyhexamethylene terephthalamide / polydodecaneamide copolymer (nylon 6T / 12) ), Polyhexamethylene adipamide / Polyhexamethylene terephthalamide / Polyhexamethylene isophthalamide copolymer (nylon 66 / 6T / 6I), Polyxylylene adipamide (nylon XD6), Polyxylylene sebacamide (nylon XD10) ), Polyhexamethylene terephthalamide / Polypentamethylene terephthalamide copolymer (nylon 6T / 5T), Polyhexamethylene terephthalamide / Poly-2-methylpentamethylene terephthalamide copolymer (nylon 6T / M5T), Polypentamethylene terephthalamide / Polydecamethylene terephthalamide copolymer (nylon 5T / 10T), polynonamethylene terephthalamide (nylon 9T), polydecamethylene terephthalamide (nylon 10T), polydodecamethylene terephthalamide (nylon 12T) and copolymers thereof Can be mentioned. Two or more of these may be blended. In addition, in this specification, "/" indicates a copolymer.

In the present invention, the melting point of the polyamide is preferably 150 ° C. or higher and lower than 300 ° C. When the melting point is 150 ° C. or higher, the heat resistance can be improved. On the other hand, when the melting point is less than 300 ° C., the processing temperature at the time of producing the resin composition can be appropriately suppressed, and the thermal decomposition of the modified polyrotaxane can be suppressed. Here, the melting point of the polyamide in the present invention is 20 ° C./min after the polyamide is cooled to 30 ° C. from the molten state at a temperature-decreasing rate of 20 ° C./min under an inert gas atmosphere using a differential scanning calorimeter. It is defined as the temperature of the endothermic peak that appears when the temperature is raised to the melting point + 40 ° C. at the heating rate of. However, when two or more endothermic peaks are detected, the temperature of the endothermic peak having the highest peak intensity is used as the melting point.

Specific examples of polyamides having a melting point of 150 ° C. or higher and lower than 300 ° C. are polycaproamide (nylon 6), polyhexamethylene adipamide (nylon 66), polypentamethylene adipamide (nylon 56), and polytetramethylene adipate. Pamide (nylon 46), polyhexamethylene sebacamide (nylon 610), polyhexamethylene dodecamide (nylon 612), polyundecaneamide (nylon 11), polydodecaneamide (nylon 12), polycaproamide / polyhexa Methylene adipamide copolymer (nylon 6/66), polycaproamide / polyhexamethylene terephthalamide copolymer (nylon 6 / 6T), polyhexamethylene adipamide / polyhexamethylene isophthalamide copolymer (nylon 66 / 6I), poly Hexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer (nylon 6T / 6I), polyhexamethylene terephthalamide / polydodecaneamide copolymer (nylon 6T / 12), polyhexamethylene adipamide / polyhexamethylene terephthalamide / polyhexa Methyleneisophthalamide copolymer (nylon 66 / 6T / 6I), polyxylylene adipamide (nylon XD6), polyhexamethylene terephthalamide / poly-2-methylpentamethylene terephthalamide copolymer (nylon 6T / M5T), polynomethylene Examples thereof include terephthalamide (nylon 9T) and copolymers thereof. In addition, you may mix two or more kinds of these.

The degree of polymerization of the polyamide according to the present invention is not particularly limited, but the relative viscosity measured at 25 ° C. in a 98% concentrated sulfuric acid solution having a polyamide concentration of 0.01 g / mL is in the range of 1.5 to 5.0. Is preferable. When the relative viscosity is in this range, the molding processability of the polyamide is good, and the toughness, rigidity, wear resistance, fatigue resistance, and creep resistance of the obtained molded product tend to be improved.

(4) Resin Composition The resin composition according to the present invention is a resin composition containing at least the above-mentioned (2) modified polyrotaxane and (3) polyamide. In addition to the modified polyrotaxane and the polyamide, the resin composition according to the present invention also contains a reaction product obtained by reacting the modified polyrotaxane with the polyamide, but it is not practical to specify the structure of the reaction product. Therefore, the present invention specifies the invention according to each component to be blended.

The blending amount of the modified polyrotaxane in the resin composition is preferably 0.01 parts by weight or more and 20 parts by weight or less with respect to 100 parts by weight of the total amount of the polyamide and the modified polyrotaxane. When the blending amount of the modified polyrotaxane is in this range, the obtained resin composition tends to be able to maintain the rigidity and thermal properties of the polyamide while exhibiting the effect of blending the modified polyrotaxane. Since the modified polyrotaxane according to the present invention has high compatibility with polyamide, even if the blending amount of the modified polyrotaxane is further reduced, the elongation at break is significantly improved while maintaining the rigidity and thermal properties of the polyamide, and the toughness is increased. Can be expressed. The amount of the modified polyrotaxane to be blended is preferably 0.01 parts by weight or more and 5 parts by weight or less, more preferably 0.01 parts by weight or more and 2.5 parts by weight or less, based on 100 parts by weight of the total amount of the polyamide and the modified polyrotaxane. Can be exemplified.

Further, the resin composition of the present invention may contain a filler, a thermoplastic resin other than polyamide, various additives and the like, as long as the object of the present invention is not impaired. By blending the filler, the strength and rigidity of the obtained molded product can be further improved. The filler may be either an organic filler or an inorganic filler, and may be either a fibrous filler or a non-fibrous filler. In addition, two or more of these may be blended.

Examples of the fibrous filler include glass fiber and carbon fiber. These may be coated or focused with a thermoplastic resin such as ethylene / vinyl acetate or a thermosetting resin such as an epoxy resin. Examples of the cross-sectional shape of the fibrous filler include a circular shape, a flat shape, an eyebrows shape, an oval shape, an elliptical shape, and a rectangular shape.

Examples of the non-fibrous filler include talc, warastenite, zeolite, sericite, mica, kaolin, clay, pyrophyllite, bentonite, asbestos, alumina silicate, non-swelling silicates such as calcium silicate, and Li-type fluorine teniolite. , Na-type fluorine teniolite, Na-type tetrasilicon fluorine mica, swellable layered silicate such as Li-type tetrasilicon fluorine mica, swellable layered silicate, silicon oxide, magnesium oxide, alumina, silica, diatomaceous earth, zirconium oxide, titanium oxide, oxidation. Metal oxides such as iron, zinc oxide, calcium oxide, tin oxide, antimony oxide, metal carbonates such as calcium carbonate, magnesium carbonate, zinc carbonate, barium carbonate, dolomite, hydrotalcite, metals such as calcium sulfate and barium sulfate. Metal hydroxides such as sulfate, magnesium hydroxide, calcium hydroxide, aluminum hydroxide, basic magnesium carbonate, smectite clay minerals such as montmorillonite, biderite, nontronite, saponite, hectrite, and soconite, vermiculite, and halloysite. , Various clay minerals such as kanemite, keniyaite, zirconium phosphate, titanium phosphate, glass beads, glass flakes, ceramic beads, boron nitride, aluminum nitride, silicon carbide, calcium phosphate, carbon black, graphite and the like. In the above-mentioned swellable layered silicate, the exchangeable cations existing between the layers may be exchanged with organic onium ions. Examples of the organic onium ion include ammonium ion, phosphonium ion, sulfonium ion and the like.

Specific examples of resins other than polyamide include polyester resin, polyolefin resin, modified polyphenylene ether resin, polysulfone resin, polyketone resin, polyetherimide resin, polyarylate resin, polyether sulfone resin, polyether ketone resin, and polythioether ketone. Examples thereof include resins, polyether ether ketone resins, polyimide resins, polyamideimide resins, and tetrafluoride polyethylene resins. In addition, you may mix two or more kinds of these.

Specific examples of various additives include heat stabilizers other than copper compounds, isocyanate-based compounds, organic silane-based compounds, organic titanate-based compounds, organic borane-based compounds, coupling agents such as epoxy compounds, and polyalkylene oxide oligoma-based compounds. , Plasticizers such as thioether compounds, ester compounds, organophosphorus compounds, organophosphorus compounds, crystal nucleating agents such as polyether ether ketones, waxes montanate, lithium stearate, metal soaps such as aluminum stearate, ethylenediamine・ Stearic acid / sebacic acid polycondensate, mold release agents such as silicone compounds, anticoloring agents such as hypophosphite, lubricants, ultraviolet inhibitors, coloring agents, flame retardants, foaming agents, etc. can be mentioned. .. When these additives are blended, the blending amount is preferably 10 parts by weight or less, and more preferably 1 part by weight or less with respect to 100 parts by weight of the polyamide in order to fully utilize the characteristics of the polyamide.

Examples of heat stabilizers other than copper compounds include N, N'-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamide) and tetrakis [methylene-3- (3', 5'-di). -T-butyl-4'-hydroxyphenyl) propionate] Phenolic compounds such as methane, phosphorus compounds, mercaptobenzoimidazole compounds, dithiocarbamic acid compounds, sulfur compounds such as organic thioic acid compounds, N, N' Examples thereof include amine compounds such as -di-2-naphthyl-p-phenylenediamine and 4,4'-bis (α, α-dimethylbenzyl) diphenylamine. In addition, you may mix two or more kinds of these.

The method for producing the polyamide resin composition according to the present invention is not particularly limited, and examples thereof include a method of kneading in a molten state and a method of mixing in a solution state. From the viewpoint of improving reactivity, a method of kneading in a molten state is preferable. Examples of the melt kneading device for kneading in a molten state include a multi-screw extruder such as a single-screw extruder, a twin-screw extruder, and a four-screw extruder, an extruder such as a twin-screw single-screw compound extruder, and a kneader. Can be mentioned. From the viewpoint of productivity, an extruder capable of continuously producing is preferable, and from the viewpoint of improving kneadability, reactivity and productivity, a twin-screw extruder is more preferable.

Next, a case where the resin composition according to the present invention is produced using a twin-screw extruder will be described as an example. The maximum resin temperature is preferably 300 ° C. or lower from the viewpoint of suppressing thermal deterioration of the modified polyrotaxane and further improving the toughness. On the other hand, the minimum resin temperature is preferably equal to or higher than the melting point of the polyamide. Here, the maximum resin temperature is the highest temperature measured by resin thermometers evenly arranged at a plurality of locations of the extruder. Further, the extrusion amount of the resin composition is preferably 0.01 kg / hr or more, more preferably 0.05 kg / hr or more per 1 rpm of screw rotation, from the viewpoint of further suppressing thermal deterioration of the polyamide and the modified polyrotaxane. Is. On the other hand, from the viewpoint of further promoting the reaction between the polyamide and the modified polyrotaxane, it is preferably 1 kg / hr or less per 1 rpm of screw rotation. Here, the extrusion amount refers to the weight (kg) of the resin composition discharged from the extruder per hour.

The resin composition thus obtained can be molded by a commonly known method, and various molded products such as sheets and films can be obtained. Examples of the molding method include injection molding, injection compression molding, extrusion molding, compression molding, blow molding, press molding and the like.

The resin composition and the molded product thereof according to the present invention can be used for various purposes such as automobile parts, electric / electronic parts, building materials, various containers, daily necessities, household goods and sanitary goods by utilizing their excellent properties. In particular, it is particularly preferably used for automobile exterior parts that require toughness and rigidity, automobile electrical parts, automobile underhood parts, automobile gear parts, housings, connectors, reflectors, and other electrical and electronic parts. Specifically, engine covers, air intake pipes, timing belt covers, intake manifolds, filler caps, throttle bodies, cooling fans and other automobile engine peripheral parts, cooling fans, radiator tank tops and bases, cylinder head covers, oil pans, etc. Automotive underhood parts such as brake pipes, fuel piping tubes, waste gas system parts, automobile gear parts such as gears, actuators, bearing retainers, bearing cages, chain guides, chain tensioners, shift lever brackets, steering lock brackets, key cylinders. , Door inner handle, door handle cowl, interior mirror bracket, air conditioner switch, instrument panel, console box, glove box, steering wheel, trim and other automobile interior parts, front fender, rear fender, fuel lid, door panel, cylinder head cover, door mirror Stays, tailgate panels, licensed garnishes, roof rails, engine mount brackets, rear garnishes, rear spoilers, trunk lids, rocker moldings, moldings, lamp housings, front grilles, mudguards, side bumpers and other automotive exterior parts, air intake manifolds, intercoolers Intake and exhaust system parts such as inlets, exhaust pipe covers, inner bushes, bearing retainers, engine mounts, engine head covers, resonators, and throttle bodies, chain covers, thermostat housings, outlet pipes, radiator tanks, oil nator, and delivery pipes. Engine cooling water system parts, connectors and wire harness connectors, motor parts, lamp sockets, sensor in-vehicle switches, automobile electrical parts such as combination switches, SMT compatible connectors, sockets, card connectors, jacks, power supply parts, switches, sensors, condenser seats Electrical and electronic components such as plates, relays, resistors, fuse holders, coil bobbins, IC and LED compatible housings, and reflectors can be preferably mentioned.

Hereinafter, the present invention will be specifically described with reference to examples. It should be noted that the examples described below are exemplary and not limited.

<Structural analysis of reactants>
The structural analysis of the reactants was carried out under the following conditions using the magnetic resonance imaging (NMR) shown below.
Equipment: AL-400 manufactured by JEOL Ltd.
Deuterated solvent: Dimethyl sulfoxide deuterated, Trifluoroacetic acid deuterated Sample concentration: Sample 1 mg / Deuterated solvent 1 mL

<Observation of phase structure of resin composition>
Observation of the phase structure in the molten state of the resin composition was carried out using an optical microscope and a hot stage.
Optical microscope body: Nikon OPTIPHOTO-POL
Melting temperature: 240 ° C

<Polyamide>
The following polyamides were used as the polyamides to be blended in the following thermoplastic resins.
Nylon 6 resin (“Amilan” (registered trademark) manufactured by Toray Industries, Inc.), ηr = 2.70, melting point 225 ° C., amide group concentration 10.5 mmol / g
Here, the above-mentioned solution viscosity ηr was measured at 25 ° C. using a 0.01 g / mL solution of 98% concentrated sulfuric acid. The melting point is determined by using a differential scanning calorimeter to lower the temperature of polyamide from the molten state to 30 ° C. at a temperature decrease rate of 20 ° C./min under an inert gas atmosphere, and then to a melting point of +40 at a heating rate of 20 ° C./min. The temperature of the endothermic peak that appears when the temperature is raised to ° C. is used. However, when two or more endothermic peaks are detected, the temperature of the endothermic peak having the highest peak intensity is taken as the melting point. The amide group concentration was calculated from the structural formula of the structural unit by the following formula.
Amide group concentration (mol / g) = (number of amide groups in structural unit / molecular weight in structural unit)

(Synthesis Example 1) Synthesis of polyrotaxane Here, the synthesis of polyrotaxane with reference to Patent Document 6 will be described. First, 10 g of polyethylene glycol (PEG) (molecular weight 20000), 100 mg of TEMPO (2,2,6,6-tetramethyl-1-piperidinyloxy radical) and 100 mg of sodium bromide in 100 mL of water. Dissolved.

After adding 0.26 g of sodium hypochlorite pentahydrate to this solution, the pH was adjusted to 11.6 by adding 1N sodium hydroxide aqueous solution, and the mixture was allowed to stand overnight at room temperature. Then, in order to decompose the surplus sodium hypochlorite, 10 mL of ethanol was added to terminate the reaction.

Subsequently, extraction with 100 mL of methylene chloride was repeated three times to extract components other than the inorganic salt, and then methylene chloride was distilled off with an evaporator to recover the solid content. Then, it was dissolved in 450 mL of warm ethanol and then allowed to stand in a refrigerator overnight to extract only PEG-carboxylic acid, which was recovered and dried.

5.0 g of PEG-carboxylic acid prepared as described above and 55 g of α-cyclodextrin (α-CD) are dissolved in 300 g of warm water, both are mixed, shaken well, and then at room temperature. It was allowed to stand overnight. The pseudo-polyrotaxane precipitated in the form of cream was freeze-dried and recovered.

35 g of pseudopolyrotaxane prepared as described above, 0.35 g of adamantanamine, 0.5 mL of diisopropylethylamine, and 1 of benzotriazole-1-yloxytris (dimethylamino) phosphonium hexafluorophosphate (BOP reagent). 9.0 g was dispersed in 200 mL of dimethylformamide (DMF) and stirred overnight at room temperature.

After stirring overnight, add 250 mL of DMF and mix, centrifuge and discard the supernatant 3 times, then add 250 mL of methanol and mix and centrifuge. The operation of discarding the supernatant liquid was repeated twice.

The obtained precipitate was dried by vacuum drying, then dissolved in dimethyl sulfoxide (DMSO), and the obtained transparent solution was added dropwise to 6 times the amount of water with respect to DMSO to precipitate polyrotaxane. .. Purified polyrotaxane was obtained by centrifuging and freeze-drying the precipitated polyrotaxane.

(Synthesis Example 2) Hydroxypropylation of polyrotaxane 10 g of polyrotaxane synthesized in Synthesis Example 1 is dissolved in 1 L of a 1 mol / L sodium hydroxide aqueous solution, 94 g of propylene oxide is added dropwise, and the mixture is subjected to a nitrogen atmosphere. Stirring was performed overnight. Then, it was neutralized with a 1 mol / L concentration hydrochloric acid aqueous solution, dialyzed with a dialysis tube, and then freeze-dried to obtain a hydroxypropylated polyrotaxane.

(Example 1) Synthesis of modified polyrotaxane In Example 1, a method for obtaining a modified polyrotaxane from the polyrotaxane prepared by the method of Synthesis Example 1 described above will be described.

<Tosylation of polyrotaxane>
1 g of polyrotaxane prepared by the method of Synthesis Example 1 was dispersed in 30 mL of pyridine and cooled in an ice bath. Then, 2.0 g of paratoluenesulfonyl chloride was added, and the reaction was carried out in an ice bath for 6 hours. Then, the solid content was precipitated by pouring the reaction solution into 500 mL of deionized water, and the solid content was recovered using a glass filter. The obtained solid content was washed with a large amount of deionized water and diethyl ether, and then vacuum dried to obtain a tosylated polyrotaxane. The tosylation of polyrotaxane was structurally analyzed by NMR.

<Amination of tosylated polyrotaxane>
1 g of the synthesized polyrotaxane tosylated was dissolved in 30 mL of dimethylformamide. This solution was added dropwise to a mixed solution of 40 mL of ethylenediamine and 20 mL of dimethylformamide, which had been preheated to 70 ° C., and the reaction was carried out at 70 ° C. for 5 hours after the completion of the dropping. Then, the reaction solution was poured into 1 L of diethyl ether to precipitate the solid content, and the precipitated solid content was recovered by centrifugation. Then, the solid content was dissolved in dimethylformamide, reprecipitated and purified in diethyl ether, and then the obtained solid content was dried to obtain an aminated polyrotaxane. The amination of polyrotaxane was structurally analyzed by NMR.

<Polycaprolactamization of amination polyrotaxane>
6.8 g of ε-caprolactam was dissolved by heating at 150 ° C. under a nitrogen flow, and 0.2 g of the above-mentioned aminoated polyrotaxane and 0.3 g of tin octylate were dissolved in 0.8 g of toluene. Added. Then, the temperature was gradually raised to 190 ° C., and then the reaction was carried out at 190 ° C. for 1 hour. The obtained reaction product was poured into 200 mL of methanol to precipitate solid content, and then vacuum dried to obtain a modified polyrotaxane having a desired lactam-derived modifying group. The structural analysis of the modified polyrotaxane was performed by NMR.

(Example 2) Resin composition of modified polyrotaxane and polyamide In Example 2, the modified polyrotaxane and the polyamide resin obtained by the above-mentioned method of Example 1 each have a modified polyrotaxane / polyamide resin composition of 5 w%. Pre-blended by blending to a ratio of / 95w% and supplied to a small twin-screw kneader (HAAKE MiniLab II micro compounder manufactured by Thermo Fisher Scientific Co., Ltd.) with a cylinder temperature of 230 ° C and a screw rotation speed of 200 rpm. Then, melt kneading was performed.

As a result of observing the phase structure using the obtained pellets, no modified polyrotaxane phase was observed with an optical microscope. From this, it can be seen that the polyamide and the modified polyrotaxane have good compatibility, and the modified polyrotaxane is finely dispersed in the polyamide.

(Example 3) Synthesis of modified polyrotaxane In Example 3, a step of obtaining a modified polyrotaxane from the polyrotaxane prepared by the method described in Synthesis Example 2 will be described.

<Tosylation of polyrotaxane>
1 g of the hydroxypropylated polyrotaxane prepared by the method of Synthesis Example 2 described above was dissolved in 30 mL of pyridine and cooled in an ice bath. Then, 2.0 g of paratoluenesulfonyl chloride was added, and the reaction was carried out in an ice bath for 6 hours. Then, the solid content was precipitated by pouring the reaction solution into 500 mL of deionized water, and the solid content was recovered using a glass filter. The obtained solid content was washed with a large amount of deionized water and diethyl ether and then vacuum dried to obtain a tosylated hydroxypropylated polyrotaxane. The tosylation of hydroxypropylated polyrotaxane was structurally analyzed by NMR.

<Amination of tosylated polyrotaxane>
1 g of the synthesized tosylated polyrotaxane was dissolved in 30 mL of dimethylformamide. This solution was added dropwise to a mixed solution of 40 mL of ethylenediamine and 20 mL of dimethylformamide that had been preheated to 70 ° C., and the reaction was carried out at 70 ° C. for 5 hours after the completion of the addition. Then, the reaction solution was poured into 1 L of diethyl ether to precipitate the solid content, and the precipitated solid content was recovered by centrifugation. Then, the solid content was dissolved in dimethylformamide, reprecipitation and purification was performed using diethyl ether, and then the obtained solid content was dried to obtain an aminoated polyrotaxane. The amination of polyrotaxane was structurally analyzed by NMR.

<Polycaprolactamization of amination polyrotaxane>
6.8 g of ε-caprolactam was dissolved by heating at 150 ° C. under a nitrogen flow, and 0.2 g of the above-mentioned aminoated polyrotaxane and 0.3 g of tin octylate were dissolved in 0.8 g of toluene. Added. Then, the temperature was gradually raised to 190 ° C., and then the reaction was carried out at 190 ° C. for 1 hour. The obtained reaction product was poured into 200 mL of methanol to precipitate solids, and the recovered solids were vacuum-dried to obtain a modified polyrotaxane having a desired lactam-derived modifying group. The structural analysis of the modified polyrotaxane was performed by NMR.

(Example 4) Resin composition of modified polyrotaxane and polyamide In Example 4, the modified polyrotaxane and the polyamide resin obtained by the method of Example 3 described above have a modified polyrotaxan / polyamide resin composition of 5 w%, respectively. Pre-blended by blending to a ratio of / 95w% and supplied to a small twin-screw kneader (HAAKE MiniLab II micro compounder manufactured by Thermo Fisher Scientific Co., Ltd.) with a cylinder temperature of 230 ° C and a screw rotation speed of 200 rpm. Then, melt kneading was performed.

As a result of observing the phase structure using the obtained pellets, no modified polyrotaxane phase was observed with an optical microscope. From this, it can be seen that the polyamide and the modified polyrotaxane have good compatibility, and the modified polyrotaxane is finely dispersed in the polyamide.

(Comparative Example 1) Resin composition of polyrotaxane having no modifying group derived from lactam and polyamide In Comparative Example 1, polyrotaxane (Advanced Soft Material Co., Ltd.) in which cyclodextrin was modified with polycaprolactone as a graft chain was used. "SELM" (registered trademark) Superpolymer SH2400P) and polyamide resin are mixed and pre-blended so that the composition of polyrotaxan / polyamide resin is 5w% / 95w%, the cylinder temperature is 230 ° C, and the screw rotation speed is increased. Was supplied to a small twin-screw kneader (HAAKE MiniLabII microcompounder manufactured by Thermo Fisher Scientific Co., Ltd.) set at 200 rpm to perform melt kneading.

As a result of observing the phase structure using the obtained pellets, it was found that the polyrotaxane phase was 3 to 6 μm, and the polyrotaxane was coarsely separated.

Further, after vacuum-drying the obtained pellets at 80 ° C. for 12 hours, a cylinder temperature: 250 ° C. and a mold temperature were used using an injection molding machine (HAAKE MinijetPro piston injection molding machine manufactured by Thermo Fisher Scientific Co., Ltd.). : An ISO527-2-5A dumbbell having a thickness of 2.0 mm was produced by injection molding under the condition of 80 ° C. This dumbbell test piece was subjected to a tensile test at a crosshead speed of 100 mm / min using a tensile tester Autograph AG-20kN (manufactured by Shimadzu Corporation) in accordance with ISO-527 to determine the tensile elongation at break and the tensile yield strength. As a result of the measurement, it was found that the elongation at break was 60% and the yield strength was 78 MPa.

(Example 5)
In Example 5, the modified polyrotaxane and the polyamide resin obtained by the method of Example 1 described above are blended so that the composition of the modified polyrotaxan / polyamide resin is 2.5 w% / 97.5 w%, respectively. It was pre-blended and supplied to a small twin-screw kneader (HAAKE MiniLabII microcompounder manufactured by Thermo Fisher Scientific Co., Ltd.) in which the cylinder temperature was set to 230 ° C. and the screw rotation speed was set to 200 rpm, and melt kneading was performed.

As a result of observing the phase structure using the obtained pellets, no modified polyrotaxane phase was observed with an optical microscope. From this, it was found that the polyamide and the modified polyrotaxane have good compatibility, and the modified polyrotaxane is finely dispersed in the polyamide.

Further, after vacuum drying the obtained pellets at 80 ° C. for 12 hours, a cylinder temperature: 250 ° C. and a mold temperature were used using an injection molding machine (HAAKE Minijet Pro piston injection molding machine manufactured by Thermo Fisher Scientific Co., Ltd.). : An ISO527-2-5A dumbbell having a thickness of 2.0 mm was produced by injection molding under the condition of 80 ° C. This dumbbell test piece was subjected to a tensile test at a crosshead speed of 100 mm / min using a tensile tester Autograph AG-20kNX (manufactured by Shimadzu Corporation) in accordance with ISO-527 to determine the tensile elongation at break and the tensile yield strength. As a result of the measurement, it was found that the elongation at break was 145% and the yield strength was 79 MPa.

(Example 6)
In Example 6, the modified polyrotaxane and the polyamide resin obtained by the method of Example 3 described above are blended so that the composition of the modified polyrotaxan / polyamide resin is 2.5 w% / 97.5 w%, respectively. It was pre-blended and supplied to a small twin-screw kneader (HAAKE MiniLabII microcompounder manufactured by Thermo Fisher Scientific Co., Ltd.) in which the cylinder temperature was set to 230 ° C. and the screw rotation speed was set to 200 rpm, and melt kneading was performed.

As a result of observing the phase structure using the obtained pellets, no modified polyrotaxane phase was observed with an optical microscope. From this, it was found that the polyamide and the modified polyrotaxane have good compatibility, and the modified polyrotaxane is finely dispersed in the polyamide.

Further, the obtained pellets were vacuum-dried at 80 ° C. for 12 hours, and using an injection molding machine (HAAKE Minijet Pro piston injection molding machine manufactured by Thermo Fisher Scientific Co., Ltd.), the cylinder temperature: 250 ° C., the mold temperature: An ISO527-2-5A dumbbell having a thickness of 2.0 mm was produced by injection molding under the condition of 80 ° C. This dumbbell test piece was subjected to a tensile test at a crosshead speed of 100 mm / min using a tensile tester Autograph AG-20kNX (manufactured by Shimadzu Corporation) in accordance with ISO-527 to determine the tensile elongation at break and the tensile yield strength. As a result of the measurement, it was found that the elongation at break was 150% and the yield strength was 80 MPa.

By comparing Comparative Example 1 and Examples 5 and 6 described above, the modified polyrotaxane of the present invention having high compatibility with polyamide has a large elongation at break while maintaining yield strength even when added in a small amount to polyamide. It turns out to improve.

As described above, according to one embodiment of the present invention, a modified polyrotaxane having good compatibility with polyamide and finely dispersed in polyamide can be obtained.

Claims (7)

(A) Modified cyclodextrin having a modifying group derived from lactam,
(B) A linear molecule that penetrates the opening of cyclodextrin in a skewered manner.
(C) A modified polyrotaxane consisting of at least a blocking group arranged so that the modified cyclodextrin does not escape.
The modified cyclodextrin having a modifying group derived from lactam has a structure represented by the general formula (II).
A modified polyrotaxane characterized by that.
-NH-R-NH- (CO- (CH ₂ ) _m - NH) _n - H ... (II)
(R: hydrocarbon group, m: an integer of 2 to 15 indicating the number of repetitions, n: an integer of 1 to 100 indicating the degree of polymerization) The modifying group derived from lactam is a modifying group derived from ε-caprolactam.
The modified polyrotaxane according to claim 1 . The linear molecule is polyethylene glycol.
The modified polyrotaxane according to claim 1 or 2 . A resin composition comprising at least a polyamide and the modified polyrotaxane according to any one of claims 1 to 3 . (A) Modified cyclodextrin having a modifying group derived from lactam,
(B) A linear molecule that penetrates the opening of cyclodextrin in a skewered manner.
(C) A modified polyrotaxane consisting of at least a blocking group arranged so that the modified cyclodextrin is not desorbed, and a polyamide are blended.
A resin composition characterized by that. A polyrotaxane consisting of cyclodextrin, a linear molecule that penetrates the opening of cyclodextrin in a skewered manner, and a blocking group arranged so that cyclodextrin is not detached, at least (a) a hydroxyl group on cyclodextrin with lactam. A method for producing a modified polyrotaxane, wherein the step of converting into a functional group capable of reacting and (b) the step of reacting the functional group on cyclodextrin with lactam are sequentially performed.
The functional group capable of reacting with the lactam is an amino group.
A method for producing a modified polyrotaxane. The lactam is ε-caprolactam.
The method for producing a modified polyrotaxane according to claim 6 , wherein the modified polyrotaxane is produced.