JPS63305158A - Molding resin composition - Google Patents

Abstract

PURPOSE:To obtain a molding resin composition prevented from decreasing in surface properties and mechanical properties during melt molding and improved in long-run moldability, by mixing a thermoplastic resin having ester bonds in the main chain with a specified ethylene/vinyl acetate copolymer saponificate and an end-blocked polyamide resin. CONSTITUTION:This molding resin composition contains a thermoplastic resin (A) having ester bonds in the main chain (e.g., polyester or polycarbonate), a low-ash, low-alkali metal ethylene/vinyl acetate copolymer saponificate (B) of an ethylene content of 20-60mol.%, a degree of saponification of the vinyl acetate part >=95mol.%, an ash content <=20ppm and an alkali metal content <=5ppm and an end-blocked polyamide resin (C) satisfying the relationship of 100.N2/(N1+N2)>=5, wherein N1 is the number of the terminal carboxyl groups (-COOH), and N2 is the number of the terminal carbonamide groups (-CONRR'), wherein R is a 1-22C hydrocarbon group and R' is H or a 1-22C hydrocargon group.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a molding resin composition whose main component is a thermoplastic resin having an ester bond in its main chain, such as polyester or polycarbonate.

BACKGROUND OF THE INVENTION Polyester and polycarbonate are widely used as so-called engineering plastics for manufacturing molded products such as mechanical appliance parts and electrical equipment parts.

Although each of these resins has its own unique and excellent physical properties, various improvements have been made in response to recent high technological innovations and strong demands for higher performance. For example, attempts have been made to improve the surface hardness and wear resistance of these resins by adding various fillers, fluororesins, molybdenum sulfide, mineral oil, and other additives.

Attempts have also been made to improve properties by blending resins; for example, in JP-A-51-73557, a saponified ethylene-vinyl acetate copolymer was added to polycarbonate to improve electrical properties (tracking resistance). ) has been shown to improve.

Problems to be Solved by the Invention However, in the improvement method by adding additives as described above, the processability and surface appearance of the molded product may deteriorate,
In reality, problems such as coloration or bleeding of additives may be observed, and in some cases may have an adverse effect on the inherent mechanical properties of the resin, and the problem has not always been solved.

The method of improving properties by blending a saponified ethylene-vinyl acetate copolymer is an interesting method, and the present inventors are also conducting various studies. When served,
There is a tendency for the surface appearance of the obtained molded product to deteriorate and for mechanical strength such as impact strength to decrease.

The present inventors have discovered that impurities, especially alkaline components, present in saponified ethylene-vinyl acetate copolymers decompose part of the polyester and polycarbonate during melt molding, causing deterioration of surface appearance and impact strength. We thought that it might cause a deterioration in mechanical strength, and as a result of intensive research, we found that
Ethylene blended into polyester and polycarbonate
As a saponified vinyl acetate copolymer, the ethylene content is 2.
0 to 60 mol%, the degree of saponification of the vinyl acetate portion is 95 mol% or more, the ash content is 20 ppm or less, and the alkali metal content is 5 ppm or less. It was discovered that the decrease in strength could be prevented, and patent applications have already been filed as Japanese Patent Application No. 182456/1982 and Japanese Patent Application No. 3709/1982.

However, subsequent studies revealed that the above composition still had room for improvement in terms of long-run moldability.

In other words, when injection molding or extrusion molding the above composition, industrially it is essential to melt and knead the composition to pelletize it in advance, but melt molding for pelletization is carried out continuously over a long period of time. If this is done, gel will be generated in the melt, and resin scum will accumulate in the extruder screw, discharge part, etc. If this is the cause, the screen or nozzle will become clogged, so stop molding temporarily. In some cases, the molding machine had to be dismantled and the deposits removed.

The present invention was achieved as a result of further research in order to eliminate such practical problems.

Means for Solving the Problems The molding resin composition of the present invention comprises a thermoplastic resin (A) having an ester bond in its main chain, an ethylene content of 20 to 60 mol%, and a degree of saponification of the vinyl acetate portion of 95. mol% or more, and the ash content is 20
ppm or less, and a low ash/low alkali metal saponified ethylene-vinyl acetate copolymer (B) having an alkali metal content of 5 ppm or less;

The number Nl of the terminal carboxyl group -Cool and the terminal carboxylic acid amide group -CONRR' (where R is the number of carbon atoms 1 to
22 hydrocarbon group, R'' is a hydrogen atom or has 1 to 2 carbon atoms
It is made of an end-capped polyamide resin (C) in which the ratio of the number of hydrocarbon groups (2) to the number N2 satisfies 100 82/(N1+N2)≧5.

In this case, the ratio by weight of the saponified ethylene-vinyl acetate copolymer (B)/thermoplastic resin (A) is 0.1/
99.9 to 20/80, polyamide resin (C)
It is particularly desirable that the weight ratio of saponified ethylene-vinyl acetate copolymer (B) is 5/95 to 50/'50.

The present invention will be explained in detail below.

, ester O@A Typical thermoplastic resins (A) having an ester bond in the main chain include polyethylene terephthalate,
Examples include polybutylene terephthalate and polycarbonate. Polyester polycarbonates can also be used.

<Polyethylene terephthalate> Polyethylene terephthalate has terephthalic acid or dimethyl terephthalate and ethylene glycol as main components, and is produced by a polycondensation reaction of these. A portion of ethylene glycol can also be converted into 8 with other glycols such as cyclohexane dimetatool.

<Polybutylene terephthalate> Polybutylene terephthalate is produced by polycondensing bis-(ω-hydroxybutyl)-terephthalate produced by transesterifying dimethyl terephthalate and 1,4-butanediol, or by polycondensing terephthalic acid and 1,4-butanediol. It is produced by any conventionally known method, such as a polycondensation reaction with -butanediol, or a method in which terephthalic acid or dimethyl terephthalate is transesterified with 1,4-diacetoxybutane, and then polycondensed.

<Polycarbonate> Polycarbonate is produced by the reaction of dihydric phenol with a carbonate precursor such as phosgene in the presence of an acid acceptor and a molecular attachment modifier, or the transesterification of dihydric phenol with a carbonate precursor such as diphenyl carbonate. Produced by reaction.

As the dihydric phenol, bisphenol A is particularly preferred, but part or all of bisphenol A may be replaced with other dihydric phenol. Further, the polycarbonate may be partially branched; for example, it may be a thermoplastic randomly branched polycarbonate obtained by reacting a polyfunctional aromatic compound with a dihydric phenol or a carbonate precursor.

<Polyester carbonate> Polyester polycarbonate is produced by, for example, reacting a dihydroxydiaryl compound such as bisphenol A with terephthaloyl chloride in the presence of an organic solvent such as methylene chloride and an acid binder such as pyridine, and then reacting this reaction product. A solution polymerization method in which phosgene is introduced and polycondensation is carried out.An alkaline aqueous solution of a dihydroxydiaryl compound is reacted with an organic catalyst solution of terephthaloyl chloride, and then phosgene is introduced into this reaction mixture to form a chloroformate group at the end. It is produced by an interfacial polymerization method in which oligomers are prepared, and then an alkaline aqueous solution of the dihydroxydiaryl compound is added for polycondensation.

The saponified ethylene-vinyl acetate copolymer (B) with low ash content φ and low alkali metal has an ethylene content of 20 to 60
A composition having a saponification degree of vinyl acetate moiety of 95 mol% or more is used. If the ethylene content is less than 20 mol%, the compatibility with the thermoplastic resin (A) will decrease, while if it exceeds 60 mol%, the surface properties, printability, etc. will decrease, or the thermal stability during molding will become unstable. It will be enough.

If the degree of saponification of the vinyl acetate moiety is less than 95 mol%, thermal stability and moisture resistance will decrease.

The saponified copolymer may contain a small amount of a comonomer such as an α-olefin other than ethylene, an unsaturated carboxylic acid compound, an unsaturated nitrile, an unsaturated amide, or an unsaturated sulfonic acid compound.

Generally, a saponified ethylene-vinyl acetate copolymer is produced by saponifying a 1-ethylene-vinyl acetate copolymer using an alkali catalyst. However, the industrial water and reagents used contain metal salts as impurities, and the saponification catalyst (alkali metal hydroxide) remains as an acetate of the alkali metal even after the reaction. Therefore, these impurities and alkali metal acetate are contained in the resin precipitated from the saponification solution.

It is essential to use a saponified ethylene-vinyl acetate combination suitable for the present invention (B) in which such impurities and alkali metal acetate are reduced to below a certain limit.

The above-mentioned ash is obtained by taking a dried saponified ethylene-vinyl acetate copolymer in a platinum evaporating dish, carbonizing it using an electric heater and a gas burner, and then placing it in an electric furnace at 400°C for 700 minutes.
The product is heated to O, completely iodized at 700°C for 3 hours, taken out from the electric furnace, left to cool for 5 minutes, left in a desiccator for 25 minutes, and the ash content is determined. shall be.

The above-mentioned alkali metals are determined by atomic absorption spectrometry using a solution in which the saponified ethylene-vinyl acetate copolymer is incinerated in the same manner as in the case of ash measurement, and the ash is dissolved in an acidic aqueous solution of hydrochloric acid under heating. .

The saponified ethylene-vinyl acetate copolymer (B) suitable for the purpose of the present invention has an ash content of 2 as defined above.
It is necessary that the ash content be 0 ppm or less, preferably 10 ppm or less; if the ash content exceeds 20 ppm, the resulting molded product will have a significant decrease in mechanical strength and deterioration in surface appearance. It is preferable that the ash content be as low as possible within the above-mentioned allowable range, but from an industrial standpoint there are limits to refining.

The lower limit is about 1 ppm.

The saponified ethylene-vinyl acetate copolymer (B) not only needs to have an ash content within the above-mentioned allowable range, but also needs to have an alkali metal content of 5 ppm or less, preferably 3 ppm or less. If the alkali metal content exceeds 5 ppm+, the mechanical strength and surface appearance of the obtained molded product will significantly decrease in the same manner as described above. The alkali metal content is preferably as low as possible within the above-mentioned allowable range, but from an industrial standpoint there is a limit to purification, so the lower limit is about 0.5 ppm.

After all, the saponified ethylene-vinyl acetate copolymer (B) in the present invention is required to have the above-mentioned copolymer composition, an ash content of 20 pptx or less, and an alkali metal content of 5 ppm or less. It will be done.

The saponified ethylene-vinyl acetate copolymer (B) having a low ash content and low alkali metal content is a saponified ethylene-vinyl acetate copolymer powder produced by saponifying an ethylene-vinyl acetate copolymer, It is obtained by thoroughly washing the particles or pellets with an aqueous solution of an acid, particularly a weak acid, to remove salts that cause ash and alkali metals, and more preferably washing with water to remove the acid attached to the resin, and drying.

Examples of weak acids used include acetic acid, propionic acid, glycolic acid, lactic acid, adipic acid, azelaic acid, geltaric acid, succinic acid, benzoic acid, inphthalic acid, and terephthalic acid. Usually, pKa at 25°C is 3.5. The above are useful.

In addition, after performing the treatment with the above-mentioned weak acid, before or after washing with water, dilute strong acids such as oxalic acid, maleic acid, and other organic acids with a pKa of 2.5 or less at 25°C, phosphoric acid, etc.
Further treatment with an aqueous solution of an inorganic acid such as sulfuric acid, nitric acid, or hydrochloric acid is desirable, which makes the alkali metal removal more efficient.

-Polyamide', C The terminal-blocked polyamide resin (C) has the number N1 of terminal carboxyl groups -CooH and the terminal carboxylic acid amide group -CONRR' (where R is a hydrocarbon group having 1 to 22 carbon atoms, R' is The ratio of hydrogen atoms or hydrocarbon groups having 1 to 22 carbon atoms to the number N2 is 100・N2/ (N1+N2
)≧5, that is, lactams with three or more membered rings, ε
- A polyamide obtained by polymerization or copolymerization of an amino acid or a dibasic acid with a diamine, etc., whose terminal carboxyl group is modified with an N-substituted amide is used. Although mono-substituted amide modification (R' is a hydrogen atom) is practical, di-substituted 7-amide modification may also be used.

The above-mentioned polyamide resin (C) is prepared by combining a polyamide raw material with ■ a monoamine having 1 to 22 carbon atoms, or ■ a carbon number 1
It is obtained by polycondensation in the presence of a monoamine of ~22 carbons and a monocarboxylic acid of carbon a2-23.

As polyamide raw materials, lactams (e-caprolactam, enantholactam, capryllactam, lauryllactam, α-pyrrolidone, α-piperidone, etc.), ω-
Amino acids (6-7 minocaproic acid, 7-aminohebutanoic acid, 9-aminononane, 11-aminoundecanoic acid, etc.), dibasic acids (adipic acid, glutaric acid, pimelic acid, speric acid, azelaic acid, sebacic acid) , undecanedioic acid, dodecadionic acid, hexadecadionic acid, hexadecenedioic acid, eicosandionic acid, eicosadienedionic acid, diglycolic acid, 2.2.4-trimethyladipic acid, xylylene dicarboxylic acid, 1.4 -cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, etc.), diamines (hexamethylenediamine, tetramethylenediamine, nonamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2゜2.4-
or 2,4.4-)dibutylhexamethylenediamine, bis-(4,4”-7minocyclohexyl)methane,
metaxylylene diamine, etc.).

Examples of monoamines having 1 to 22 carbon atoms include aliphatic monoamines (methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, 2-ethylhexylamine, nonylamine).

Decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, octadecylamine, octadecylamine, eicosylamine, tocodylamine, etc.), alicyclic monoamines (cyclohexylamine, methylcyclohexyl amines, etc.), aromatic monoamines (benzylamine, β-phenylethylamine, etc.), symmetrical secondary amines (N,N-dimethylamine, N,N-diethylamine, N,N-dipropylamine, N,N-dibutylamine) , N,N-diethylamine, N,N-dioctylamine, N,N-didecylamine, etc.), hybrid secondary amines (
N-methyl-N-ethylamine, N-methyl-N-butylamine, N-methyl-N-octadecylamine, N-
ethyl-N-hexadecylamine, N-ethyl-N-octadecylamine, N-propyl-N-hexadecylamine, N-methyl-N-cyclohexylamine, N-methyl-N-benzylamine, etc.).

As monocarboxylic acids having 2 to 23 carbon atoms, aliphatic monocarboxylic acids S (acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, capric acid, pelargonic acid, undecanoic acid, lauric acid, tridecane acids, myristic acid, myristoleic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, arachidic acid, behenic acid, etc.), alicyclic monocarboxylic acids (cyclohexanecarboxylic acid, methylcyclohexanecarboxylic acid, etc.), aromatic Examples include monocarboxylic acids (benzoic acid, toluic acid, ethylbenzoic acid, phenylacetic acid, etc.).

In addition to the above monoamines or monoamines and monocarboxylic acids, aliphatic diamines (ethylene diamine, trimethylene diamine, tetramethylene diamine, pentamethylene diamine, hexamethylene diamine,
Heptamethylene diamine, octamethylene diamine, nonamethylene diamine, decamethylene diamine, undecamethylene diamine, dodecamethylene diamine, tridecamethylene diamine, hexadecamethylene diamine, octadecamethylene diamine, 2,2.4- or 2,4 ．．
4-) dibutylhexamethylenediamine, etc.), alicyclic diamines (cyclohexanediamine, methylcyclohexanediamine, bis-(4,4'-7minocyclohexyl)methane, etc.), aromatic diamines (xylylenediamine, etc.), fatty acids Group dicarboxylic acids (malonic acid, succinic acid, curtaric acid, adipic acid, pimelic acid, speric acid, azelaic acid, sebacic acid, undecanedioic acid, toticanedioic acid, tridecadionic acid, tetradecadionic acid, hexadecadioic acid, octadecadioic acid) dionic acid, octadecenedioic acid, eicosandioic acid, eicosanedioic acid, tocosandioic acid, 2,2,4-trimethyladipic acid, etc.)
, alicyclic dicarboxylic acid 1%i (1,4-cyclohexanedicarboxylic acid, etc.), aromatic dicarboxylic acid (terephthal resistant,
isophthalic acid, phthalic acid, xylylene dicarboxylic acid, etc.)
Diamines such as diamines and dicarboxylic acids can coexist.

The reaction for producing the polyamide resin (C) may be started according to a conventional method using the polyamide raw material described above. The above carboxylic acid and amine can be added at any stage from the start of the reaction to the start of the reaction under reduced pressure. The carboxylic acid and amine may be added simultaneously or separately.

The amount of carboxylic acid and amine used is 1 mole of polyamide raw material (as the amount of carboxyl group and amino group).
(monomer or monomer unit that constitutes a repeating unit)
2 to 20 meq 1 mol, preferably 3 to 19 meq 1 mol) per 1 mol) (The equivalent amount of amine group is the amount of amino group that reacts with 1 equivalent of carboxylic acid in l:1 to form an amide bond. 1 equivalent).

If the amount used is too small, it will not be possible to produce a polyamide resin suitable for the purpose of the present invention, while if it is too large, the physical properties of the polyamide resin will be adversely affected.

The reaction pressure is preferably 400 Torr or less, preferably 300 Torr or less in the final stage of the reaction. If the pressure at the end of the reaction is high, the desired relative viscosity cannot be obtained.

The time for the reduced pressure reaction is desirably 0.5 hours or more, and usually 1 to 2 hours.

100 NRR' that the polyamide resin (C) has at the end
The hydrocarbon group represented by R or Ro in the group includes aliphatic hydrocarbon groups (methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, octadecyl group, eicosyl group, tocosyl group), alicyclic hydrocarbon group ( cyclohexyl group, methylcyclohexyl group, cyclohexylmethyl group, etc.), aromatic hydrocarbon group (phenyl group, toluyl group, benzyl group, β-phenylethyl group, etc.)
can be given.

-C0NRR' of terminal -〇〇H group of polyamide resin
The conversion ratio to -COOH groups is controlled by the presence of an amine or an amine and a carboxylic acid during the production of the polyamide resin, but the conversion ratio of -COOH groups to 5 mol% or more, especially 10
It is preferable that mol% or more is converted to 100 NRR' groups, and the amount of unconverted -COOH groups is less than 50 eq/gφ polymer, especially 40 ILeq/gφ polymer.
It is preferable that the amount of conversion is less than g.polymer.If the degree of this conversion is small, the desired effect cannot be expected. On the other hand, increasing the degree of conversion is not inconvenient from the point of view of physical properties, but it makes production difficult, so it is best to limit the amount of unmodified terminal carboxyl groups to a level of l g eq / g o polymer. be.

The hydrocarbon groups represented by R and Ro in the -CONRR' group can be measured by gas chromatography after hydrolyzing the polyamide resin (C) using hydrochloric acid. -C
OOH groups can be measured by dissolving the polyamide resin (C) in benzyl alcohol and titrating the solution with 0, IN caustic soda.

In addition to the above-mentioned 100NRR' groups, the terminal groups of the polyamide resin (C) include 1C derived from the polyamide raw material.
There are OOH groups and -NH, groups.

The terminal amide 7 group may or may not be modified, but it is preferably modified with the above-mentioned hydrocarbon group because of good fluidity and melt stability.

-NHz group can be measured by dissolving the polyamide resin (C) in phenol and titrating with 0.05N hydrochloric acid.

The relative viscosity [ηrel] of the polyamide resin (C) is J
According to IS K 8810, concentration 16 in 98% sulfuric acid
, 2 to 6, preferably 2 to 5, measured at a temperature of 25°C
It is. If the relative viscosity is too low, it will be difficult to form into strands and chips, which will be inconvenient in manufacturing. - If the relative viscosity is too high, moldability will be poor.

It is desirable that the blending ratio of each of the resins (A), (B) and (C) above be selected from the following ranges.

First, saponified ethylene-vinyl acetate copolymer (B)/
The proportion of the thermoplastic resin (A) is not particularly limited, but
Preferably, the weight ratio is selected from the range of 0.1/99.9 to 20780. When the proportion of the saponified substance (B) is less than this range, the effect of the blending of the saponified substance (B) is noticeable, whereas when the proportion of the saponified substance (B) is greater than this range, the thermoplastic resin (A) The original physical properties are impaired,
It becomes less practical.

Further, the ratio of polyamide resin (C)/saponified ethylene-vinyl acetate copolymer (B) is not particularly limited, but is preferably selected from a range of 5/95 to 5015'0 by weight. If the proportion of the polyamide resin (C) is less than this range, the moldability during pellet production or extrusion molding will decrease;
C), if 1ul1 is more than this range, thermoplastic 1]! The amount of the saponified ethylene-vinyl acetate copolymer (B) blended into (A) is relatively reduced, and the desired effect of improving the thermoplastic resin (A) cannot be sufficiently achieved.

The composition of the present invention consisting of the above (A), (B) and (C) includes a plasticizer (such as a polyhydric alcohol), a stabilizer, a surfactant, a crosslinking substance (an epoxy compound, a polyvalent metal salt, Known additives such as inorganic or organic polybasic acids or salts thereof), fillers, dyes and pigments, reinforcing materials (glass fibers, carbon fibers, etc.), lubricants, foaming agents, etc. can also be blended. Also other thermoplastic resins, such as polyolefins, polyamides, polyvinyl chloride, polyvinylidene chloride, ABS
It is also possible to mix resin, polyurethane, etc.

K skin removal April 1 As a molding method, a method is usually adopted in which one composition is once melt-kneaded and pelletized, and the pellets are then injection molded or extruded, but blow molding and other known melt molding methods are used. Laws are also enforceable.

The melt molding temperature varies depending on the type of resin, but the temperature at the screw compression section or the discharge section is 180 to 320℃.
It is often a degree.

When extrusion molding is employed, the resin composition of the present invention can also be coextruded with other thermoplastic resins. In this case, the counterpart resins include polyolefin resins, polyamide resins, polyester resins, polycarbonate resins, polyacetal resins, polyvinyl chloride resins, polyvinylidene chloride resins, acrylic resins, styrene resins, and vinyl esters. Examples include polyester resins, polyurethane resins, chlorinated polyolefin resins, and vinyl alcohol resins.

Molded products, coextrusion molded products, and melt-coated products after melt molding are subjected to heat treatment, cooling, rolling, -axial or biaxial stretching, printing, dry lamination, solution or melt coating, bag making, and deep drawing, as necessary. 1 box processed.

Processing or processing such as tube processing or split processing can be performed.

The molded product obtained from the resin composition of the present invention can be used as a packaging material,
Equipment parts (general mechanical equipment parts, electrical/electronic equipment parts, auto parts, marine/aircraft parts, optical/clock parts, etc.), building materials,
It is useful as agricultural materials, textile products, daily necessities, etc.

Function In the present invention, the thermoplastic resin (A) having an ester bond in its main chain constitutes the main component.

The saponified ethylene-vinyl acetate copolymer (B) having a low ash content and a low alkali metal content plays the role of imparting wear resistance and impact resistance to the thermoplastic resin (A).

The end-capped polyamide resin (C) plays a role in ensuring long-run moldability when the saponified ethylene-vinyl acetate copolymer (B) with low ash and low alkali metal content is blended with the thermoplastic resin (A). fulfill.

EXAMPLES Next, the molding resin composition of the present invention will be further explained with reference to Examples. The terms "1 part" and "%" below are expressed on a weight basis unless otherwise specified.

In addition, the measurement of physical property values and the determination of moldability are as follows.

Impact strength: Notched Izot impact strength (KgIICII/cl) based on ASTM 02513, however,
Only when polycarbonate is used, the thickness of the test piece is 1
/8".

Surface Hardness: Rockwell Hardness (Scale M) according to ASTM 0785.

Wear resistance: Taper wear based on ASTM 01175 (wearing wheel 09-17, load 1 kg, 1000 revolutions).

Long run formability: 2 continuous extrusions for pelletizing
After 4 hours, the extruder was disassembled and the state of discoloration of the remaining resin was observed and evaluated in four stages: excellent, good, fair, and poor.

Examples 1-6, Comparative Examples 1-6 "Resin used" The following resins were prepared.

CI Saku A (A-1)
Polyethylene terephthalate (rRT533J, manufactured by Nippon Nippet Co., Ltd., melting point 255°C) (A-2) Polybutylene terephthalate (“Barox 310J, manufactured by General Electric Co., Ltd., melting point 232°C)” (A-3) Polycarbonate (manufactured by Mitsubishi Gas Chemical Co., Ltd.) "Nipiron S-1000J, melting point 250°C) (B-1) 1000 parts of a 40% methanol solution of ethylene-vinyl acetate copolymer with an ethylene content of 40 mol% was charged into a pressure-resistant reactor and heated to 110°C with stirring. Next, 40 parts of a 6% methanol solution of sodium hydroxide and 2500 parts of methanol were continuously charged, and a saponification reaction was carried out for 2.5 hours while distilling by-product methyl acetate and excess methanol from the system. A saponified ethylene-vinyl acetate copolymer with a degree of saponification of the vinyl acetate portion of 99.0% was obtained.

While adding 450 parts of 30% water-containing methanol to the saponified liquid, excess methanol was distilled off.1. Resin concentration 39
% water/methanol (composition ratio 3/7) solution.

A water/methanol mixture of the above-mentioned saponified ethylene-vinyl acetate copolymer at a temperature of 50°C was poured through a nozzle with a hole diameter of 4+am. Water/methanol (mixing ratio 9/l) coagulating liquid tank (width 100 m) maintained at 5°C at a rate of L/hr
mm, length 4000m5, depth Zo.

Im) was extruded into a strand. After the coagulation is completed, a take-up roller attached to the end of the coagulation liquid tank (linear speed 2 m/Peng i)
After step (n), the strand-like material was cut with a cutter to obtain white, porous pellets with a diameter of 41 cm and a length of 4 cm.

The ash content of the saponified ethylene-vinyl acetate copolymer pellets is 7,400 PpH, and the sodium metal content is 48.
It was 00pp■.

Next, a washing operation (weak acid washing) in which 100 parts of the pellets were immersed in 300 parts of a 0.3% acetic acid aqueous solution and stirred at 30° C. for 1 hour was repeated twice. Subsequently, after filtering the slurry, the obtained pellets were again mixed with 300 parts of water to form a slurry, and a washing operation (water washing) of stirring at 30° C. for 1 hour was repeated three times.

The ash content of the saponified ethylene-vinyl acetate copolymer pellets after the above washing operation is 6 ppm, and the sodium metal content is 2.
．． It was 7 ppm.

This saponified ethylene-vinyl acetate copolymer (B-1
).

(B-2) Prior to the water washing, the pellets after weak acid washing were further immersed in 230 parts of a 0.003% phosphoric acid aqueous solution and stirred at 30°C for 1 hour (strong acid washing). Then, the same water washing operation as in the case of production (B-1) was repeated three times.

The resulting saponified ethylene-vinyl acetate copolymer pellets had an ash content of 10 ppm and a sodium metal content of 1.
It was 4 ppm.

This saponified ethylene-vinyl acetate copolymer (B-2
).

(B-3) For comparison, saponified ethylene-vinyl acetate copolymer pellets with an ash content of 30 pp+s and a sodium metal content of 10 ppm were prepared according to the manufacturing method of (B-1) above (however, the number of washings was reduced). Manufactured.

This saponified ethylene-vinyl acetate copolymer (B-3
).

Incidentally, the ash content and sodium metal content were determined in accordance with the following.

<Ash content> Approximately 80 g of the dried sample was accurately weighed, and approximately log of it was placed in a platinum evaporation dish with constant weight, and carbonized with an electric heater. After carbonization, approximately 10 g of each sample was added and the same operation was repeated. Finally, I heated it with a gas burner and baked it until there was no smoke.

The platinum evaporation dish was placed in an electric furnace at about 400°C, most of it covered with a magnetic crucible lid, and the temperature was gradually raised to 700°C. After being held at 700°C for 3 hours to completely incinerate, it was taken out from the electric furnace, allowed to cool for 5 minutes, and then left in a desiccator for 25 minutes, and the ash content was accurately weighed.

<Sodium metal> Approximately 10 g of the dried sample was accurately weighed, placed in a platinum crucible, and incinerated in the same manner as above. Special grade hydrochloric acid 21 in platinum crucible
and pure water 31 were added and heated with an electric heater to dissolve. The above solution was poured into a 501 volumetric flask with pure water, and further pure water was added up to the marked line to prepare a sample for atomic absorption spectrometry.

A separately prepared standard solution (sodium metal lppm.

Atomic absorbance was measured using hydrochloric acid (0.5N) as a control solution, and the amount of sodium metal was determined from the absorbance ratio.

The measurement conditions are as follows.

Equipment: Hitachi 180-30 atomic absorption/flame spectrophotometer Wavelength: 589. On intestinal frame: acetylene-air/polyamide gas C (C-t) ε-caprolactam 60 in a 200 fL autoclave
kg, water 1.2 kg, octadecylamine 3.38 me
q/mol and stearic acid 3.31 Jseq/m
At was charged, the reactor was sealed in a nitrogen atmosphere, and the temperature was raised to 250" O. After stirring and reacting under pressure for 2 hours, the pressure was gradually released to 200 Torr, and the reaction was continued under reduced pressure for 2 hours. went.

Next, after nitrogen was introduced and the pressure was restored to normal pressure, stirring was stopped and strands were taken out and made into chips. Unreacted upper particles were extracted and removed using clean water and dried.

The characteristic values of the obtained polyamide resin (C-1) were as follows.

Terminal carboxyl group = 2oμeq/g・Polymer terminal amino group: 21 geq/g・Polymer lo
om N2/ (N1+N2): 60 relative viscosity [
ηrell: 2.89 (C-2) The amount of octadecylamine charged was 8.81 meq/ma
t, except that 8.81 meq/mol of adipic acid was used instead of 3.39 meq/mol of stearic acid (
A polyamide resin (C-2) having the following characteristic values was obtained in the same manner as in the case of C-1) production.

Terminal carboxyl group: 20 p-eq/go polymer terminal amino group = 21 μeq/g・polymer 1
00@N2/ (Nl+N2): 80 relative viscosity [η
rell: 2.50 [Molding conditions] (Pelletization) The resin compositions shown in Table 1 below were extruded at the following extrusion temperature using a single screw extruder equipped with a full flight screw (screw diameter 45 mm). At the same time, it was pelletized using a pelletizer.

When using (A-1) 270℃ When using (A-2) 250℃ When using (A-3) 280℃ <Injection molding> Using the pellets obtained above, the following injection molding Injection molding was performed under the following conditions: Eve injection molding machine Injection pressure: 900 to 1200 kg/cm2' Injection time = lO seconds Mold temperature: 50'C! Cooling time: 20 seconds The results are shown in Table 1.

Examples 7 to 12, Comparative Examples 7 to 12 Pelletization and injection molding were performed according to the above-mentioned Examples and Comparative Examples, except that the mixing ratio of components (A), (B), and (C) was changed.

The results are shown in Table 2.

Example 13 As saponified ethylene-vinyl acetate copolymer (B) with low moisture content and low alkali metal content, ash content is 8 ppm, sodium metal content is 2.9 ppm, and ethylene content is 30 mol%.
The same experiment as in Example 3 was conducted except that a saponified ethylene-vinyl acetate copolymer (B-4) having a degree of saponification of vinyl acetate of 89.0% was used.

Good long run formability, impact strength 8.1Kg@cm/
It was cm.

Example 14 The same procedure was carried out except that the saponified ethylene-vinyl acetate copolymer (B-4) used in Example 13 was used as the saponified ethylene-vinyl acetate copolymer CB) with low moisture content and low alkali metal content. An experiment similar to Example 9 was conducted.

Excellent long run formability, Rockwell hardness 95M, wear resistance 8mg, impact strength 5.0Kg@am/c+a
Met.

Effects of the Invention The molding resin composition of the present invention has a thermoplastic resin (A) having an ester bond in its main chain as a main component.

Since saponified ethylene-vinyl acetate copolymer (B) with low ash and low alkali metal content was mixed with this as a saponified ethylene-vinyl acetate copolymer, thermoplastic resin ( Decomposition and deterioration of the ester group in A) is not promoted.

In addition, the above saponified ethylene-vinyl acetate copolymer (B
) is effectively prevented from decreasing in long-run moldability due to the addition of the end-blocking polyamide resin (C).

Claims (1)

[Claims] 1. Thermoplastic resin (A) having an ester bond in its main chain;
The ethylene content is 20 to 60 mol%, the degree of saponification of the vinyl acetate portion is 95 mol% or more, and the ash content is 20 p.
pm or less and an alkali metal content of 5 ppm or less, a low ash/low alkali metal saponified ethylene-vinyl acetate copolymer (B), and the number Nl of terminal carboxyl groups -COOH and terminal carboxylic acid amide groups -CONRR' (R is a hydrocarbon group having 1 to 22 carbon atoms, R' is a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms) and the number N2 satisfies the following: 100・N2/(N1+N2)≧5 A molding resin composition comprising a capped polyamide resin (C). 2. The ratio of saponified ethylene-vinyl acetate copolymer (B)/thermoplastic resin (A) is from 0.1/99.9 to 0.1/99.9 by weight.
20/80, and the weight ratio of polyamide resin (C)/saponified ethylene-vinyl acetate copolymer (B) is 5/95 to 50/50. Resin composition for use.