JP2018193410A - Resin additive, and masterbatch and resin composition using the same - Google Patents

Abstract

To provide a resin additive which can effectively suppress occurrence of isocyanate gas at the time of production of masterbatch and a resin composition when a carbodiimide compound is used as an additive for improving hydrolysis resistance of a resin; 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.SOLUTION: There are provided a resin additive containing a carbodiimide compound (A) and a heterocyclic amine compound (B), and masterbatch and a resin composition containing the resin additive and a resin (C) and a method for producing them.SELECTED DRAWING: None

Description

  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.
However, 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.

For example, regarding a polyester resin, 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.
According to the aliphatic polyester resin composition described in Patent Document 1, 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. As a result, a large amount of isocyanate gas, which is an irritating decomposition gas, is generated, so it is necessary to restrict the working environment and ensure safety.

For such a problem, for example, 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.
Further, in 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 | occurrence | production of can be suppressed.

International Publication No. 2008/010355 International Publication No. 2010/071213 JP 2014-139284 A

  The resin composition described in Patent Document 2 is such that a compound having one carbodiimide group in one cyclic structure does not liberate an isocyanate compound even if it reacts with a polyester terminal. However, as a result of the reaction of the cyclic carbodiimide compound with the carboxyl group at the end of the polyester, 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.

  On the other hand, according to the polyester resin composition described in Patent Document 3, generation of isocyanate gas is suppressed, but the suppression effect is still not sufficient.

  Therefore, when a carbodiimide compound is used as an additive for improving the hydrolysis resistance of a polyester resin or the like, there is a demand for a technique for more effectively suppressing the generation of isocyanate gas during heat processing or melt kneading of the resin. .

  The present invention has been made in order to solve the above-described problems. When 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. Provided are 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.

That is, the present invention provides the following [1] to [13].
[1] A resin additive used in at least one of a polyester resin and a polyamide resin, which includes a carbodiimide compound (A) and a heterocyclic amine compound (B), and does not include a surfactant. Resin additive.
[2] The 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.
[3] The resin additive according to [1] or [2], wherein the heterocyclic amine compound (B) is at least one of pyrazole, dimethylpyrazole, and imidazole.
[4] The above-mentioned [1] to [3], wherein 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.
[5] The heterocyclic amine compound (B) according to any one of the above [1] to [4], which 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.

[6] A resin (C) and the resin additive according to any one of [1] to [5] above, wherein the resin (C) is at least one of a polyester resin and a polyamide resin. Is a masterbatch.
[7] The master batch according to [6], wherein the content of the carbodiimide compound (A) is 0.5 to 30 parts by mass with respect to 100 parts by mass of the resin (C).

[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 used. A method for producing a masterbatch by melt-kneading.

[9] 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 composition which is any 1 type.
[10] A resin composition obtained by blending the master batch according to [6] or [7] with the resin (C).
[11] The resin composition according to [9] or [10], wherein the content of the carbodiimide compound (A) is 0.1 to 10 parts by mass with respect to 100 parts by mass of the resin (C).

[12] 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.
[13] A method for producing a resin composition, comprising melt-kneading the master batch according to the above [6] or [7] and the resin (C).

According to the present invention, when a carbodiimide compound is 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.

  Hereinafter, the resin additive of the present invention, a masterbatch using the resin additive and a manufacturing method thereof, and a resin composition using the resin additive and a manufacturing method thereof will be described in detail.

[Resin additive]
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.

<Carbodiimide compound (A)>
The carbodiimide compound (A) is a compound containing a carbodiimide group (—N═C═N—), and is used to improve 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. From the viewpoint of reducing the amount of isocyanate gas generated, 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. Of these, 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. For example, carbodiimides such as organic phosphorus compounds and organometallic compounds It can synthesize | combine by the decarboxylation condensation reaction of diisocyanate using a catalyst. Specific examples of the diisocyanate 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. Among these, 4,4'-diphenylmethane diisocyanate and 1,3,5-triisopropylbenzene-2,4-diisocyanate are preferable from the viewpoint 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. Specific examples of the diisocyanate 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. Among these, 4,4'-dicyclohexylmethane diisocyanate is preferable from the viewpoint of high stability and improving the hydrolysis resistance of the resin.

In addition, 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 polymerization degree 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 the melt kneading of the resin.

<Heterocyclic amine compound (B)>
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 the decomposition temperature are values measured by a thermogravimetric / differential thermal analysis (TG-DTA) apparatus.

  Specific examples of the heterocyclic amine compound (B) 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, the amount is preferably 0.1 to 50 parts by mass with respect to 100 parts by mass of the carbodiimide compound (A).

[Master Badge]
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). Thus, when a masterbatch containing the resin and the resin additive of the present invention is used, the carbodiimide compound (A) is improved in uniform dispersibility when producing a hydrolysis-resistant resin composition, and carbodiimide is used. Generation | occurrence | production of the isocyanate gas derived from a compound (A) can be suppressed easily.

<Resin (C)>
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) , 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. Of these, polyethylene terephthalate, polybutylene terephthalate, polybutylene succinate, polyhydroxyalkanoic acid or polylactic acid is preferably used from the viewpoint of industrial availability, recycling and the like.
Examples of the polyamide resin 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. It is preferable that it is 5-30 mass parts, More preferably, it is 1-20 mass parts, More preferably, it is 2-15 mass parts.

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.
In addition, from the viewpoint of effectively suppressing the generation of isocyanate gas, 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. For example, the resin (C) can be melt-kneaded with a single-screw or twin-screw extruder, a roll mixer, or the like.
In addition, during melt-kneading, additives other than the components of the resin additive may be added as long as the effects of the present invention are not impaired. For example, 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 Examples include 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;

[Resin composition]
The resin composition of the present invention is obtained by blending the resin additive of the present invention with the resin (C). Alternatively, 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. Moreover, since the resin (C) here is the same as the resin (C) in the master batch, the description thereof is omitted.

  In the resin composition, 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. .

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. When using a master batch, (3) a method of melting and kneading a mixture in which the resin (C) and the master batch are mixed in advance, and (4) adding the master batch to the molten resin (C) and melting the mixture. Examples thereof include a kneading method. Among these, from the viewpoint of production efficiency, the method (3) or (4) using a master batch is preferable, and the method (3) is more preferable.
In the methods (1) and (2), from the viewpoint of effectively suppressing the generation of isocyanate gas, at the time of melt kneading, the carbodiimide compound (A) of the components of the resin additive is preceded. Alternatively, it is preferable that 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.
As the molding method of the resin composition, 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.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited by this.

[Production of resin composition]
In the examples, comparative examples and reference examples, the following are used as representative examples of the carbodiimide compound (A) and the heterocyclic amine compound (B) (above, resin additive) and the resin (C). Each resin composition and masterbatch shown in the following Tables 1 to 4 were manufactured by the following methods for adding various resin additives.
<Carbodiimide compound (A)>
Aromatic monocarbodiimide: bis (diisopropylphenyl) carbodiimide; “STABAXOL 1” manufactured by LANXESS
Aromatic polycarbodiimide: polydiphenylmethane carbodiimide; “Carbodilite 10M-SP” manufactured by Nisshinbo Chemical Co., Ltd.
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 seen as a decomposition temperature by TG-DTA up to 400 ° C. : No peak seen as decomposition temperature up to 400 ° C. with TG-DTA <Resin (C)>
(Polyester resin)
・ PET: Polyethylene terephthalate; “TRN-8550FF” manufactured by Teijin Limited
・ PBT: Polybutylene terephthalate; “Planac” manufactured by Toyobo Co., Ltd.
PLA: Polylactic acid; “Ingeo 4032D” manufactured by Nature Works LLC
(Polyamide resin)
・ Nylon 6: “UBE nylon” manufactured by Ube Industries, Ltd.

<Adding method of resin additive>
I: A mixture obtained by previously mixing the carbodiimide compound (A) and the heterocyclic amine compound (B) with the melted resin (C) was added and kneaded.
II: The heterocyclic amine compound (B) was added to the molten resin (C) and kneaded, and then the carbodiimide compound (A) was added and kneaded.
III: Resin (C) and the master batch prepared by the method of adding I were mixed and melt-kneaded.

<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).

(Examples 2-4, 8-11)
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. Was prepared (addition method: III).

(Comparative Example 1)
In 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.

(Comparative Example 2)
In 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.

(Comparative Example 3)
In Example 10, a PET resin composition was produced in the same manner as in Example 10 except that the heterocyclic amine compound (B) was not added.

(Reference Example 1)
As a resin (C), only PET was melted at 280 ° C. with a lab mixer, and then kneaded for 3 minutes to produce a PET resin composition blank.

<PBT resin>
Table 2 below shows the composition of the produced PBT resin composition and master batch.

(Examples 12 and 13)
After melting 49.5 parts by mass of PBT as a resin (C) at 280 ° C. with a laboratory mixer, a resin in which a carbodiimide compound (A) and a heterocyclic amine compound (B) are mixed in advance in the composition shown in Table 2 below. Additives were added and kneaded for 3 minutes to produce a PBT resin composition. (Addition method: I).

(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) Manufacture of a 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 Was prepared (addition method: III).

(Comparative Example 4)
In 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.

(Reference Example 2)
As a resin (C), only PBT was melted at 280 ° C. with a laboratory mixer, and then kneaded for 3 minutes to produce a blank of the PBT resin composition.

<PLA resin>
Table 3 below shows the composition of the produced PLA resin composition and master batch.

(Examples 17 and 21)
Resin in which 49.5 parts by mass of PLA as resin (C) was melted at 210 ° C. with a lab mixer, and then carbodiimide compound (A) and heterocyclic amine compound (B) were mixed in advance in the formulation shown in Table 3 below. The additive was added and kneaded for 3 minutes to produce a PLA resin composition (addition method: I).

(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) Manufacture 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).

(Comparative Example 5)
In 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.

(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.

(Reference Example 3)
As a resin (C), only PLA was melted at 210 ° C. by a lab mixer, and then kneaded for 3 minutes to produce a PLA resin composition blank.

<Nylon 6 resin>
Table 4 below shows the composition of the produced nylon 6 resin composition and master batch.

(Examples 22 and 26)
After 49.5 parts by mass of nylon 6 as a resin (C) was melted at 280 ° C. with a laboratory mixer, the carbodiimide compound (A) and the heterocyclic amine compound (B) were mixed in advance in the composition shown in Table 4 below. The resin additive was added and kneaded for 3 minutes to produce a nylon 6 resin composition (addition method: I).

(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 | dissolving 45.0 mass parts of nylon 6 as resin (C) at 280 degreeC with a laboratory mixer, 5.0 mass parts of aromatic monocarbodiimide as a carbodiimide compound (A) and A resin additive in which 0.5 part by mass of dimethylpyrazole as a heterocyclic amine compound (B) was previously mixed was added and kneaded for 3 minutes to produce a nylon 6 resin-based masterbatch (addition method: I) .

(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).

(Comparative Example 7)
In Example 22, 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.

(Comparative 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.

(Reference Example 4)
As a resin (C), only nylon 6 was melted at 280 ° C. with a laboratory mixer, and then kneaded for 3 minutes to produce a nylon 6 resin composition blank.

[Measurement of isocyanate gas generation amount]
In the above-mentioned Examples, Comparative Examples and Reference Examples, during the melting of the resin (C) and the kneading of each compounding composition, the isocyanate gas generation amount (gas concentration) from the resin inlet of the lab mixer was measured using an isocyanate gas measuring instrument (Honeywell Corporation). “Chemkey gas monitor TLD-1” (manufactured by Chem.); Detectable range 2-60 ng / L).
These measurement results are shown in Tables 1 to 4.

[Evaluation of hydrolysis resistance of resin composition]
Each resin composition produced in the above Examples, Comparative Examples and Reference Examples was pulverized with a small pulverizer for laboratories, then sheeted to a thickness of 1 mm by hot pressing under the following conditions, and further crystallized. The crystallized sheet was cut into a 1 cm × 10 cm strip to obtain a measurement sample, which was wet-heat treated under the following processing conditions.
Hot press conditions PET and PBT: 270 ° C
PLA: 190 ° C
Nylon 6: 280 ° C
Wet heat treatment conditions PET and PBT: 121 ° C., water vapor pressure 2 atm
PLA: 80 ° C., 95% RH
Nylon 6: 121 ° C., water vapor pressure 2 atm
After wet heat treatment for a predetermined time, the tensile strength of each measurement sample was measured with a universal material testing machine (manufactured by Instron; model 5582), and the tensile strength retention was calculated according to the following formula.
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.
These evaluation results are shown in Tables 1 to 4.

As is apparent from the results shown in Tables 1 to 4, according to the resin additive of the present invention, when a carbodiimide compound is used as an additive for improving the hydrolysis resistance of the resin, the resin composition is produced at the time of production. It was found that generation of isocyanate gas can be effectively suppressed. It was also confirmed that the hydrolysis resistance imparted by the carbodiimide compound is hardly affected by the use of the resin additive.
Moreover, it was recognized that generation of isocyanate gas can be effectively suppressed even during the production of the master batch (Examples 6, 15, 19, and 24).

Claims (13)

  A resin additive used for at least one of a polyester resin and a polyamide resin, which includes a carbodiimide compound (A) and a heterocyclic amine compound (B), and does not include a surfactant. .   The resin additive according to claim 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 resin additive according to claim 1 or 2, wherein the heterocyclic amine compound (B) is at least one of pyrazole, dimethylpyrazole and imidazole.   The said carbodiimide compound (A) is at least any one of aromatic monocarbodiimide, aromatic polycarbodiimide, aliphatic monocarbodiimide, and aliphatic polycarbodiimide, The any one of Claims 1-3. Resin additive.   The resin additive according to any one of claims 1 to 4, wherein 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).   A master batch comprising the resin additive according to any one of claims 1 to 5 and a resin (C), wherein the resin (C) is at least one of a polyester resin and a polyamide resin.   The master batch according to claim 6, wherein a content of the carbodiimide compound (A) is 0.5 to 30 parts by mass with respect to 100 parts by mass of the resin (C).   It is a manufacturing method of the masterbatch of Claim 6 or 7, Comprising: Manufacture of a masterbatch which melt-kneads the resin additive of any one of Claims 1-5, and the said resin (C). Method.   The resin additive according to any one of claims 1 to 5 is blended with a resin (C), and the resin (C) is at least one of a polyester resin and a polyamide resin. , Resin composition.   The resin composition formed by mix | blending the masterbatch of Claim 6 or 7 with the said resin (C).   The resin composition according to claim 9 or 10, wherein a content of the carbodiimide compound (A) is 0.1 to 10 parts by mass with respect to 100 parts by mass of the resin (C).   The resin additive according to any one of claims 1 to 5 and a resin (C) are melt-kneaded, and the resin (C) is at least one of a polyester resin and a polyamide resin. A method for producing a resin composition.   The manufacturing method of the resin composition which melt-kneads the masterbatch of Claim 6 or 7, and the said resin (C).