WO2017057703A1 - Additif pour résine, mélange maître mettant en oeuvre cet additif et composition de résine - Google Patents

Additif pour résine, mélange maître mettant en oeuvre cet additif et composition de résine Download PDF

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Publication number
WO2017057703A1
WO2017057703A1 PCT/JP2016/079076 JP2016079076W WO2017057703A1 WO 2017057703 A1 WO2017057703 A1 WO 2017057703A1 JP 2016079076 W JP2016079076 W JP 2016079076W WO 2017057703 A1 WO2017057703 A1 WO 2017057703A1
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resin
additive
mass
resin composition
parts
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PCT/JP2016/079076
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English (en)
Japanese (ja)
Inventor
高橋　郁夫
善宏 山崎
彰 谷口
沙織 小谷
西川　直毅
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日清紡ケミカル株式会社
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Publication of WO2017057703A1 publication Critical patent/WO2017057703A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers

Definitions

  • the present invention relates to a resin additive used in manufacturing a resin composition such as a polyester resin or a polyamide resin, a masterbatch using the resin additive, a manufacturing method thereof, and a resin composition using the resin additive.
  • the present invention relates to a product and a manufacturing method thereof.
  • Polyester resins such as PET are excellent in transparency, mechanical strength, melt stability, solvent resistance, and polyamide resins such as nylon are excellent in mechanical strength, flexibility, chemical resistance, etc. Therefore, they are widely used for fibers, films, sheets, etc., and are also used for recycling.
  • polyester resins and polyamide resins are obtained by polycondensation such as ester bonds and amide bonds, and have the property of being easily hydrolyzed at these bonding sites due to deterioration over time. For this reason, a carbodiimide compound is added to the resin composition for the purpose of improving hydrolysis resistance.
  • Patent Document 1 describes that the hydrolysis resistance of an aliphatic polyester resin composition is improved by adding an aromatic polycarbodiimide compound to the aliphatic polyester resin.
  • hydrolysis of the aliphatic polyester resin is suppressed, but during mixing at a temperature equal to or higher than the melting temperature of the aliphatic polyester resin, the carboxyl of the polyester resin The group reacts with the carbodiimide group of the aromatic carbodiimide compound to decompose the aromatic carbodiimide compound.
  • isocyanate gas which is an irritating decomposition gas
  • polyester resin compositions that generate a large amount of isocyanate gas when used for injection molding, the mold is very dirty, the yield of molded products is reduced, and the mold must be washed frequently. As a result, the production efficiency of the molded product is reduced.
  • Patent Document 2 describes that according to a resin composition in which a polyester and a cyclic carbodiimide compound are mixed, malodor due to free isocyanate can be suppressed.
  • Patent Document 3 a polyester resin composition containing a polyester resin and an aromatic carbodiimide and further an aliphatic carbodiimide is a decomposition gas derived from an aromatic carbodiimide added to improve the hydrolysis resistance of the polyester resin. It is described that generation
  • the resin composition described in Patent Document 2 is a compound having one carbodiimide group in one cyclic structure, and does not liberate an isocyanate compound even if it reacts with a polyester terminal.
  • an isocyanate group remains at the end of the polyester resin. Since the remaining isocyanate group further reacts with other terminal groups such as hydroxyl groups, the polyester is thickened, resulting in deterioration of processability, and the isocyanate group may be detached.
  • the present invention has been made in order to solve the above-described problems.
  • a carbodiimide compound is used as an additive for improving the hydrolysis resistance of a polyester resin or a polyamide resin
  • a masterbatch or a resin composition is produced.
  • a resin additive capable of effectively suppressing the generation of isocyanate gas a masterbatch using the resin additive and a method for producing the same, and a resin composition using the resin additive and a method for producing the same. It is for the purpose.
  • the present invention is based on the finding that a predetermined heterocyclic amine compound is effective as a resin additive in suppressing generation of isocyanate gas derived from a carbodiimide compound.
  • a resin additive according to [1] wherein the heterocyclic amine compound (B) has a vaporization temperature of 100 to 300 ° C. and a decomposition temperature of more than 300 ° C.
  • the carbodiimide compound (A) is at least one of aromatic monocarbodiimide, aromatic polycarbodiimide, aliphatic monocarbodiimide, and aliphatic polycarbodiimide.
  • the resin additive according to any one of the above.
  • the heterocyclic amine compound (B) is 0.1 to 50 parts by mass with respect to 100 parts by mass of the carbodiimide compound (A). The resin additive as described.
  • [8] A method for producing a masterbatch according to [6] or [7] above, wherein the resin additive according to any one of [1] to [5] and the resin (C) are combined.
  • the resin additive according to any one of [1] to [5] above is blended with the resin (C), and the resin (C) is at least one of a polyester resin and a polyamide resin.
  • the resin additive according to any one of [1] to [5] above and a resin (C) are melt-kneaded, and the resin (C) is at least one of a polyester resin and a polyamide resin.
  • the manufacturing method of the resin composition which is any 1 type.
  • a method for producing a resin composition comprising melt-kneading the master batch according to the above [6] or [7] and the resin (C).
  • a carbodiimide compound when used as an additive for improving the hydrolysis resistance of a polyester resin or a polyamide resin, the generation of isocyanate gas during the production of a masterbatch or a resin composition is effectively suppressed. It is possible to provide a resin additive, and a master batch and a resin composition using the resin additive. Therefore, according to the present invention, a masterbatch or a resin composition of a polyester resin or polyamide resin having hydrolysis resistance while effectively suppressing generation of irritating isocyanate gas and ensuring a safe working environment. Can be manufactured.
  • the resin additive of the present invention is used for at least one of a polyester resin and a polyamide resin. And it contains a carbodiimide compound (A) and a heterocyclic amine compound (B) and does not contain a surfactant. According to such an additive, a heterocyclic amine compound (B) is imparted to a resin having an easily hydrolyzed bond site, such as an ester bond or an amide bond, by the carbodiimide compound (A), while providing hydrolysis resistance. ) Can suppress generation of isocyanate gas derived from the carbodiimide compound (A).
  • the resin additive may be prepared by mixing the carbodiimide compound (A) and the heterocyclic amine compound (B) in advance, or both components may be added at the time of use. .
  • the reason why the generation of isocyanate gas is suppressed is that the isocyanate gas generated by thermal decomposition of the reaction product of the carboxyl group or amino group of the polyester resin or polyamide resin and the carbodiimide group of the carbodiimide compound (A) is vaporized at the same time. This is considered to be because it reacts with the heterocyclic amine compound (B) to be changed to a compound different from isocyanate.
  • the surfactant also has the effect of suppressing the generation of isocyanate gas, like the heterocyclic amine compound (B), but the resin additive of the present invention does not contain a surfactant.
  • the carbodiimide compound (A) is a compound containing a carbodiimide group (—N ⁇ C ⁇ N—), and is used for improving the hydrolysis resistance of the resin.
  • the carbodiimide compound (A) is preferably an aromatic monocarbodiimide, an aromatic polycarbodiimide, an aliphatic monocarbodiimide, or an aliphatic polycarbodiimide. Among these, it may be used alone or in combination of two or more.
  • aliphatic monocarbodiimide or aliphatic polycarbodiimide is preferably used, but from the viewpoint of suppressing viscosity increase and preventing coloration in consideration of resin processability, aromatic monocarbodiimide is used.
  • Carbodiimide or aromatic polycarbodiimide is preferably used.
  • Aromatic monocarbodiimide is a carbodiimide compound in which one carbodiimide group is directly bonded to an aromatic ring.
  • Specific examples thereof include diphenylcarbodiimide, bis (methylphenyl) carbodiimide, bis (methoxyphenyl) carbodiimide, bis ( Nitrophenyl) carbodiimide, bis (dimethylphenyl) carbodiimide, bis (diisopropylphenyl) carbodiimide, bis (di-t-butylphenyl) carbodiimide and the like.
  • bis (diisopropylphenyl) carbodiimide is preferred from the viewpoint of improving the hydrolysis resistance of the resin.
  • An aromatic polycarbodiimide is a carbodiimide compound having two or more carbodiimide groups in the molecule, and the carbodiimide group is directly bonded to an aromatic ring.
  • carbodiimides such as organic phosphorus compounds and organometallic compounds It can synthesize
  • diisocyanate examples include 1,5-naphthalene diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4′-diphenyldimethylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4 -Tolylene diisocyanate, 2,6-tolylene diisocyanate, 3,3 ', 5,5'-tetraisopropylbiphenyl-4,4'-diisocyanate, 1,3,5-triisopropylbenzene-2,4-diisocyanate, etc. Is mentioned. These may be used alone or in combination of two or more. Of these, 4,4'-diphenylmethane diisocyanate and 1,3,5-triisopropylbenzene-2,4-diisocyanate are preferred from the viewpoints of high stability and improving the hydrolysis resistance of the resin.
  • Aliphatic monocarbodiimide is a carbodiimide compound in which one carbodiimide group is directly bonded to carbon other than an aromatic ring.
  • Specific examples thereof include dicyclohexylcarbodiimide, diisopropylcarbodiimide, N-ethyl-N ′-(3- And dimethylaminopropyl) carbodiimide. Of these, dicyclohexylcarbodiimide is preferred from the viewpoint of improving the hydrolysis resistance of the resin.
  • An aliphatic polycarbodiimide is a polycarbodiimide having two or more carbodiimide groups in the molecule, and the carbodiimide group is bonded to a carbon atom other than an aromatic ring, such as an organic phosphorus compound or an organometallic compound. It can be synthesized by a decarboxylation condensation reaction of diisocyanate using a carbodiimidization catalyst.
  • diisocyanate examples include hexamethylene diisocyanate, cyclohexane-1,4-diisocyanate, isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, methylcyclohexane diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, xylylene diene Examples include isocyanate and tetramethylxylylene diisocyanate. These may be used alone or in combination of two or more. Of these, 4,4'-dicyclohexylmethane diisocyanate is preferred from the viewpoint of high stability and improving the hydrolysis resistance of the resin.
  • aromatic polycarbodiimide or aliphatic polycarbodiimide can be sealed by reacting with a monofunctional compound having reactivity with a diisocyanate-terminated isocyanate group used for synthesis, and the degree of polymerization can be adjusted.
  • Examples of such compounds include monoisocyanates such as phenyl isocyanate, tolyl isocyanate, isopropyl phenyl isocyanate and cyclohexyl isocyanate; alcohols such as methanol, isopropyl alcohol, phenol and polyethylene glycol monomethyl ether; amines such as butylamine, diethylamine and cyclohexylamine; propion Examples thereof include carboxylic acids such as acid and benzoic acid.
  • the degree of polymerization of the aromatic polycarbodiimide or the aliphatic polycarbodiimide is preferably 2 to 200, more preferably 5 to 30 from the viewpoint of suppressing the generation of isocyanate gas during melt kneading of the resin.
  • the heterocyclic amine compound (B) has an action of suppressing generation of isocyanate gas derived from the carbodiimide compound (A). For this reason, from the viewpoint of effectively suppressing the generation of isocyanate gas at the time of melt kneading of the resin, it is preferable to vaporize without decomposition near the melting temperature of the added polyester resin or polyamide resin. It is preferable that the temperature is 100 to 300 ° C. and the decomposition temperature exceeds 300 ° C.
  • the vaporization temperature and decomposition temperature are values measured by a thermogravimetric / differential thermal analysis (TG-DTA) apparatus.
  • heterocyclic amine compound (B) examples include pyrrolidine, piperidine, piperazine, morpholine, quinuclidine, pyrrole, pyrazole, imidazole, pyridine, pyridazine, pyrimidine, pyrazine, oxazole, and thiazole. These may be used alone or in combination of two or more. Of these, pyrazole, dimethylpyrazole or imidazole is preferable, and dimethylpyrazole is more preferable from the viewpoint of industrial availability, reactivity with isocyanate gas, and volatility during melt kneading with a resin.
  • the content of the heterocyclic amine compound (B) in the resin additive does not significantly reduce the hydrolysis resistance imparted by the carbodiimide compound (A), or the resin melts without coloring the resin. From the viewpoint of sufficiently reducing the amount of isocyanate gas generated during kneading, it is preferably 0.1 to 50 parts by mass, more preferably 0.5 to 30 parts by mass with respect to 100 parts by mass of the carbodiimide compound (A). More preferably, it is 1 to 20 parts by mass.
  • the master batch of the present invention contains the resin additive of the present invention and the resin (C). That is, it includes a carbodiimide compound (A), a heterocyclic amine compound (B), and a resin (C).
  • the carbodiimide compound (A) is improved in uniform dispersibility when producing a hydrolysis-resistant resin composition, and carbodiimide is used.
  • production of the isocyanate gas derived from a compound (A) can be suppressed easily.
  • the resin (C) is at least one of a polyester resin and a polyamide resin. These resins can improve hydrolysis resistance by the addition of the carbodiimide compound (A).
  • Polyester resins include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polybutylene succinate (PBS), polybutylene succinate adipate (PBSA), polybutylene adipate terephthalate (PBAT), polyhydroxyalkanoic acid (PHA) And polylactic acid (PLA), polyethylene naphthalate, polyarylate, ethylene terephthalate-isophthalate copolymer, and the like. These may be used alone or in combination of two or more.
  • polyethylene terephthalate, polybutylene terephthalate, polybutylene succinate, polyhydroxyalkanoic acid or polylactic acid is preferably used from the viewpoint of industrial availability, recycling and the like.
  • polyamide resin examples include nylon 6, nylon 11, nylon 66, nylon 12, nylon 610, nylon 6T, and the like.
  • the content of the carbodiimide compound (A) in the master batch is 0 with respect to 100 parts by mass of the resin (C) from the viewpoint of improving the hydrolysis resistance of the resin composition produced using the master batch.
  • the amount is preferably 5 to 30 parts by mass, more preferably 1 to 20 parts by mass, and still more preferably 2 to 15 parts by mass.
  • the master batch can be produced by melt-kneading the resin additive and the resin (C). That is, it is obtained by melt-kneading at least the carbodiimide compound (A) and the heterocyclic amine compound (B) and the resin (C). According to such a production method, it is possible to produce a master batch while ensuring a safe working environment by simply suppressing the generation of isocyanate gas derived from the carbodiimide compound (A) during melt kneading of the resin.
  • Specific embodiments of the method for producing the masterbatch include (1) a method of melt-kneading a mixture in which the resin (C) and the resin additive are mixed in advance, and (2) the resin into the molten resin (C).
  • Examples thereof include a method of adding an additive and kneading.
  • the heterocyclic amine compound (B) is present before or simultaneously with the carbodiimide compound (A) among the components of the resin additive during melt kneading. It is preferable to be added to the resin (C).
  • the melt kneading means is not particularly limited, and can be performed using a known kneader.
  • the resin (C) can be melt-kneaded with a single-screw or twin-screw extruder, a roll mixer, or the like.
  • additives other than the components of the resin additive may be added as long as the effects of the present invention are not impaired.
  • inorganic fillers such as silica, alumina, sand, clay, and mineral; reinforcing agents such as needle-like inorganic materials; colorants such as titanium oxide, stabilizers such as radical scavengers and antioxidants; metal hydrates, halogen-based materials
  • colorants such as titanium oxide, stabilizers such as radical scavengers and antioxidants
  • metal hydrates halogen-based materials
  • flame retardants such as flame retardants and phosphorus flame retardants
  • crystal nucleating agents such as talc
  • antibacterial agents such as silver ions, copper ions and zeolites containing these
  • antifungal agents and the like are examples of the like.
  • the resin composition of the present invention is obtained by blending the resin additive of the present invention with the resin (C).
  • the master batch of the present invention is blended with the resin (C).
  • the master batch is distinguished from the resin composition, and the master batch is not included in the resin composition referred to in the present invention.
  • the resin (C) here is the same as the resin (C) in the master batch, the description thereof is omitted.
  • the content of the carbodiimide compound (A) among the components of the resin additive is based on 100 parts by mass of the resin (C) from the viewpoint of improving the hydrolysis resistance of the resin composition. 0.1 to 10 parts by mass, more preferably 0.3 to 5 parts by mass, and still more preferably 0.5 to 3 parts by mass.
  • the resin composition can be produced by melt-kneading the resin additive and the resin (C). That is, it is obtained by melt-kneading at least the carbodiimide compound (A) and the heterocyclic amine compound (B) and the resin (C). Moreover, the said resin composition can be manufactured also by melt-kneading the said masterbatch and resin (C). According to such a production method, it is possible to produce a resin composition while ensuring a safe working environment by simply suppressing the generation of isocyanate gas derived from the carbodiimide compound (A) during melt kneading of the resin. . Furthermore, with the suppression of the generation of isocyanate gas, the resin composition also has the effect of suppressing mold stains during injection molding using this.
  • Specific embodiments of the method for producing the resin composition include (1) a method of melt-kneading a mixture in which the resin (C) and the resin additive are mixed in advance, and (2) the molten resin (C) Examples thereof include a method of adding a resin additive and kneading.
  • a method of melting and kneading a mixture in which the resin (C) and the master batch are mixed in advance examples thereof include a kneading method.
  • the method (3) or (4) using a master batch is preferable, and the method (3) is more preferable.
  • the carbodiimide compound (A) of the components of the resin additive is preceded.
  • the heterocyclic amine compound (B) is added to the resin (C).
  • Additives other than the melt-kneading means and the resin additive components are the same as those in the above-described masterbatch production method.
  • a known method such as an injection molding method, a film molding method, a blow molding method, a foam molding method, or the like can be used. It can be formed into various forms such as a shape, and processed products of materials and members for various uses can be obtained. Specifically, it can be used for various uses such as electrical and electronic equipment members such as housings of electrical appliances, building materials, automobile parts, daily necessities, medical supplies, agricultural supplies, and the like.
  • Aliphatic polycarbodiimide polydicyclohexylmethane carbodiimide; “Carbodilite LA-1” manufactured by Nisshinbo Chemical Co., Ltd. ⁇ Heterocyclic amine compound (B)> Dimethylpyrazole: manufactured by Otsuka Chemical Co., Ltd .; vaporization temperature: 120 ° C., decomposition temperature: no peak that appears to be decomposed to 400 ° C.
  • Tensile strength retention rate (%) (tensile strength after wet heat treatment for a predetermined time / initial tensile strength) ⁇ 100 The time until the tensile strength retention was 50% was defined as the hydrolysis resistance time. The longer the hydrolysis resistance time, the better the hydrolysis resistance.
  • PET resin [PET resin] Table 1 below shows the composition of the produced PET resin composition and master batch.
  • Example 1 As resin (C), 49.5 parts by mass of PET was melted at 280 ° C. with a lab mixer (Laboplast Mill “Segment Mixer KF70V” manufactured by Toyo Seiki Seisakusho Co., Ltd .; the same shall apply hereinafter), and then as a carbodiimide compound (A) A resin additive in which 0.5 part by weight of aromatic monocarbodiimide and 0.05 part by weight of dimethylpyrazole as a heterocyclic amine compound (B) are mixed in advance is added and kneaded for 3 minutes to produce a PET resin composition. (Addition method: I).
  • Example 2 A carbodiimide compound (A), a heterocyclic amine compound (B), and a resin (C) were blended as shown in Table 1 below, and a PET resin composition was produced in the same manner as in Example 1 except that.
  • Example 5 After 49.5 parts by mass of PET as the resin (C) was melted at 280 ° C. with a laboratory mixer, 0.05 part by mass of dimethylpyrazole was added as the heterocyclic amine compound (B) and kneaded for 30 seconds. Next, 0.5 parts by mass of aromatic monocarbodiimide was added as the carbodiimide compound (A) and kneaded for 2 minutes 30 seconds to produce a PET resin composition (addition method: II).
  • Example 6 Production of master batch After melting 45.0 parts by mass of PET as a resin (C) at 280 ° C with a lab mixer, 5.0 parts by mass of aromatic monocarbodiimide as a carbodiimide compound (A) and complex A resin additive in which 0.5 part by mass of dimethylpyrazole as a cyclic amine compound (B) was mixed in advance was added and kneaded for 3 minutes to produce a PET resin-based masterbatch (addition method: I).
  • Example 7 45.0 parts by mass of PET as the resin (C) and 5.05 parts by mass of the PET resin-based masterbatch produced in Example 6 were mixed and kneaded at 280 ° C. for 3 minutes in a lab mixer to obtain a PET resin composition.
  • Example 7 45.0 parts by mass of PET as the resin (C) and 5.05 parts by mass of the PET resin-based masterbatch produced in Example 6 were mixed and kneaded at 280 ° C. for 3 minutes in a lab mixer to obtain a PET resin composition.
  • additional method: III 45.0 parts by mass of PET as the resin (C) and 5.05 parts by mass of the PET resin-based masterbatch produced in Example 6 were mixed and kneaded at 280 ° C. for 3 minutes in a lab mixer to obtain a PET resin composition.
  • Example 1 a PET resin composition was produced in the same manner as in Example 1 except that the heterocyclic amine compound (B) was not added.
  • Example 8 a PET resin composition was produced in the same manner as in Example 8 except that the heterocyclic amine compound (B) was not added.
  • Example 3 a PET resin composition was produced in the same manner as in Example 10 except that the heterocyclic amine compound (B) was not added.
  • Example 14 After 49.5 parts by mass of PBT as the resin (C) was melted at 280 ° C. with a laboratory mixer, 0.05 part by mass of dimethylpyrazole was added as the heterocyclic amine compound (B) and kneaded for 30 seconds. Next, 0.5 parts by mass of aromatic monocarbodiimide was added as the carbodiimide compound (A) and kneaded for 2 minutes and 30 seconds to produce a PBT resin composition (addition method: II).
  • Example 15 Production of master batch After melting 45.0 parts by mass of PBT as a resin (C) at 280 ° C with a laboratory mixer, 5.0 parts by mass of an aromatic monocarbodiimide as a carbodiimide compound (A) and a complex A resin additive in which 0.5 part by mass of dimethylpyrazole as a cyclic amine compound (B) was mixed in advance was added and kneaded for 3 minutes to produce a PBT resin-based master batch (addition method: I).
  • Example 16 45.0 parts by mass of PBT as the resin (C) and 5.05 parts by mass of the PBT resin-based masterbatch produced in Example 15 were mixed and kneaded at 280 ° C. for 3 minutes in a lab mixer to obtain a PBT resin composition.
  • Example 16 45.0 parts by mass of PBT as the resin (C) and 5.05 parts by mass of the PBT resin-based masterbatch produced in Example 15 were mixed and kneaded at 280 ° C. for 3 minutes in a lab mixer to obtain a PBT resin composition.
  • Example 16 45.0 parts by mass of PBT as the resin (C) and 5.05 parts by mass of the PBT resin-based masterbatch produced in Example 15 were mixed and kneaded at 280 ° C. for 3 minutes in a lab mixer to obtain a PBT resin composition.
  • Example 16 45.0 parts by mass of PBT as the resin (C) and 5.05 parts by mass of the PBT resin-based masterbatch produced in Example 15 were mixed and kneaded
  • Example 12 a PBT resin composition was produced in the same manner as in Example 12 except that the heterocyclic amine compound (B) was not added.
  • PLA resin Table 3 below shows the composition of the produced PLA resin composition and master batch.
  • Example 18 After 49.5 parts by mass of PLA as the resin (C) was melted at 210 ° C. with a lab mixer, 0.05 part by mass of dimethylpyrazole was added as the heterocyclic amine compound (B) and kneaded for 30 seconds. Next, 0.5 part by mass of aromatic monocarbodiimide was added as the carbodiimide compound (A) and kneaded for 2 minutes 30 seconds to produce a PLA resin composition (addition method: II).
  • Example 19 Production of master batch After melting 45.0 parts by mass of PLA as a resin (C) at 210 ° C with a lab mixer, 5.0 parts by mass of aromatic monocarbodiimide as a carbodiimide compound (A) and complex A resin additive in which 0.5 part by mass of dimethylpyrazole as a cyclic amine compound (B) was mixed in advance was added and kneaded for 3 minutes to produce a PLA resin-based master batch (addition method: I).
  • Example 20 As a resin (C), 45.0 parts by mass of PLA and 5.05 parts by mass of a PLA resin-based masterbatch produced in Example 19 were mixed, and kneaded at 210 ° C. for 3 minutes in a lab mixer to obtain a PLA resin composition. Was prepared (addition method: III).
  • Example 17 the PLA resin composition was produced in the same manner as in Example 17 except that the heterocyclic amine compound (B) was not added.
  • Example 6 (Comparative Example 6) In Example 21, a PLA resin composition was produced in the same manner as in Example 21 except that the heterocyclic amine compound (B) was not added.
  • nylon 6 resin Table 4 below shows the composition of the produced nylon 6 resin composition and master batch.
  • Example 23 As resin (C), 49.5 parts by mass of nylon 6 was melted at 280 ° C. with a laboratory mixer, 0.05 parts by mass of dimethylpyrazole was added as a heterocyclic amine compound (B), and kneaded for 30 seconds. Next, 0.5 part by mass of aromatic monocarbodiimide was added as the carbodiimide compound (A) and kneaded for 2 minutes and 30 seconds to produce a nylon 6 resin composition (addition method: II).
  • Example 24 Manufacture of a masterbatch After melt
  • Example 25 As a resin (C), 45.0 parts by mass of nylon 6 and 5.05 parts by mass of a nylon 6 resin-based masterbatch produced in Example 24 were mixed and kneaded at 280 ° C. for 3 minutes in a lab mixer. Six resin compositions were prepared (addition method: III).
  • Example 7 a nylon 6 resin composition was produced in the same manner as in Example 22 except that the heterocyclic amine compound (B) was not added.
  • Example 8 A nylon 6 resin composition was produced in the same manner as in Example 26 except that the heterocyclic amine compound (B) was not added in Example 26.

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  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

L'invention concerne un additif pour résine qui permet, lorsqu'un composé carbodiimide est utilisé en tant qu'additif améliorant la résistance à l'hydrolyse d'une résine, de supprimer efficacement la production de gaz isocyanate au moment de la production d'un mélange maître, d'une composition de résine ou similaire. L'invention concerne également un mélange maître mettant en oeuvre l'additif pour résine susmentionné ainsi que son procédé de production et une composition de résine mettant en oeuvre l'additif pour résine susmentionné ainsi que son procédé de production. Plus spécifiquement, l'invention concerne: un additif pour résine qui contient un composé carbodiimide (A) et un composé amine hétérocyclique(B); un mélange maître et une composition résine contenant l'additif pour résine susmentionné et (C) une résine; et un procédé de production de ceux-ci.
PCT/JP2016/079076 2015-10-01 2016-09-30 Additif pour résine, mélange maître mettant en oeuvre cet additif et composition de résine WO2017057703A1 (fr)

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JP2015196166A JP2018193410A (ja) 2015-10-01 2015-10-01 樹脂添加剤、並びにそれを用いたマスターバッチ及び樹脂組成物

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CN114213822A (zh) * 2021-12-09 2022-03-22 厦门建霖健康家居股份有限公司 一种改性绿色可降解材料及其制备方法

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JPH1036469A (ja) * 1996-07-26 1998-02-10 Japan Synthetic Rubber Co Ltd 熱硬化性樹脂
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WO2016163284A1 (fr) * 2015-04-06 2016-10-13 日清紡ケミカル株式会社 Composé polycarbodiimide modifié, agent de durcissement, et composition de résine thermodurcissable

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Publication number Priority date Publication date Assignee Title
JPH1036469A (ja) * 1996-07-26 1998-02-10 Japan Synthetic Rubber Co Ltd 熱硬化性樹脂
JP2004189860A (ja) * 2002-12-11 2004-07-08 Toyo Ink Mfg Co Ltd 縮合型熱可塑性樹脂組成物及びその利用
JP2010253740A (ja) * 2009-04-23 2010-11-11 Riken Technos Corp 真空成型用シート
JP2011052122A (ja) * 2009-09-02 2011-03-17 Mitsubishi Plastics Inc 難燃性熱収縮チューブ及び該チューブで被覆された部材
JP2014129500A (ja) * 2012-09-14 2014-07-10 Fujifilm Corp 芳香族ポリエステルフィルム、太陽電池モジュール用バックシートおよび太陽電池モジュール
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WO2016163284A1 (fr) * 2015-04-06 2016-10-13 日清紡ケミカル株式会社 Composé polycarbodiimide modifié, agent de durcissement, et composition de résine thermodurcissable

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114213822A (zh) * 2021-12-09 2022-03-22 厦门建霖健康家居股份有限公司 一种改性绿色可降解材料及其制备方法

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