JP2002047421A - Antidegradant, thermoplastic resin composition, and molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an antidegradant and a thermoplastic resin composition which have excellent inhibitory performance against the degradation by the hydrolysis of condensation type thermoplastic resins, and a molded article of a thermoplastic resin which has excellent mechanical properties, surface state, and the like. SOLUTION: An aliphatic polycarbodiimide compound is incorporated into the antidegradant for the condensation type thermoplastic resin. Further, this antidegradant is incorporated into the thermoplastic resin composition. Furthermore, the molded articles can be obtained from the resin composition for molding which comprises this antidegradant and the condensation type thermoplastic resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a deterioration inhibitor for a condensation type thermoplastic resin, a thermoplastic resin composition containing the same, and a molded article.

[0002]

2. Description of the Related Art Condensation type thermoplastic resins such as polyesters are conventionally used as resins having relatively high heat resistance and are widely used in films, sheets, fibers, containers, etc., and are also used for indoor and outdoor building materials. I have. These molded products are used in harsh environments such as high temperatures and outdoors, and because they are melt-kneaded in the molding process, they are oxidized and hydrolyzed with ultraviolet light, heat, alkali, and moisture over time. At present, degradation such as decomposition is likely to occur. Also, this deterioration is due to inorganic filler,
There is a problem that it is particularly accelerated in the presence of a metal, a metal oxide, a dye or a pigment, and causes discoloration, a decrease in molecular weight, a decrease in mechanical properties, and the like, thereby greatly reducing the commercial value of various molded articles.

[0003] In order to reduce such deterioration of the condensation type thermoplastic resin, for example, hindered phenol type antioxidant, phosphoric acid type stabilizer, cuprous chloride or cupric chloride and 2-mercaptobenzimidazole, Attempts have been made to add additives such as oxides of alkaline earth metals such as calcium oxide to suppress hydrolysis of the resin, which is a cause of deterioration, due to the heat stabilizing action of the additives. However, due to the insufficient water absorption and compatibility of the metal, the deterioration suppressing performance of these additives is not satisfactory. Causing the following problems:

Therefore, instead of suppressing the hydrolysis, cross-linking of the hydrolyzed condensed thermoplastic resin with a cross-linking agent has been studied. For example, an isocyanate group-containing compound, an epoxy group-containing compound, and an aromatic carbodiimide compound are used. (JP-A-5-163612, JP-A-8-7
No. 3719, Japanese Patent Publication No. 11-506487) have been reported.

[0005]

However, these compounds react with water to deactivate them, cause marked coloring of molded articles, and are liable to self-condensate because of their aromatic nature. Because of insufficient reaction with the mold thermoplastic resin, satisfactory deterioration suppression performance could not be obtained. Furthermore, streaks due to self-condensation products of the cross-linking agent, which did not occur before, are likely to be generated on the surface of the molded product (streaking phenomenon), and aggregates are easily generated due to high-temperature processing. Agglomerates also had a new secondary problem of causing muscle pulling. In particular, when a very high degree of dispersibility is required for a molded product, for example, when spinning a fiber having a diameter of about 10 microns or more at a high speed, or when forming a film, the self-condensate or agglomerate is generated. In many cases, thread breakage during spinning and clogging of a filter of a melt spinning machine occur, making the molding itself difficult or reducing the strength of the film.

On the other hand, from the viewpoint of ease of handling and preservation of the working environment during use, a masterbatch in which a crosslinking agent is dispersed at a high concentration in a solid condensable thermoplastic resin at room temperature is suitable for a suitable condensed thermoplastic resin. It has been used as a product that is diluted with resin and used for molding. However, since the cross-linking agent and the condensation type thermoplastic resin are melt-kneaded at a high temperature using a kneader, the cross-linking agent reacts with moisture as described above during the dispersion process, or the self-condensation reaction is accelerated, thereby causing the cross-linking. The crosslinking performance of the agent is deactivated,
As a result, there has been a problem that the reaction with the condensation type thermoplastic resin becomes insufficient and the deterioration suppressing performance becomes insufficient.

By the way, in recent years, recycling of polyester has been attempted as a representative of the condensation type thermoplastic resin by the enforcement of the recycling law. The recovered polyester is
Due to the considerable hydrolysis caused by the heat history during molding, melting and pulverization, a decrease in the mechanical strength due to a reduction in molecular weight has occurred. A method of suppressing the decrease has been adopted, and the recycling has been promoted mainly in relation to fibers. However, although this method has the advantage that it can be carried out in common with many resins, it causes a problem that when the required amount of new resin exceeds the amount of wear of the resin in the recovery stage, the recovered resin becomes excessive. . Therefore, if the reduction in the mechanical strength (reduction in molecular weight) of the recovered resin can be suppressed, the problem of excess of the recovered resin can be solved, and on the other hand, it can be reused for uses other than fiber, and waste Recycling system can be maintained in the future. Therefore, at present, improvement of mechanical properties by suppressing the reduction of the molecular weight of these recovered resins is greatly expected.

In view of the above, the present invention provides a thermoplastic resin composition (masterbatch, molded pellet) and a deterioration inhibitor excellent in performance of preventing (deteriorating deterioration) due to hydrolysis of a condensation type thermoplastic resin, and An object of the present invention is to provide a thermoplastic resin molded product having excellent mechanical properties and surface condition.

[0009]

SUMMARY OF THE INVENTION The inventors of the present invention use a high molecular weight polycarbodiimide and an aliphatic polycarbodiimide to prevent degradation of a condensation type thermoplastic resin, particularly a dehydration condensation type thermoplastic resin due to hydrolysis. The inventors have found that the system is effective, and have completed the present invention.

That is, the deterioration inhibitor according to the present invention is a deterioration inhibitor for a condensation type thermoplastic resin and is characterized by containing at least an aliphatic polycarbodiimide compound. Thus, the deterioration inhibitor of the present invention comprises
Since an aliphatic polycarbodiimide compound is used as the active ingredient, it is possible to provide an excellent inhibitory effect on degradation due to hydrolysis of a condensation-type thermoplastic resin, particularly, a dehydration-condensation-type thermoplastic resin due to reduction in molecular weight. . Since the reaction rate of an aliphatic polycarbodiimide compound is lower than that of an aromatic compound, self-condensation and aggregation of polycarbodiimide compounds such as aromatic compounds are suppressed. As a result, the deterioration inhibitory function of the deterioration inhibitor (crosslinking performance)
And the condensate and agglomerate resulting from the deterioration inhibitor do not lower the surface condition or mechanical strength of the molded article. This polycarbodiimide compound crosslinks the terminal groups such as carboxyl groups of the hydrolyzed condensed thermoplastic resin to form a three-dimensional structure, thereby reducing the molecular weight of the resin and accompanying mechanical strength (physical properties). It is thought that it is preventing.

[0011] In a preferred embodiment, the deterioration inhibitor further comprises a dispersant. In that case, the content of the aliphatic polycarbodiimide compound is 0.01 to 60.
% By weight, and the content of the dispersant is preferably 40 to 99.99% by weight. Further, it is preferable that the dispersant is selected from fatty acid amide, fatty acid ester and tackifier resin.

Next, the thermoplastic resin composition according to the present invention comprises the deterioration inhibitor according to the present invention and a condensation type thermoplastic resin and / or a non-condensation type thermoplastic resin. . By containing the deterioration inhibitor of the present invention, the composition is excellent in performance of suppressing deterioration due to hydrolysis of the condensation type thermoplastic resin. This thermoplastic resin composition is a concept including a masterbatch used by being diluted with a molding resin at the time of molding, and molded pellets to be directly used for molding. However, a composition containing a deterioration inhibitor and a non-condensable thermoplastic resin but not containing a condensed thermoplastic resin is exclusively used for masterbatch which is diluted with the condensed thermoplastic resin and provided for molding. In a preferred embodiment, the condensation type thermoplastic resin is a polyester resin, and the non-condensation type thermoplastic resin is a polyolefin resin.

Next, the thermoplastic resin molded article according to the present invention is obtained from a molding resin composition containing the deterioration inhibitor according to the present invention and a condensation type thermoplastic resin. In a preferred embodiment, the condensation type thermoplastic resin is a polyester resin. The resin composition for molding further comprises:
It may contain a non-condensation type thermoplastic resin, preferably a polyolefin resin.

In the present invention, the condensation type thermoplastic resin is a thermoplastic resin obtained by increasing the molecular weight by a condensation reaction, and a typical example thereof is a polycondensation type thermoplastic resin obtained by repeating only the condensation reaction. . The non-condensation type thermoplastic resin is a thermoplastic resin obtained by increasing the molecular weight by a reaction other than the condensation reaction, and a typical example thereof is an unsaturated polymerization type thermoplastic resin obtained by a chain polymerization reaction.

[0015]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The deterioration inhibitor according to the present invention contains an aliphatic polycarbodiimide compound.

The aliphatic polycarbodiimide compound (A) (hereinafter simply referred to as "polycarbodiimide")
Has two carbodiimide bonds in the molecule (polymer main chain).
And is obtained by reacting any aliphatic isocyanate compound. If the degree of polymerization (n) is too large, the stability of the polycarbodiimide itself may deteriorate, so that it is preferably 3 to 20, and particularly preferably 5 to 12.
The molecular weight is preferably 500 or more, and is preferably about 10,000 or less from the viewpoint of reactivity.

Examples of the aliphatic isocyanate used as a raw material include hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, polyfunctional aliphatic isocyanate, block polyfunctional aliphatic isocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate,
Examples thereof include a water additive of an aromatic isocyanate, and one or more of these can be preferably used. Alternatively, an aromatic isocyanate may be reacted to form an aromatic polycarbodiimide and then hydrogenated to obtain an aliphatic isocyanate.

In a preferred embodiment, the deterioration inhibitor of the present invention contains a dispersant (B). This enhances the dispersibility of the deterioration inhibitor (polycarbodiimide (A) and other additives in the deterioration inhibitor) when mixed with the molding resin, and further enhances the deterioration suppression performance and mechanical properties of the molded product. Can be enhanced. In particular, when the polycarbodiimide (A) has a low melting point and is difficult to handle, it is preferable to add a dispersant.

The dispersant (B) to be used is not particularly limited as long as it has good compatibility with the molding resin. Preferably, at least one of fatty acid amide, fatty acid ester and tackifier resin is used. Can be used. Any one or more means that, for example, fatty acid amides and fatty acid esters may be combined, or one or more fatty acid amides and one or more fatty acid esters may be combined.

Among the dispersants (B), fatty acid amides include, for example, stearic acid amide, behenic acid amide,
Palmitic acid amide, lauric acid amide, erucic acid amide, oleic acid amide, methylene bisbehenic acid amide,
Methylenebisstearic acid amide, ethylenebisstearic acid amide, ethylenebisoleic acid amide, hexamethylenebisstearic acid amide, hexamethylenebisoleic acid amide, ricinoleic acid amide, 12-hydroxystearic acid amide, and the like. Species or two or more species can be preferably used.

Among the dispersants (B), the fatty acid ester is
It is an ester compound of a mono- or dicarboxylic acid and a monohydric or polyhydric alcohol, and any one or more of them can be used.

Examples of the alcohol component include methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, hexyl alcohol, nonyl alcohol, octyl alcohol, decyl alcohol, lauryl alcohol, stearyl alcohol, isopropyl alcohol, 2-ethylhexyl alcohol, and nonylphenyl. Monohydric alcohols such as alcohol, octylphenyl alcohol, benzyl alcohol, and trimethylolpropane diallyl ether; ethylene glycol, propylene glycol, 1,4-butanediol, and 1,3
-Butanediol, 2,3-butanediol, diethylene glycol, dipropylene glycol, trimethylene glycol, triethylene glycol, polyoxyethylene glycol, polyoxypropylene glycol,
1,5-pentanediol, 1,6-hexanediol, neopentyldiol, 2,2,4-trimethylpentanediol, hydrogenated bisphenol, 2,2-di (4-hydroxypropoxyphenyl) propane, pentaerythritol diallyl ether , 2-ethyl-1,
Dihydric alcohols such as 3-hexanediol and other alkylene glycols; glycerin, pentaerythritol, sorbitol, mannitol, trimethylolmethane, trimethylolethane, trimethylolpropane,
And polyhydric alcohols such as dursit. These can be used alone or in combination of two or more.

Examples of the acid component include lauric acid,
Stearic acid, palmitic acid, oleic acid, erucic acid,
Caproic acid, caprylic acid, myristic acid, succinic acid, behenic acid, linoleic acid, stearyl lactic acid, lactic acid, acetic acid, citric acid, phthalic acid, benzoic acid, erucic acid, montanic acid, ricinoleic acid, naphthenic acid, hydroxystearic acid, Monocarboxylic acids (monobasic acids) such as hydroxypalmitic acid, hydroxyeicoic acid, acrylic acid and methacrylic acid; dicarboxylic acids such as oxalic acid, maleic acid, fumaric acid, itaconic acid, aconitic acid, citraconic acid and terephthalic acid ( Dibasic acids), and these can be used alone or as a mixture of two or more.

Among the dispersants (B), examples of the tackifying resin include terpene resins mainly containing one or more of monoterpenes such as α-pinene, β-pinene and limonene, sesquiterpenes, diterpenes and polyterpenes. And its hydrogenated terpene resin; abietic acid, diabietic acid,
A modified rosin resin (rosin ester) in which a rosin such as neoabietic acid, levopimaric acid, pimaric acid, dextropimaric acid, and an organic acid mainly containing hydrogenated rosin are esterified with a polyhydric alcohol containing glycerin or pentaerythritol. A petroleum resin mainly containing monoolefin containing a styrene-based compound having 5 to 9 carbon atoms, coumarone, indene, cyclopentadiene, dicyclopentadiene, or the like, or a hydrogenated petroleum resin thereof; More than one species can be preferably used.

The degradation inhibitor of the present invention can be in any form such as powder, granule or bead.
In the case of beads, the dispersant has a melting point of 16 due to the manufacturing process of kneading in a semi-molten state.
It is preferably 0 ° C. or lower. This makes it easy to receive the shearing stress of the mixing / stirring / kneading machine at the time of bead production, and the polycarbodiimide (A) and the dispersant (B) are efficiently mixed / kneaded under high shearing stress so that both are sufficiently mixed. This makes it possible to obtain an anti-deterioration agent which is uniform and has excellent distribution to the diluted (molding) resin during molding. In other words, if the melting point of the dispersant is too high, the dispersant is not melted when producing beads, or the viscosity is too high even if it is melted, so that dispersion processing with polycarbodiimide becomes difficult. Absent. In addition, from the viewpoints of handleability at the time of production of the deterioration preventing agent (the dispersant itself does not stick), mixing property with the molding resin at the time of molding, and rigidity of the molded product,
The melting point of the dispersant is preferably 50 ° C. or higher. In the present invention, the melting point is a peak temperature of the melting point,
More specifically, it is the peak temperature of the melting point measured by a differential scanning calorimeter under a nitrogen gas flow at a temperature rising rate of 10 ° C./min.

When the dispersant (B) is added because the melting point of the polycarbodiimide (B) is too low or the like, the polycarbodiimide (A) in the deterioration inhibitor is used in order to exhibit the intended deterioration suppressing performance. Content is 0.01% by weight
It is preferable that it is above. From the viewpoint of ensuring compatibility with the molding resin, transparency of the molded product, and a surface state free from bleed, etc., the content of the dispersant (B) is 99.9% by weight.
The following is preferred. On the other hand, the content of the polycarbodiimide (A) is 60% by weight or less from the viewpoint of eliminating stickiness and blocking of the polycarbodiimide itself due to the low melting point and securing dispersibility with the molding resin. Due to the reason, the content of the dispersant (B) is 40.
It is preferred that the content be at least 10 wt%.

The deterioration inhibitor of the present invention and the thermoplastic resin composition to be described later can contain various additives which are commonly used within a range not to impair the effects of the present invention. Examples of additives include stabilizers such as antioxidants and anti-tarnish agents, light-stable weathering agents including ultraviolet absorbers, lubricants, mold release agents, halogen-based or non-halogen-based flame retardants, antistatic agents, and foaming agents. Agents, coupling agents, antibacterial and antifungal agents and the like. In particular, for coloring purposes, an arbitrary coloring agent such as a dye or a pigment can be blended. Further, for the purpose of improving the mechanical properties of the molded article, a reinforcing agent such as an inorganic filler or glass fiber may be added.

The method for producing the deterioration inhibitor of the present invention is not particularly limited. For example, when the two components of the polycarbodiimide (A) and the dispersant (B) are used as essential components (if necessary, Add various additives), mix with Henschel mixer or disperser, kneader, roll mill, super mixer, Henschel mixer, sugi mixer, vertical granulator, high speed mixer, fur matrix, ball mill, steel mill, sand mill, vibration mill The mixture is melted, kneaded and dispersed by an attritor, an extruder or the like to obtain the deterioration inhibitor of the present invention in any form of powder, granules or beads. If the polycarbodiimide is localized in the deterioration preventing agent, during extrusion molding or injection molding, agglomerates may be generated due to self-condensation of the polycarbodiimide. It is preferable to mix them.

The degradation inhibitor of the present invention can be used in various ways in which a condensation type thermoplastic resin is used in order to prevent degradation due to hydrolysis of the condensation type thermoplastic resin (that is, to suppress resin deterioration due to reduction in molecular weight). It can be used in various applications in the field. That is, in addition to being used for molded articles of thermoplastic resin, for example, by adding an appropriate amount to a varnish for printing ink, a binder for paint, or the like, it can also be used to suppress deterioration of these.

Next, the thermoplastic resin composition (X) of the present invention
Contains the deterioration inhibitor of the present invention and a thermoplastic resin (C), that is, a condensation type thermoplastic resin (C1) and / or a non-condensation type thermoplastic resin (C2).

The thermoplastic resin composition (X) may contain a polycarbodiimide (A) at a high concentration, and may be a pelletized masterbatch which is diluted with a molding (diluting) thermoplastic resin during molding. Alternatively, it may be a pellet having a relatively low polycarbodiimide (A) concentration and being directly used for molding without being diluted with a thermoplastic resin for molding, and the form thereof is not limited. However, as for the thermoplastic resin not containing the condensation type thermoplastic resin (C1) (composition X containing A and C2),
It is used only for master batches which are diluted with a condensing type thermoplastic resin for molding and used for molding. Between C1 and C
When two or two or more thermoplastic resins are used in combination of two or C1 and C2, it is preferable to select ones having good compatibility with each other.

Examples of the condensation type thermoplastic resin include polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyarylate, polyolefin copolymerized polyester, and thermoplastic polyester; polyamide resins, polyimide resins, polycarbonate resins, polysulfone resins; Amino resins, polyurethane resins and the like.
More than one species can be preferably used. Among them, a polyester resin is preferably used.

Examples of the non-condensable thermoplastic resin include crystalline or amorphous polypropylene, low- or high-density polyethylene, polybutene, polymethylpentene, a copolymer of α-olefin and ethylene or propylene, and ethylene-vinyl acetate copolymer. Polyolefin resins such as polymers, ethylene-acrylic acid copolymers, ethylene-methacrylic acid copolymers, ethylene-maleic anhydride copolymers, propylene-maleic anhydride copolymers; polystyrene resins, acrylonitrile-butadiene-styrene ( ABS) copolymer, acrylonitrile-EPDM-styrene (AES)
Copolymers, acrylic resins, polybutadienes, polyacetal resins, polyether resins, polyvinyl acetate, polyvinyl chloride, polyvinylidene chloride and the like can be mentioned, and one or more of these can be preferably used.
Among them, a polyolefin resin is preferably used.

When the thermoplastic resin composition (X) of the present invention is used as a masterbatch, the content of polycarbodiimide (A) can be used to prevent the intended deterioration without impairing the mechanical properties of the molded article. To get the effect economically,
The content is preferably 0.2% by weight or more, and from the viewpoint of facilitating production of the master batch itself and homogenization with the molding resin, it is preferably 40% by weight or less, and particularly preferably 5 to 30% by weight. It is more preferable if there is. On the other hand, when the thermoplastic resin composition (X) of the present invention is used as molded pellets, the content of the polycarbodiimide (A) is set at 0. 0 from the viewpoint of preventing the intended deterioration and obtaining sufficient mechanical properties. It is preferably at least 01% by weight, while
From the viewpoint of suppressing the coloring of the molded article caused by the polycarbodiimide and securing the flexibility, the content is preferably 10% by weight or less.

The method for producing the thermoplastic resin composition (X) is not particularly limited, but the thermoplastic resin (C) is added, mixed, and dispersed in a deterioration inhibitor (compounded and dispersed in advance). Alternatively, the respective components of the deterioration inhibitor and the thermoplastic resin (C) may be mixed and dispersed at a time. In the former case, the thermoplastic resin (C) is supplied to a co-rotating twin-screw extruder, and a side-feeder or another suction device is used to supply a deterioration preventing agent in the middle of the extruder, thereby melt-kneading. Dispersion can also be performed continuously.

The thermoplastic resin composition (X) of the present invention can be suitably added to other thermoplastic resins to suppress deterioration of a molded article, and can be used in combination with the above-mentioned deterioration inhibitor of the present invention. Similarly, an appropriate amount can be added to various types of condensed thermoplastic resins to help suppress their deterioration.

Next, the molded article of the thermoplastic resin according to the present invention comprises the deterioration inhibitor of the present invention and a condensation type thermoplastic resin (C1).
And obtained from a molding resin composition (Y) containing: As the condensation type thermoplastic resin (C1), those described above can be used, and particularly, a polyester resin is preferably used.

The resin composition (Y) for molding can be prepared by adding at least the condensation type thermoplastic resin (C1) to the deterioration inhibitor of the present invention, and also comprises the thermoplastic resin composition (X) of the present invention. ) May be used as it is, or it may be prepared by adding another condensed and / or non-condensed thermoplastic resin (C) as needed. In addition, this resin composition (Y) may contain various additives as needed. It should be noted that the thermoplastic resin composition (X) of the present invention comprises a deterioration inhibitor and a non-condensable thermoplastic resin (C).
If the composition contains (2) (does not contain C1), it is necessary to newly add a condensation-type thermoplastic resin (C1) in order to obtain a resin composition (Y) for molding. Thereby, a molded article in which the function of the deterioration inhibitor of the present invention is exhibited can be obtained. As the thermoplastic resin (C) optionally further added, a resin having good compatibility between the resins can be arbitrarily selected from the above-described exemplary resins.

The molded article of the present invention can be formed by extrusion molding, injection molding,
It may be obtained by any method of blow molding. At the time of molding, the resin composition for molding (Y) can be used in an undried state. Extrusion molding using the molding resin composition (Y) containing the deterioration inhibitor of the present invention,
In particular, when a thin film such as a film is subjected to extrusion molding, it is possible to obtain a film excellent in transparency and excellent in surface state without occurrence of streaks or the like with high productivity. Further, when the resin composition (Y) is used for injection molding or blow molding, a molded article having excellent mechanical properties and excellent hydrolysis resistance can be obtained.

[0040]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to examples. In the following description, parts are parts by weight, and% is% by weight.
Respectively.

(1) Production of beads (Examples 1 to 7) 20 parts of component (A) and 80 parts of component (B) shown in Table 1 (however, in Example 7, (A) was used without using (B)) 100 parts) was premixed with a Henschel mixer, and the beads were produced while stirring and semi-melting at 80 ° C. for about 10 minutes. The average particle diameter of the obtained beads is 1.0 m
m. In the table, “aliphatic PC-1” is an aliphatic polycarbodiimide using hydrogenated diphenylmethane diisocyanate as a raw material: dicyclohexylmethane-4,4-polycarbodiimide (Nisshinbo Co., Ltd. “Carbodilite HM”).
V-8CA ") and" aliphatic PC-2 "are polycarbodiimides using hexamethylene diisocyanate as a raw material: hexamethylene polycarbodiimide (Aldrich),
"Aliphatic PC-3" is polycarbodiimide using methylhexamethylene diisocyanate as a raw material: 3-methylhexamethylene polycarbodiimide (Aldrich),
“Fatty acid ester” is 12-hydroxystearic acid triglyceride (Kawaken Chemical Co., Ltd. “K3 wax”), “fatty acid amide” is ethylene bisstearic acid amide (Nippon Oil & Fats Co., Ltd. “Alflow H50T”),
"Tackifier resin" is a pentaerythritol ester of hydrogenated rosin (Rikataku P)
H ") and" fatty acid salt "indicate calcium stearate (Mizusawa Chemical Industry Co., Ltd." Stabinex NTC1 "), respectively.

(Comparative Examples 1 to 5) In place of the aliphatic polycarbodiimide (A) used in Examples 1 to 7, the following component (A) was used, and a fatty acid ester was used as a dispersant (B). However, in Comparative Example 1, (B) was not used (A)
100 parts, Comparative Example 5 did not use (A) but (B) 100
Part), and beads were produced in the same manner as in Examples 1 to 7. Comparative Examples 1 and 2: Aromatic polycarbodiimide using toluene diisocyanate as a raw material: tolylene-2,4-
Polycarbodiimide ("Aromatic PC" in the table, Rhein Chemie) Comparative Example 3: Mixture of 10 parts of cupric chloride and 10 parts of 2-mercaptobenzimidazole ("Non-PC-" in the table)
1 ") Comparative Example 4: Calcium oxide (" non-PC-2 "in the table)

(2) Production of mill base (Examples 8 to 14, Comparative Examples 6 to 10) 50 parts of component (A) and 50 parts of component (B) shown in Table 1 (however,
And in Comparative Example 6, (B) was not used, (A) 100 parts,
In Comparative Example 10, (A) was not used and (B) was 100 parts).
The mixture was melt-kneaded at 120 ° C. using a three-roll mill and then coarsely pulverized with a Henschel mixer to produce a powdery mill base.

(3) Production of Master Batch (Examples 15 to 21, Comparative Examples 11 to 15) 20 parts of component (A), 10 parts of component (B), and component (C) shown in Table 1 were commercially available polyethylene terephthalate ( Unitika Ltd. “Unipet RT553”, intrinsic viscosity: 0.8603) 70 parts (however, in Example 21 and Comparative Example 11, (B) was not used, (A) 20 parts and (C) 80 parts, Comparative Example) In No. 15, (A) was not used, (B) (10 parts) and (C) (90 parts) were premixed with a Henschel mixer, and a screw diameter of 6 was used.
5 mm, fed to a single screw extruder with an L / D value of 32;
Pellets at 50 rpm and a set temperature of 270 ° C.
Master batch was obtained.

(4) Production of molded pellet 1 (Examples 22 to 28, Comparative examples 16 to 20) 0.5 part of component (A), 2.5 parts of component (B), and component (C) shown in Table 2 )
97 parts (however, in Example 28 and Comparative Example 16, (B) was not used, (A) 0.5 part and (C) 99.5 parts,
In Comparative Example 20, (A) was not used, and (B) 2.5 parts and (C) 97.5 parts) were premixed with a Henschel mixer to give a screw diameter of 58 mm and an L / D value of 42 in the same biaxial direction. Feed to the rotary screw extruder, rotate at 350r
At 270 ° C. and at a set temperature of 270 ° C., the mixture was extruded and cut with a pelletizer to obtain a polyester compound (formed pellet 1).

(5) Production of colored master batch (Examples 29 to 35, Comparative Examples 21 to 25) 10 parts of component (A), 3 parts of component (B), and 27 parts of component (C) shown in Table 2 ( However, in Example 35 and Comparative Example 21, (B) was not used, and 10 parts of (A) and (C) were 30 parts. In Comparative Example 25, (A) was not used, and 3 parts of (B) and (C) 37 were not used. ), As a coloring agent, 60 parts of titanium oxide ("Taipei CR80", Ishihara Sangyo Co., Ltd.) was added, and these were premixed with a Henschel mixer. A batch was manufactured.

(6) Production of molded pellet 2 (Examples 36 to 42, Comparative Examples 26 to 30) 0.5 part of component (A), 3 parts of component (B), and component (C) shown in Table 2 Polylactic acid resin (Mitsui Chemicals Co., Ltd. "Lacia H-100
J ", 96.5 parts (intrinsic viscosity: 0.9785) (however,
In Example 42 and Comparative Example 26, (B) was not used and (A) 0.5 part and (C) 99.5 parts were not used. In Comparative Example 30, (A) was not used and (B) 3 parts and (C) were not used. 97 parts) were premixed with a Henschel mixer to produce a polyester compound (molded pellet 2) in the same manner as in the above-mentioned (4), except that the set temperature was 220 ° C.

[0048]

[Table 1]

[Table 2]

(7) Evaluation test (1) Beads obtained in the above Examples and Comparative Examples
(2) Mill base, (3) master batch, (4) molded pellet 1, (5) colored master batch, and (6) molded pellet 2 were evaluated as follows.

A. Productivity evaluation was evaluated according to the following criteria. ：: Smooth production without strand breaks or pulsating flow △: Slight pulsating flow occurs, but production is possible without strand breaking ×: Strand rupture, pulsating flow or foaming occurs and production is impossible

B. Evaluation of Film Molded Product The obtained beads, mill base, masterbatch, coloring masterbatch and polyester resin (intrinsic viscosity: 0.8603, melting point peak temperature: 243 ° C.) as a molding resin were mixed with a component (A) concentration of 0 The mixture was mixed at a ratio of 0.5% (the same dilution ratio was also used for components not containing component (A)), and the molding temperature was set to 29 using a T-die film molding machine (manufactured by Toyo Seiki).
It was melt-extruded at 0 ° C. and 60 rpm to obtain a film-shaped molded product having a film thickness of 30 μm. Molded pellets 1 and 2 were similarly formed into films with the same compositions. However, the molding temperature of the molded pellet 2 was 220 ° C. Evaluation tests on the film strength and the film state of the obtained film were performed as shown below.

B1. Film strength The tensile strength of the film was measured according to JIS K7113, and the strength retention of the film obtained from only the polyester resin for molding with respect to the tensile strength (assumed to be 100%) was determined and evaluated according to the following criteria. ：: strength retention of 100% or more ：: strength retention of 95% or more and less than 100% Δ: strength retention of 90% or more and less than 95% ×: strength retention of less than 90% b2. Film State The presence or absence of film cracks, bumps, coloring, and smoothness of the film were visually evaluated according to the following criteria. ◎: Very good ：: No problem in practical use ：: Problem with any of film cracking, coloring, spots and smoothness ×: Poor

C. Evaluation of Mechanical Properties of Injection Molded Product The obtained beads, mill base, masterbatch, colored masterbatch and polyester resin (same as those used in b) have a component (A) concentration of 0.5%. And the mixture is subjected to a back pressure of 10 k with an injection molding machine.
Injection molding was performed at g / cm ² to obtain a plate. Plates were obtained from the molded pellets 1 and 2 in the same manner with the same composition. Each of the obtained plates was subjected to three tests of tensile strength, flexural modulus, and Izod impact strength. The retention of mechanical properties of each plate was determined by setting the value of the plate consisting of only the polyester resin for molding to 100%, and evaluated based on the following criteria from the retention of mechanical properties in three tests. ：: 96% or more in all △: 90% or more and less than 96% in the test x: 1 in the case of less than 90% in the test

D. Hydrolysis evaluation d1. Intrinsic viscosity value The obtained beads, mill base, masterbatch, coloring masterbatch and polyester resin (same as those used in b) are mixed so that the concentration of the component (A) becomes 0.5%, The mixture was screwed with a diameter of 30 mm,
Feed to a single screw extruder with L / D value of 30 and rotate at 100 rpm
m, and pelletized under the conditions of a set temperature of 270 ° C. to produce a polyester compound. Molded pellets 1 and 2 were used as they were. After drying the obtained polyester compound at 140 ° C. for 2 hours, 100 m
0.5 g was weighed into a 1 volumetric flask, and 100 ml of a phenol: tetrachloroethane = 1: 1 solution was accurately added.
This was stirred and dissolved at 100 ° C. for 1.5 hours to obtain a measurement sample. However, in a polyester compound from a pigmented master batch containing a pigment, phenol:
After dissolving in a 1: 1 solution of tetrachloroethane, the pigment was removed by a centrifuge to obtain a measurement sample. For the measurement, a capillary viscosity automatic measuring device (Shibayama Scientific Co., Ltd. “SS-60”
0-L2 type)), the retention of the intrinsic viscosity value of each polyester compound was determined with the case of the polyester resin for molding taken as 100%, and evaluated according to the following criteria. ：: Retention rate of intrinsic viscosity value of 96% or more Δ: Retention rate of intrinsic viscosity value of 90% or more and less than 96% ×: Retention rate of intrinsic viscosity value of less than 90%

D2. Weight Change Using the injection molded plate prepared in c above, the weight before and after immersion in a 10% aqueous solution of sodium hydroxide at 40 ° C. for 200 hours was measured. The weight retention rate of each plate was determined by setting the weight before immersion to 100%, and evaluated according to the following criteria. ：: Weight retention of 96% or more Δ: Weight retention of 90% or more and less than 96% ×: Weight retention of less than 90%

E. Evaluation of pigment dispersibility If there are many undispersed pigments in the coloring master batch,
Since the mesh was clogged with the extrusion, the pigment dispersion state in the obtained colored master batch was evaluated by obtaining the pressure rise value at the tip of the extruder. Using a single-screw extruder having a screw diameter of 20 mm and a wire mesh of 1450 mesh attached at the tip, 400 g of each of the obtained colored master batches was extruded as a pigment component. The difference between the pressure applied at the beginning of extrusion and the pressure applied to the mesh when extruding 400 g (pressure increase at the tip of the extruder: kg / cm ² ) was determined. The pressure rise value is 100k
If it is not more than g / cm ^2, it can be judged as good. Tables 3 to 5 show the above results.

[0057]

[Table 3]

[Table 4]

[Table 5]

In the above Examples, a granulated product (beads) having good hardness and blocking resistance of the particles and a mill base having good appearance and good blocking resistance could be obtained. In addition, all of the master batches, colored master batches, and molded pellets of the examples could be obtained smoothly without causing strand breaks or pulsation. In the examples using the aliphatic polycarbodiimide compound, the excellent deterioration suppressing function suppresses the molecular weight reduction and the like due to hydrolysis of the molding (or base) polyester resin, and the polycarbodiimide itself has its own property. Since the condensation was suppressed, it was possible to obtain a molded product excellent in surface condition and mechanical properties as compared with the comparative example with high productivity.

[0059]

The deterioration inhibitor according to the present invention is excellent in the performance of suppressing deterioration of the condensation type thermoplastic resin due to hydrolysis, and
Since the coloring of the resin and the generation of condensate and agglomerate due to the deterioration inhibitor during molding are suppressed, a molded article having good mechanical properties and surface condition can be provided by using this.
In addition, by using the deterioration inhibitor or the thermoplastic resin composition of the present invention particularly for a polyester resin, deterioration (reduction in molecular weight) of the recovered polyester resin and reduction in mechanical strength can be suppressed. Reuse for various uses can be expected.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08K 5/29 C08K 5/29 C08L 23/00 C08L 23/00 67/00 ZAB 67/00 ZAB 93/00 93/00 C09K 15/22 C09K 15/22 F-term (reference) 4F071 AA02 AA14 AA43 AA44 AA71 AC10 AC12 AE05 AE18 AF01 BB05 BB06 BC01 BC03 BC04 4H025 AA31 AC07 4J002 AA01W BB00W CE00X CF00W EHFD EP 007

Claims (9)

[Claims] 1. A deterioration inhibitor for a condensation type thermoplastic resin, which comprises an aliphatic polycarbodiimide compound. 2. The deterioration inhibitor according to claim 1, further comprising a dispersant. 3. The deterioration inhibitor according to claim 2, wherein the content of the aliphatic polycarbodiimide compound is 0.01 to 60% by weight, and the content of the dispersant is 40 to 99.99% by weight. . 4. The deterioration inhibitor according to claim 2, wherein the dispersant is selected from a fatty acid amide, a fatty acid ester, and a tackifier resin. 5. A thermoplastic resin composition comprising the deterioration inhibitor according to claim 1 and a condensation type thermoplastic resin and / or a non-condensation type thermoplastic resin. 6. The thermoplastic resin composition according to claim 5, wherein the condensation type thermoplastic resin is a polyester resin. 7. The thermoplastic resin composition according to claim 5, wherein the non-condensable thermoplastic resin is a polyolefin resin. 8. A thermoplastic resin molded product obtained from a resin composition for molding containing the deterioration inhibitor according to claim 1 and a condensation type thermoplastic resin. 9. The thermoplastic resin molded article according to claim 8, wherein said condensation type thermoplastic resin is a polyester resin.