TW201730247A - Resin additive, and master batch and resin composition using same - Google Patents

Abstract

Provided are a resin additive, a master batch using said resin additive and a production method for same, and a resin composition using said resin additive and a production method for same, capable of effectively suppressing the generation of isocyanate gas at the time a master batch or a resin composition is produced, when using a carbodiimide compound as an additive to improve the hydrolysis resistance of a resin. The present invention provides: a resin additive comprising (A) a carbodiimide compound and (B) a heterocyclic amine compound; and a master batch and a resin composition comprising said resin additive and (C) a resin, and production methods for same.

Description

Resin additive, and masterbatch and resin composition using the same

The present invention relates to a resin additive used in the production of a resin composition such as a polyester resin or a polyamide resin, a masterbatch using the above resin additive, a method for producing the same, and a resin composition using the resin additive and Its manufacturing method.

The polyester resin such as PET is excellent in transparency, mechanical strength, melt stability, solvent resistance, and the like, and the polyamide resin such as nylon is excellent in mechanical strength, flexibility, chemical resistance, and the like. It is widely used in fibers, films, sheets, etc., and is also used for recycling.

However, the polyester resin and the polyamide resin are obtained by agglomeration of a so-called ester bond or a guanamine bond, and these bond sites have a property of being easily hydrolyzed by deterioration over time. Therefore, in order to improve the hydrolysis resistance, a carbodiimide compound is added to the resin composition.

For example, in the polyester resin, Patent Document 1 discloses that the aromatic polyester resin composition is blended with an aromatic polycarbodiimide compound to improve the hydrolysis resistance of the aliphatic polyester resin composition.

According to the aliphatic polyester resin composition described in Patent Document 1, although hydrolysis of the aliphatic polyester resin can be suppressed, in the mixing of the aliphatic polyester resin at a melting temperature or higher, the carboxyl group and the aromatic carbon of the polyester resin The carbodiimide group of the diimine compound undergoes a reaction, and the aromatic carbodiimide compound decomposes. As a result, since an isocyanate gas which is a stimulating decomposition gas is generated in a large amount, it is necessary to limit the working environment and ensure safety. In addition, when the polyester resin composition having a large amount of isocyanate gas is used for injection molding, the mold has a large amount of dirt, and the mold is required to be cleaned frequently because of the low yield of the molded article, and the production efficiency of the molded article is also caused. reduce.

For example, Patent Document 2 describes a resin composition obtained by mixing a polyester and a cyclic carbodiimide compound, thereby suppressing malodor caused by free isocyanate.

Further, Patent Document 3 describes a polyester resin composition containing a polyester resin, an aromatic carbodiimide, and an aliphatic carbodiimide, and can be added from the viewpoint of improving the hydrolysis stability of the polyester resin. The decomposition gas of aromatic carbodiimide is produced.

[Previous Technical Literature] [Patent Literature]

Patent Document 1: International Publication No. 2008/010355

Patent Document 2: International Publication No. 2010/071213

Patent Document 3: Japanese Laid-Open Patent Publication No. 2014-139284

The resin composition described in Patent Document 2 is a compound having one carbodiimide group in one cyclic structure, and is a compound which does not release an isocyanate compound even when reacted at the end of the polyester. However, as a result of the reaction of the cyclic carbodiimide compound with the carboxyl group at the terminal of the polyester, the isocyanate group remains at the end of the polyester resin. The residual isocyanate group further reacts with other terminal groups such as a hydroxyl group, so that the polyester is viscous, causing deterioration in workability, and the isocyanate group is also detached.

On the other hand, according to the polyester resin composition described in the above Patent Document 3, the generation of the isocyanate gas can be suppressed, but the effect of suppression cannot be said to be sufficient.

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

The present invention has been made to solve the above problems, and an object of the present invention is to provide an effective use of a carbodiimide compound as an additive for improving the hydrolysis resistance of a polyester resin or a polyamide resin. A resin additive for producing isocyanate gas at the time of production of a product, a masterbatch using the above resin additive, a method for producing the same, and a resin composition using the resin additive and a method for producing the same.

The present invention is based on the fact that it is found that the specified heterocyclic amine compound is effective as a resin additive before the production of the isocyanate gas from the carbodiimide compound is suppressed, and is completed.

That is, the present invention provides the following [1] to [13].

[1] A resin additive which is a resin additive for at least any one of a polyester resin and a polyamide resin, which comprises a carbodiimide compound (A) and a heterocyclic amine compound (B), and does not include an interface. Active agent.

[2] The resin additive according to the above [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 the above [1] or [2] wherein the heterocyclic amine compound (B) is at least one of pyrazole, dimethylpyrazole and imidazole.

[4] The resin additive according to any one of [1] to [3] wherein the carbodiimide compound (A) is an aromatic monocarbodiimide or an aromatic polycarbodiene. At least any one of an imine, an aliphatic monocarbodiimide, and an aliphatic polycarbodiimide.

[5] The resin additive according to any one of the above [1] to [4], wherein the heterocyclic amine compound (B) is 0.1 to 50 with respect to 100 parts by mass of the carbodiimide compound (A). Parts by mass.

[6] A masterbatch comprising the resin (C) and the resin additive according to any one of the above [1] to [5], wherein at least any one of the resin (C)-based polyester resin and the polyamide resin One.

[7] The masterbatch according to the above [6], wherein the content of the carbodiimide compound (A) is from 0.5 to 30 parts by mass based on 100 parts by mass of the resin (C).

[8] The method of producing a masterbatch according to the above [6] or [7], wherein the resin additive according to any one of the above [1] to [5], The resin (C) is melt-kneaded.

[9] A resin composition obtained by blending the resin additive according to any one of the above [1] to [5] to a resin (C), wherein the resin (C) is a polyester resin and a polyfluorene At least any one of the amine resins.

[10] A resin composition obtained by blending the master batch described in the above [6] or [7] with the resin (C).

[11] The resin composition according to the above [9] or [10], wherein the content of the carbodiimide compound (A) is 0.1 to 10 parts by mass based on 100 parts by mass of the resin (C).

[12] A method for producing a resin composition, which is obtained by melt-kneading a resin additive according to any one of the above [1] to [5], wherein the resin (C) is a polyester resin and At least any one of polyamine resins.

[13] A method for producing a resin composition, which comprises subjecting the master batch described in the above [6] or [7] to the resin (C).

According to the present invention, it is possible to effectively suppress the generation of isocyanate gas in the production of the master batch and the resin composition when the carbodiimide compound is used as an additive for improving the hydrolysis resistance of the polyester resin or the polyamide resin. A resin additive, and a masterbatch and a resin composition using the same.

Therefore, according to the present invention, it is possible to produce a masterbatch and a resin composition of a polyester resin having a hydrolysis resistance, a polyamide resin, and a resin composition while effectively suppressing the generation of an irritating isocyanate gas and ensuring a safe working environment.

[Formation of the Invention]

Hereinafter, the resin additive of the present invention, a masterbatch using the above resin additive, a method for producing the same, and a resin composition using the resin additive and a method for producing the same 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. Further, the carbodiimide compound (A) and the heterocyclic amine compound (B) are not included in the surfactant. According to such an additive, a resin having a solubilized bonding site of a so-called ester bond or a guanamine bond can be imparted with hydrolysis resistance by a carbodiimide compound (A) while a heterocyclic amine compound can be used. (B) Inhibiting the production of an isocyanate gas derived from the carbodiimide compound (A).

Further, the resin additive may be one prepared by mixing and mixing the carbodiimide compound (A) and the heterocyclic amine compound (B) in advance, or may be added separately when used.

As a reason for suppressing the generation of the isocyanate gas, it is considered that the reaction between the carboxyl group and the amine group of the polyester resin and the polyamide resin and the carbodiimide group of the carbodiimide compound (A) is thermally decomposed. The isocyanate gas is converted into a compound different from the isocyanate by reacting with the heterocyclic amine compound (B) which is simultaneously vaporized.

Further, the surfactant has an action of suppressing the generation of isocyanate gas similarly to 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, one type may be used alone or two or more types may be used in combination. From the viewpoint of lowering the amount of production of the isocyanate gas, it is preferred to use an aliphatic monocarbodiimide or an aliphatic polycarbodiimide, but from the viewpoint of suppressing the increase in viscosity and preventing coloration in view of the processability of the resin. In particular, an aromatic monocarbodiimide or an aromatic polycarbodiimide is preferably used.

The aromatic monocarbodiimide-based one carbodiimide group is directly bonded to the aromatic carbodiimide compound, and specific examples thereof include diphenylcarbodiimide and bis(methylphenyl). Carbodiimide, bis(methoxyphenyl)carbodiimide, bis(nitrophenyl)carbodiimide, bis(dimethylphenyl)carbodiimide, bis(diisopropylbenzene) Carbodiimide, bis(di-tertiary-butylphenyl)carbodiimide, and the like. Among 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 a molecule, and the carbodiimide group is directly bonded to an aromatic ring, for example, by using an organic It is synthesized by a decarboxylation condensation reaction of a diisocyanate of a carbodiimidation catalyst such as a phosphorus compound or an organometallic compound. Specific examples of the diisocyanate include 1,5-naphthalene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, and 1,3-stretch. Phenyl diisocyanate, 1,4-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6- Toluene diisocyanate, 3,3',5,5'-tetraisopropylbiphenyl-4,4'-diisocyanate, 1,3,5-triisopropylbenzene-2,4-diisocyanate or the like. These may be used alone or in combination of two or more. Among these, 4,4'-diphenylmethane diisocyanate and 1,3,5-triisopropylbenzene-2 are preferable from the viewpoint of high stability and improvement of hydrolysis resistance of the resin. , 4-diisocyanate.

The aliphatic monocarbodiimide-based one carbodiimide group is directly bonded to a carbon carbodiimide compound other than the aromatic ring, and specific examples thereof include dicyclohexylcarbodiimide and diisopropyl. Carbodiimide, N-ethyl-N'-(3-dimethylaminopropyl)carbodiimide, and the like. Among 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 a molecule and a carbodiimide group bonded to a carbon atom other than the aromatic ring, for example, It is synthesized by a decarboxylation condensation reaction of a diisocyanate of a carbodiimidation catalyst such as an organophosphorus compound or an organometallic compound. Specific examples of the diisocyanate include hexamethylene diisocyanate, cyclohexane-1,4-diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, and methylcyclohexane. Alkyl diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, xylene diisocyanate, tetramethylxylene diisocyanate, and the like. These may be used alone or in combination of two or more. Among these, 4,4'-dicyclohexylmethane diisocyanate is preferred from the viewpoint of high stability and improvement of hydrolysis resistance of the resin.

In addition, an aromatic polycarbodiimide or an aliphatic polycarbodiimide can be used as an isocyanate at the end of the diisocyanate used in the synthesis. The reactive monofunctional compound is reacted to thereby terminate the polymerization degree. Examples of such a compound include monoisocyanates such as phenyl isocyanate, toluene isocyanate, isopropylphenyl isocyanate, and cyclohexyl isocyanate; and alcohols such as methanol, isopropyl alcohol, phenol, and polyethylene glycol monomethyl ether; An amine such as butylamine, diethylamine or cyclohexylamine; a carboxylic acid such as propionic acid or benzoic acid.

The degree of polymerization of the aromatic polycarbodiimide or the aliphatic polycarbodiimide is preferably from 2 to 200, more preferably from 5 to 30, from the viewpoint of suppressing generation of isocyanate gas during melt-kneading of the resin.

<Heterocyclic Amine Compound (B)>

The heterocyclic amine compound (B) has a function of suppressing the generation of an isocyanate gas derived from the carbodiimide compound (A). Therefore, from the viewpoint of effectively suppressing the generation of the isocyanate gas during the melt-kneading of the resin, it is preferable to vaporize without decomposing in the vicinity of the melting temperature of the added polyester resin or the polyamide resin. It is a vaporization temperature of 100~300 °C and a decomposition temperature of more than 300 °C.

The aforementioned vaporization temperature and 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, and piperidin. , Porphyrin, Quinuclidine, pyrrole, pyrazole, imidazole, pyridine, hydrazine Pyrimidine, pyridyl , Oxazole, thiazole. These may be used alone or in combination of two or more. Among these, from the viewpoints of ease of industrial availability, reactivity with an isocyanate gas, and volatility during melt-kneading of a resin, pyrazole, dimethylpyrazole or imidazole is preferred. Jia is dimethylpyrazole.

The viewpoint of the fact that the hydrolysis resistance imparted by the carbodiimide compound (A) is remarkably lowered, the resin is not colored, and the amount of isocyanate gas generated when the resin is melt-kneaded is sufficiently lowered, The content of the heterocyclic amine compound (B) in the resin additive is preferably from 0.1 to 50 parts by mass, more preferably from 0.5 to 30 parts by mass, even more preferably from 1 to 20 parts by mass, per 100 parts by mass of the imine compound (A).

[masterbatch]

The masterbatch of the present invention comprises the resin additive of the present invention and the resin (C). That is, the carbodiimide compound (A), the heterocyclic amine compound (B), and the resin (C) are contained. In this way, when a masterbatch comprising a resin and a resin additive of the present invention is used, the uniform dispersibility of the carbodiimide compound (A) can be improved while producing a resin composition having hydrolysis resistance. The production of the isocyanate gas from the carbodiimide compound (A) is simply suppressed.

<Resin (C)>

The resin (C) is at least one of a polyester resin and a polyamide resin. These resins can be improved by the addition of the carbodiimide compound (A) to improve hydrolysis resistance.

Examples of the polyester resin include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polybutylene succinate (PBS), and polysuccinic acid/two. Polybutylene succinate adipate (PBSA), polybutylene adipate terephthalate (PBAT), polyhydroxyalkanoic acid (PHA), polylactic acid (PLA) ), polyethylene naphthalate, polyarylate, terephthalic acid-isophthalic acid-ethylene glycol copolyester (poly(ethylene) Terephthalate-co-isophthalate)). These may be used alone or in combination of two or more. Among these, it is suitable to use polyethylene terephthalate, polybutylene terephthalate, and polybutylene succinate from the viewpoints of industrial ease of use and recycling. Ester, polyhydroxyalkanoic acid or polylactic acid.

Examples of the polyamide resin include nylon 6, nylon 11, nylon 66, nylon 12, nylon 610, and nylon 6T.

The content of the carbodiimide compound (A) in the master batch is preferably from 100 parts by mass based on 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. 0.5 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 can be obtained by at least melting and kneading the carbodiimide compound (A) and the heterocyclic amine compound (B) with the resin (C).

According to such a production method, the master batch can be produced while suppressing the generation of the isocyanate gas from the carbodiimide compound (A) while ensuring a safe working environment during the melt-kneading of the resin.

Specific examples of the method for producing the master batch include (1) a method of melt-kneading a mixture in which a resin (C) and the resin additive are previously mixed, and (2) a molten resin (C). A method of adding the aforementioned resin additive and kneading the same.

Further, from the viewpoint of effectively suppressing the generation of the isocyanate gas, at the time of melt-kneading, it is preferred to introduce a heterocyclic amine compound before or at the same time as the carbodiimide compound (A) in the component of the aforementioned resin additive. B) Add to resin (C).

The melt-kneading means is not particularly limited and can be carried out using a well-known kneader. For example, the resin (C) can be melt-kneaded by a uniaxial or biaxial extruder, a roll mixer or the like.

Moreover, in the case of melt-kneading, an additive other than the components of the above-mentioned resin additive may be added to the extent that the effects of the present invention are not impaired. For example, inorganic fillers such as vermiculite, alumina, sand, clay, and slag; reinforcing agents such as acicular inorganic materials; stabilizers such as titanium oxide; radical scavengers; stabilizers such as antioxidants; and metal hydration; A flame retardant such as a halogen-based flame retardant or a phosphorus-based flame retardant; a nucleating agent such as talc; a silver ion, a copper ion, an antibacterial agent containing a zeolite or the like; an antifungal agent.

[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 masterbatch of the present invention is blended in the resin (C).

Further, the master batch is different from the resin composition described above, and the resin composition of the present invention does not include the master batch. In addition, since the resin (C) here is the same as the resin (C) in the above-mentioned master batch, description is abbreviate|omitted.

In the resin composition, the content of the carbodiimide compound (A) in the component of the resin additive is 100 parts by mass based on 100 parts by mass of the resin (C) from the viewpoint of improving the hydrolysis resistance of the resin composition. It is preferably 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 can be obtained by at least melting and kneading the carbodiimide compound (A) and the heterocyclic amine compound (B) with the resin (C).

Further, the resin composition may be produced by melt-kneading the master batch and the resin (C).

According to such a production method, the resin composition can be produced while suppressing the generation of the isocyanate gas from the carbodiimide compound (A) while ensuring a safe working environment during the melt-kneading of the resin.

Further, the resin composition can suppress the generation of the isocyanate gas, and can also have an effect of suppressing the fouling of the mold when the injection molding is performed.

Specific examples of the method for producing the resin composition include (1) a method of melt-kneading a mixture in which a resin (C) and the resin additive are previously mixed, and (2) a molten resin (C). A method in which the aforementioned resin additive is added and kneaded. Further, in the case of using a master batch, (3) a method of melt-kneading a mixture of the resin (C) and the master batch previously mixed, and (4) adding the master batch to the molten resin (C) And a method of melt-kneading, etc. Among these, from the viewpoint of production efficiency, the method of (3) or (4) of the master batch is preferred, and the method of (3) is more preferred.

Further, in the methods (1) and (2), from the viewpoint of effectively suppressing the generation of the isocyanate gas, in the melt-kneading, the carbodiimide compound in the component of the resin additive is preferably used. The heterocyclic amine compound (B) is added to the resin (C) before or at the same time as (A).

The additives other than the melt-kneading means and the components of the above-described resin additive are the same as those in the above-described method for producing a master batch.

As a method of forming the resin composition, a well-known method such as an injection molding method, a film molding method, a blow molding method, or a foam molding method can be used, and a film or a sheet can be formed by using a temperature higher than a melting temperature of the resin. In various forms such as a shape or a block shape, a material or a processed product of a variety of uses can be obtained. Specifically, it can be used for various purposes such as electrical and electronic equipment components such as housings for electrified products, building materials, automobile parts, daily necessities, medical products, and agricultural products.

[Examples]

Hereinafter, the present invention will be described in detail by way of examples, but the invention is not limited thereto.

[Manufacture of Resin Composition]

In the examples, the comparative examples, and the reference examples, the carbodiimide compound (A), the heterocyclic amine compound (B) (the above is a resin additive), and the resin (C) are represented by the following examples. Each resin composition and master batch shown in the following Tables 1 to 4 were produced by the method of adding various resin additives shown below.

<Carbodiimide Compound (A)>

‧Aromatic monocarbodiimide: bis(diisopropylphenyl)carbodiimide; "Stabaxol 1" manufactured by Lanxess Co., Ltd.

‧Aromatic polycarbodiimide: polydiphenylmethane carbodiimide; "CARBODILITE 10M-SP" manufactured by Nisshinbo Chemical Inc.

‧ aliphatic polycarbodiimide: polydicyclohexylmethane carbodiimide; "CARBODILITE LA-1" manufactured by Nisshinbo Chemical Inc.

<Heterocyclic Amine Compound (B)>

‧ Dimethylpyrazole: manufactured by Otsuka Chemical Co., Ltd.; vaporization temperature 120 ° C, decomposition temperature: no peak as decomposition after TG-DTA up to 400 °C

‧Imidazole: manufactured by Shikoku Chemical Industry Co., Ltd.; vaporization temperature 130 °C, decomposition temperature: no peak as decomposition after TG-DTA up to 400 °C

<Resin (C)>

(polyester resin)

‧PET: polyethylene terephthalate; "TRN-8550FF" manufactured by Teijin Co., Ltd.

‧PBT: polybutylene terephthalate; "PLANAC" manufactured by Toyobo Co., Ltd.

‧PLA: Polylactic acid; "Ingeo 4032D" manufactured by NatureWorks LLC

(polyamide resin)

‧Nylon 6: UBE Nylon Co., Ltd. made "UBE Nylon"

<Addition method of resin additive>

I: A premixed carbodiimide compound (A) and a heterocyclic amine compound (B) are added to the molten resin (C) and kneaded.

II: After the heterocyclic amine compound (B) is added to the molten resin (C) and kneaded, the carbodiimide compound (A) is added and kneaded.

III: A mixed resin (C) and a masterbatch produced by the above-described method of adding I, and melt-kneaded.

[Evaluation method]

In the production of each of the resin compositions or the respective master batches of the above examples, comparative examples and reference examples, various evaluations were carried out by the methods described below. The results of these measurements are also shown in Tables 1 to 4.

<isocyanate gas generation amount (gas concentration)>

During the melting of the resin (D) and the kneading of the respective blending compositions, the amount of isocyanate gas (gas concentration) from the resin inlet of the laboratory mixer is used, and the isocyanate gas measuring device (Honeywell) The company's "ChemKey Gas Monitor TLD-1"; detectable range 2~60Ng/L).

<Hydrolysis resistance of resin composition>

Each of the resin compositions produced was pulverized by a laboratory small-sized pulverizer, and then flaky to a thickness of 1 mm by hot pressing under the following conditions, and further crystallized. The crystallized sheet was cut into a short booklet of 1 cm × 10 cm, and as a measurement sample, wet heat treatment was performed under the following treatment conditions.

Hot pressing condition

PET and PBT: 270 ° C

PLA: 190 ° C

Nylon 6: 280 ° C

Wet heat treatment condition

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 the wet heat treatment for a predetermined period of time, the tensile strength of each test sample was measured by a universal material testing machine (manufactured by INSTRON; Model 5582). The degree of tensile strength retention was calculated according to the following formula.

Tensile strength retention ratio (%) = (tensile strength after initial heat treatment / initial tensile strength) × 100

The time until the tensile strength retention rate became 50% was defined as the hydrolysis resistance time. The longer the hydrolysis resistance time, the more excellent the hydrolysis resistance.

<Mold dirt>

Each of the resin compositions produced was molded into a molded article of 100 mm × 100 mm × 1 mm by a continuous injection using a steel mold using a steel mold under the molding conditions shown below.

Forming conditions

Cylinder temperature: 280 ° C

Mold temperature: 60 ° C

Cycle time: 40 seconds

The dirt (mist and oil film) adhered to the formed mold was visually confirmed and wiped with a wiping cloth to evaluate. The evaluation criteria are as follows.

Evaluation basis

A: There is no white mist or iridescent oil film on the surface of the mold.

B: The surface of the mold slightly produces a white mist and an iridescent oil film, but the dirt can be easily wiped off.

C: The surface of the mold produces a white mist, an iridescent oil film, and it is difficult to wipe off the dirt.

D: The surface of the mold obviously produces a white mist, an iridescent oil film, and the dirt cannot be wiped off.

In addition, regarding the dirt of the unevaluated mold, it is marked as "-" in Tables 1 to 4.

[PET resin]

The blending composition of the produced PET resin composition and the master batch is shown in Table 1 below.

(Example 1)

By using a laboratory mixer (LABO PLASTOMILL "Segment mixer KF70V" manufactured by Toyo Seiki Seisakusho Co., Ltd.; the same applies hereinafter), 49.5 parts by mass of PET as the resin (C) is melted at 280 ° C, and premixed as carbon is added. 0.5 parts by mass of the aromatic monocarbodiimide of the diimine compound (A) and 0.05 parts by mass of a dimethylpyrazole as a heterocyclic amine compound (B), and kneaded for 3 minutes to produce PET resin composition (addition method: I).

(Examples 2 to 4, 8 to 11)

The PET was produced in the same manner as in Example 1 except that the carbodiimide compound (A), the heterocyclic amine compound (B), and the resin (C) were blended as shown in the following Table 1. Resin composition.

(Example 5)

After melting 49.5 parts by mass of the resin (C) at 280 ° C by a laboratory mixer, 0.05 parts by mass of dimethylpyrazole as a heterocyclic amine compound (B) was added and kneaded for 30 seconds. . Then, 0.5 parts by mass of the aromatic monocarbodiimide as the carbodiimide compound (A) was added and kneaded for 2 minutes and 30 seconds to prepare a PET resin composition (addition method: II).

(Example 6) Manufacturing of masterbatch

Using a laboratory mixer, 280 ° C as a resin (C) After 45.0 parts by mass of the PET is melted, 5.0 parts by mass of the aromatic monocarbodiimide as the carbodiimide compound (A) and 0.5 parts by mass of the dimethylpyridine as the heterocyclic amine compound (B) are added in advance. A resin additive obtained by azole was kneaded for 3 minutes to prepare a masterbatch of a PET resin matrix (addition method: I).

(Example 7)

A masterbatch of 45.0 parts by mass of PET as the resin (C) and 5.05 parts by mass of the PET resin substrate produced in Example 6 was mixed and kneaded at 280 ° C for 3 minutes using a laboratory mixer to prepare a PET resin composition. (Additional method: III).

(Comparative Example 1)

In the same manner as in Example 1, except that the heterocyclic amine compound (B) was not added, the PET resin composition was produced.

(Comparative Example 2)

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)

A PET resin composition was produced in the same manner as in Example 10 except that the heterocyclic amine compound (B) was not added.

(Refer to Example 1)

A PET which is a resin (C) was melted at 280 ° C using a laboratory mixer and kneaded for 3 minutes to obtain a blank sample of a PET resin composition.

[PBT resin]

The blending composition of the produced PBT resin composition and the master batch is shown in Table 2 below.

(Examples 12 and 13)

After the PBT of 49.5 parts by mass as the resin (C) was melted at 280 ° C by a laboratory mixer, the carbodiimide compound (A) and the heterocyclic amine were mixed in advance with the blending composition shown in Table 2 below. The resin additive obtained by the compound (B) was kneaded for 3 minutes to produce a PBT resin composition. (Add method: I).

(Example 14)

After the PBT of 49.5 parts by mass of the resin (C) was melted at 280 ° C in a laboratory mixer, 0.05 parts by mass of dimethylpyrazole as a heterocyclic amine compound (B) was added and kneaded for 30 seconds. . Next, 0.5 part by mass of the aromatic monocarbodiimide as the carbodiimide compound (A) was added and kneaded for 2 minutes and 30 seconds to prepare a PBT resin composition (addition method: II).

(Example 15) Production of masterbatch

After the PBT of 45.0 parts by mass of the resin (C) was melted at 280 ° C in a laboratory mixer, 5.0 parts by mass of the aromatic monocarbodiimide as a carbodiimide compound (A) was added in advance. A resin additive obtained by kneading the resin additive of 0.5 parts by mass of dimethylpyrazole as the heterocyclic amine compound (B) for 3 minutes to produce a PBT resin matrix (addition method: I).

(Embodiment 16)

A PBT resin composition was prepared by mixing 45.0 parts by mass of PBT as a resin (C) and 5.05 parts by mass of a PBT resin matrix prepared in Example 15 by a laboratory mixer at 280 ° C for 3 minutes. (add Addition method: III).

(Comparative Example 4)

A PBT resin composition was produced in the same manner as in Example 12 except that the heterocyclic amine compound (B) was not added.

(Refer to Example 2)

Only a PBT which is a resin (C) was melted at 280 ° C by a laboratory mixer and kneaded for 3 minutes to obtain a blank sample of a PBT resin composition.

[PLA resin]

The blending composition of the produced PLA resin composition and the master batch is shown in Table 3 below.

(Examples 17, 21)

After using a laboratory mixer, 49.5 parts by mass of the PLA as the resin (C) was melted at 210 ° C, and then the addition was carried out in advance as shown in Table 3 below. A resin additive obtained by mixing a carbodiimide compound (A) and a heterocyclic amine compound (B) was kneaded for 3 minutes to prepare a PLA resin composition (addition method: I).

(Embodiment 18)

After melting 49.5 parts by mass of the resin (C) at a temperature of 210 ° C in a laboratory mixer, 0.05 parts by mass of dimethylpyrazole as a heterocyclic amine compound (B) was added and kneaded for 30 seconds. . Next, 0.5 parts by mass of the aromatic monocarbodiimide as the carbodiimide compound (A) was added and mixed for 2 minutes and 30 seconds to prepare a PLA resin composition (addition method: II).

(Example 19) Production of masterbatch

After melting 45.0 parts by mass of the resin (C) as a resin (C) by a laboratory mixer, 5.0 parts by mass of the aromatic monocarbodiimide previously mixed as the carbodiimide compound (A) was added. A resin additive obtained by kneading the resin additive of 0.5 parts by mass of dimethylpyrazole as the heterocyclic amine compound (B) for 3 minutes to produce a masterbatch of a PLA resin matrix (addition method: I).

(Embodiment 20)

A masterbatch of 45.0 parts by mass of PLA as the resin (C) and 5.05 parts by mass of the PLA resin matrix produced in Example 19 was mixed and kneaded at 210 ° C for 3 minutes using a laboratory mixer to prepare a PLA resin composition. (Addition method: III).

(Comparative Example 5)

In the same manner as in Example 17, except that the heterocyclic amine compound (B) was not added, the PLA resin composition was produced.

(Comparative Example 6)

In Example 21, the heterocyclic amine compound (B) was not added, and The PLA resin composition was produced in the same manner as in Example 21.

(Refer to Example 3)

Only the PLA which is the resin (C) was melted at 210 ° C by a laboratory mixer and kneaded for 3 minutes to obtain a blank sample of the PLA resin composition.

[Nylon 6 resin]

The blending composition of the manufactured nylon 6 resin composition and the master batch is shown in Table 4 below.

(Examples 22 and 26)

After melt-mixing 49.5 parts by mass of the resin (C) at a temperature of 280 ° C using a laboratory mixer, the carbodiimide compound (A) and the impurities mixed in advance with the blending composition shown in Table 4 below were added. The resin additive obtained by the cyclic amine compound (B) was kneaded for 3 minutes to produce a nylon 6 resin composition (addition method: I).

(Example 23)

Using a laboratory mixer, 280 ° C as a resin (C) After 49.5 parts by mass of the nylon 6 was melted, 0.05 parts by mass of dimethylpyrazole as the heterocyclic amine compound (B) was added and kneaded for 30 seconds. Then, 0.5 parts by mass of the aromatic monocarbodiimide as the carbodiimide compound (A) was added and kneaded for 2 minutes and 30 seconds to prepare a nylon 6 resin composition (addition method: II).

(Example 24) Production of masterbatch

After melt-mixing 45.0 parts by mass of the resin (C) at a temperature of 280 ° C using a laboratory mixer, 5.0 parts by mass of the aromatic mono-carbon sub-premixed as a carbodiimide compound (A) was added. A resin additive obtained by mixing an amine with 0.5 parts by mass of dimethylpyrazole as the heterocyclic amine compound (B) and kneading for 3 minutes to produce a masterbatch of a nylon 6 resin matrix (addition method: I).

(Embodiment 25)

A masterbatch of 45.0 parts by mass of the resin (C) and 65.0 parts by mass of the nylon 6 resin matrix produced in Example 24 was mixed and kneaded at 280 ° C for 3 minutes using a laboratory mixer. Nylon 6 resin composition (addition method: III).

(Comparative Example 7)

In the same manner as in Example 22 except that the heterocyclic amine compound (B) was not added, the Nylon 6 resin composition was produced.

(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.

(Refer to Example 4)

Manufacture of nylon 6 as a resin (C) using a laboratory mixer After melting at 280 ° C and kneading for 3 minutes, it was used as a blank sample of the nylon 6 resin composition.

As is apparent from the results shown in Tables 1 to 4, it is found that the resin additive according to the present invention can effectively suppress the production of the resin composition when the carbodiimide compound is used as an additive for improving the hydrolysis resistance of the resin. Production of isocyanate gas. Further, it was also confirmed that the hydrolysis resistance imparted by the carbodiimide compound was hardly affected by the use of the above-described resin additive. In addition, it is confirmed that the more the generation of the isocyanate gas is suppressed, the more the stain of the mold at the time of injection molding of the produced resin composition is suppressed.

Further, it has been found that the production of the master batch (Examples 6, 15, 19, and 24) can effectively suppress the generation of the isocyanate gas.

Claims (13)

A resin additive for a resin additive for at least any one of a polyester resin and a polyamide resin, comprising a carbodiimide compound (A) and a heterocyclic amine compound (B) Does not contain a surfactant. The resin additive of 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 any one of pyrazole, dimethylpyrazole and imidazole. The resin additive according to any one of claims 1 to 3, wherein the carbodiimide compound (A) is an aromatic monocarbodiimide, an aromatic polycarbodiimide, an aliphatic monocarbodiimide, and a fat. At least any one of the polycarbodiimides. 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 based on 100 parts by mass of the carbodiimide compound (A). A masterbatch comprising the resin additive according to any one of claims 1 to 5 and a resin (C) which is at least one of a polyester resin and a polyamide resin. The masterbatch of claim 6, wherein the content of the carbodiimide compound (A) is from 0.5 to 30 parts by mass based on 100 parts by mass of the resin (C). A method of producing a masterbatch, which is a method of producing a masterbatch according to claim 6 or 7, which melt-kneads the resin additive according to any one of claims 1 to 5 with the resin (C). A resin composition which is a tree according to any one of claims 1 to 5 The fat additive is blended into the resin (C), which is at least one of a polyester resin and a polyamide resin. A resin composition obtained by blending a master batch as claimed in claim 6 or 7 with the resin (C). The resin composition of claim 9 or 10, wherein the content of the carbodiimide compound (A) is 0.1 to 10 parts by mass based on 100 parts by mass of the resin (C). A method of producing a resin composition, which comprises melt-kneading a resin additive according to any one of claims 1 to 5 with a resin (C) which is at least one of a polyester resin and a polyamide resin. Any one. A method for producing a resin composition obtained by melt-kneading a master batch as claimed in claim 6 or 7 with the resin (C).