JP3374870B2 - Method for producing oxymethylene copolymer resin composition - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention
Methylene copolymer resin composition, especially for color pigments
Preparation of the copolymer resin composition having improved thermal stability
Related to the fabrication method. 2. Description of the Related Art Trioxane has a CC bond in a molecule.
Oxymethylene obtained by copolymerizing cyclic ether
Copolymer is sometimes abbreviated as oxymethylene copolymer.
Easily decompose from the end of the copolymer component,
Autoxidation causing degradation with backbone breakage
Has a significant loss of thermal stability as a result of these decompositions
It is also well known. In addition, carbon black, acid,
When a coloring pigment such as titanium oxide is blended,
Of the oxymethylene copolymer is further accelerated,
Plastic material of the copolymer, which greatly impairs the stability
It is also true that it is difficult to use it as. Until now, autoxidation by the addition of a stabilizer
Degradation of the copolymer, thereby improving the thermal stability of the copolymer.
Of the copolymer component by
The unstable structure is decomposed and removed from the terminal, whereby the copolymer
To improve the thermal stability of
Stabilization techniques have been proposed. Improvement of thermal stability of oxymethylene copolymer
Of technology to achieve the goal by blending various stabilizers
The following are examples. For example,
JP-A-5-22508 discloses sterically hindered phenol and charcoal.
Alkaline earth metal salts of fatty acids having a prime number of 10 to 22 and / or
Alternatively, the hydroxide of alkaline earth metal may be
No. 6748 discloses a sterically hindered phenol and a compound having 2 carbon atoms.
Alkaline earth metal salts of 2 to 36 fatty acids are disclosed in
No. 44227 discloses a polyamide and a C12-C3 compound.
5 fatty acids, calcium fatty acids having 12 to 35 carbon atoms
Salts, calcium of 12-35 aliphatic alcohols
Or at least one of the group consisting of magnesium salts
Is disclosed in Japanese Patent Publication No. Sho 62-58387,
Amine-substituted triazine compounds and sterically hindered phenols
And alkali or alkaline earth metal hydroxides, inorganic
Combination of acid, carboxylate or alkoxide
The combination is disclosed in Japanese Patent Application Laid-Open No. 4-63857.
Polyhydric alcohol having 10 to 10 and having 22 to 32 carbon atoms
Of polyhydric alcohols derived from higher fatty acids
Alkaline earth of acid esters and fatty acids having 12 to 35 carbon atoms
Combinations of metal salts have been proposed. Improvement of thermal stability of oxymethylene copolymer
The following is a specific example of a technique performed by heat melting treatment.
Things are raised. For example, Japanese Patent Publication No. 39-8071
Reports include roll mills, labo plast mills, and vented hens
Use shell mixer, Banbury mixer and extruder
The method of heat melting treatment is disclosed in Japanese Patent Publication No. 58-1145.
No. 0 discloses degassing using an extruder under reduced pressure.
Melt-kneading from the surface, and then using a surface-renewal type mixer.
A method for performing degassing purification has been proposed. Also these
The heat melting stabilization method can be performed even in the presence of a conventionally known stabilizer.
It is also shown that it can be performed. However, these
Depending on the technology, the thermal stability of the oxymethylene copolymer
Is improved, but still inadequate, and
Indicates that the decrease in thermal stability when coloring
It was not good. SUMMARY OF THE INVENTION In order to solve the present invention,
The challenge is to color the oxymethylene copolymer.
Color pigments such as carbon black and titanium oxide
When blended, the thermal stability of the copolymer is greatly impaired.
That is to prevent that. [0008] The present invention is to solve the problem.
Challenges in stabilizing oxymethylene copolymers
With respect to 100 parts by weight of the oxymethylene copolymer,
(A) 0.01 to 5 parts by weight of sterically hindered phenol
(B) 0.01 to 7 parts by weight of an amine-substituted triazine compound
And (C) hydroxylation of alkali metal or alkaline earth metal
Group consisting of a substance, or an inorganic acid salt or an alkoxide
At least one of the metal-containing compounds represented by
1 to 5 parts by weight of (D) fatty acid having 10 to 36 carbon atoms
Potassium metal or alkaline earth metal salt 0.001-5
Part by weight and (E) a polyhydric alcohol having 2 to 10 carbon atoms
And higher fatty acids having 10 to 32 carbon atoms
At least one fatty acid ester of polyhydric alcohol
-5.0 parts by weight and / or (F) having 10 or more carbon atoms
One or more of higher fatty acid amides having a long chain 0.01 to
Oxymethylene copolymer tree blended with 5.0 weight
The fat mixture is raised by 100 ° C. from the melting point of the copolymer.
Temperature range up to the maximum temperature, such as an extruder
Using a continuous melt-kneading device, remove from the vent port under reduced pressure.
It is characterized by performing melt stabilization processing while performing gas.
With improved thermal stability, especially for color pigments
This was achieved by a method for producing the copolymer resin composition. In the present invention, the oxymethylene copolymer is
Is preferably 0.4 to 40 mol% in the oxymethylene main chain.
Or oxyalkylene units of 0.4 to 10 mol%.
A copolymer. Such a copolymer is formaldehyde
And / or cyclic oligomers thereof, such as trioxa
Cyclic or tetraoxane in the presence of a polymerization catalyst
By acting ter or cyclic acetal
can get. As the polymerization catalyst, a general cationic polymerization catalyst
Although it is used, a compound containing boron fluoride is particularly preferable.
Hydrates and coordination complex compounds are used,
Boron trifethylene boron coordination complex
Sheets are particularly preferred. Used as a comonomer
The cyclic ether or cyclic acetal has the following general formula
Refers to the compound represented by (1). [0010] Where R ₁ , R _Two , R _Three , And R _Four Is the same
One or different, such as hydrogen atom, alkyl group, etc.
Or an alkyl group substituted with halogen. R _Five Is meth
A len group or an oxymethylene group or
Methylene group substituted by a kill group or halogenated alkyl group
Or an oxymethylene group (where n is an integer of 0 to 3)
Which is a number) or a general formula (2),
A divalent group represented by (3) (in this case, n is 1
And m is an integer of 1 to 4.) Alkyl above
The group has 1 to 5 carbon atoms, the hydrogen atom of which is 0 to 5
May be substituted with up to three halogen atoms, especially chlorine atoms
No. Specific cyclic acetal or cyclic acetate
As ter, ethylene oxide, propyleneoxy
Do, epichlorohydrin, and 1,3-dioxola
1,3-dioxepane, 1,3,5-trioxepane
, 1,3,6-trioxocan, etc.
Can be. Oxymethylene obtained by polymerization reaction
The copolymer is diethylamine, triethylamine, di-i
so-propylamine, tri-iso-propylamido
, Mono-n-butylamine, dibutylamine, trib
Shown by specific examples of tylamine, piperidine, morpholine, etc.
Primary, secondary and tertiary amines, alkali and alkaline earth metals
Hydroxide and trivalent organophosphorus compounds used alone
Known methods, or these compounds are treated with water, meta
Nol, acetone, methyl ethyl ketone, benzene,
Known for use in the form of a solution dissolved in solvents such as ruene
Deactivation and removal treatment of the catalyst
it can. Among these, methods using tertiary amines
And trivalent organophosphorus shown in JP-B-55-42085
The method of deactivating the catalyst using a compound is a preferable method.
One. [0013] The resin composition of the present invention is used in the method.
The component (A), sterically hindered phenol, is basically
Having at least one structure represented by the general formula (4)
(Wherein R ₆ And R ₇ Is an alkyl group,
Represents a substituted alkyl group. ). Embedded image Specific examples of sterically hindered phenols include:
2,2'-methylene-bis (4-methyl-6-t-butyi
Phenol), 4,4'-methylene-bis (2,6-
Di-t-butylphenol), 1,3,5-trimethyl
-2,4,6-tris (3,5-di-t-butyl-4-
Hydroxobenzyl) benzene, 3,5-di-t-butyi
4-Hydroxybenzyldimethylamine, stearyl
-3,5-di-t-butyl-4-hydroxybenzyl
Phosphonate, diethyl-3,5-di-t-butyl-4
-Hydroxybenzylphosphonate, 2,6,7-tri
Oxa-1-phospha-bicyclo [2,2,2] -oct
To-4-yl-methyl-3,5-di-t-butyl-4-
Hydroxyhydrocinnamate, 3,5-di-t-buty
4-Hydroxyphenyl-3,5-distearyl-
Thiotriazylamine, 2 (2′-hydroxy-3 ′,
5'-di-t-butylphenyl) -5-chlorobenzoto
Riazole, 2,6-di-t-butyl-4-hydroxy
Methylphenol, 2,4-bis- (n-octylchi
E) -6- (4-Hydroxy-3,5-di-t-butyl)
Anilino) -1,3,5-triazine, N, N′-hex
Samethylene bis (3,5-di-t-butyl-4-hydro
Xy-hydrocinnamamide), octadecyl-3-
(3,5-di-butyl-4-hydroxyphenyl) pro
Pionate, 1,6-hexanediol-bis [3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate], pentaerythrityl-tetrakis
[3- (3,5-di-tert-butyl-4-hydroxyphenyl)
Enyl) propionate], triethylene glycol-
Bis [3- (3,5-dimethyl-4-hydroxyphenyl)
Le) propionate], triethylene glycol-bis
[3- (3-tert-butyl-5-methyl-4-hydroxy
Phenyl) propionate] triethylene glycol-
Bis [3- (3,5-di-t-butyl-4-hydroxy
Phenyl) propionate], 2,2'-thiodiethyl
-Bis [3- (3,5-di-t-butyl-4-hydroxy)
Cyphenyl) propionate] and the like.
However, preferred among these are those represented by the general formula (5).
Is a compound having at least one or more of the following structures: Embedded image That is, as preferred examples of these,
Is, among the above, N, N′-hexamethylenebis (3,
5-di-t-butyl-4-hydroxy-hydrocinnama
Mido), octadecyl-3- (3,5-di-butyl-4)
-Hydroxyphenyl) propionate, 1,6-hexyl
Sundiol-bis [3- (3,5-di-t-butyl-
4-hydroxyphenyl) propionate], pentae
Lislicyl-tetrakis [3- (3,5-di-t-butyl)
Ru-4-hydroxyphenyl) propionate],
Ethylene glycol-bis [3- (3,5-dimethyl
-4-hydroxyphenyl) propionate], trie
Tylene glycol-bis [3- (3-t-butyl-5-
Methyl-4-hydroxyphenyl) propionate]
Ethylene glycol-bis [3- (3,5-di-t-
Butyl-4-hydroxyphenyl) propionate],
2,2'-thiodiethyl-bis [3- (3,5-di-t
-Butyl-4-hydroxyphenyl) propionate]
Corresponds to this. Also, more preferable among these are
Is 1,6-hexanediol-bis [3- (3,5
-Di-t-butyl-4-hydroxyphenyl) propio
Pentaerythrityl-tetrakis [3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Le) propionate], triethylene glycol-bis
[3- (3,5-dimethyl-4-hydroxyphenyl)
Propionate], triethylene glycol-bis [3
-(3-t-butyl-5-methyl-4-hydroxyphene
Nyl) propionate] triethylene glycol-bis
[3- (3,5-di-t-butyl-4-hydroxyphene)
Nyl) propionate], 2,2′-thiodiethyl-bi
[3- (3,5-di-tert-butyl-4-hydroxyphenyl)
Enyl) propionate]. Used in the resin composition production method of the present invention
The component (B), the amine-substituted triazine compound, is basically
Has an amine substitution having a structure represented by the general formula (6).
Triazines or the amino-substituted triazines and e
At least one of the initial polycondensates with
To taste. Embedded image Where R ₈ , R ₉ , R _Ten Is a hydrogen atom, halogen
Atom, hydroxyl group, alkyl group, alkoxy group, aryl
Group, hydrogenated aryl group, amino group, or substituted amino group
And at least one of them is an amino group or
It is a substituted amino group. An amine-substituted triazine compound, or
First of amino-substituted triazine compound and formaldehyde
Specific examples of the polycondensate include guanamine, melamine,
N-butylmelamine, N-phenylmelamine, N, N-
Diphenylmelamine, N, N-diallylmelamine, N,
N ', N "-triphenylmelamine, N, N', N"-
Trimethylolmelamine, benzoguanamine, 2,4-
Diamino-6-methyl-sym-triazine, 2,4-
Diamino-6-butyl-sym-triazine, 2,4-
Diamino-6-benzyloxy-sym-triazine,
2,4-diamino-6-butoxy-sym-triazi
2,4-diamino-6-cyclohexyl-sym-
Triazine, 2,4-diamino-6-chloro-sym-
Triazine, 2,4-diamino-6-mercapto-sy
m-triazine, amelin (N, N, N ', N'-tetra
Lacyanoethyl benzoguanamine) or phorine with them
Examples include an initial polycondensate with mualdehyde. Inside
Also melamine, methylol melamine, benzoguanami
And water-soluble melamine-formaldehyde resins are particularly preferred.
New Used in the method for producing a resin composition of the present invention.
The component (C) contains an alkali metal or an alkaline earth metal.
Hydroxide or the same inorganic acid salt or the same alkoxide
However, as inorganic salts, carbonates, phosphates, silicates,
Borates, etc. are raised.
Oxide, ethoxide and the like can be mentioned. Among these
Preferred are hydroxides of alkaline earth metals,
Although acid salts and alkoxides are more preferable,
Calcium hydroxide, magnesium hydroxide, potassium hydroxide
Calcium carbonate and magnesium carbonate. Used in the method for producing a resin composition of the present invention.
The component (D) is an alkali fatty acid having 10 to 36 carbon atoms.
A metal or alkaline earth metal salt, preferably
Saturated or unsaturated fatty acids having 10 to 36 carbon atoms
Alkaline earth metal salts of magnesium,
Means salt, barium, strontium, etc.
However, it is more preferable that the saturated
Sum or alkaline earth metal salts of unsaturated fatty acids
You. Preferred specific examples of fatty acids include lauric acid,
Lumitic acid, stearic acid, behenic acid, montanic acid, 1
2-hydroxystearic acid, oleic acid, erucic acid, etc.
Is raised. Used in the method for producing a resin composition of the present invention.
The fatty acid ester of the polyhydric alcohol (E) has a carbon number of
Polyhydric alcohol having 2 to 10 and 10 to 32 carbon atoms
Derived from higher fatty acids, preferably having 22 to 32 carbon atoms
Is an ester compound represented by the following formula:
Examples of coal include glycerin, diglycerin,
Antaerythritol, sorbitan, ethylene glycol
, Diethylene glycol, trimethylolmethane,
Rietyrolethane raised and preferred higher fatty acids
Is a higher fatty acid having 22 to 32 carbon atoms.
Behenic acid, cerotic acid, montanic acid, laccelic acid
And the like. Used in the resin composition production method of the present invention
(F) A higher fatty acid having a long chain having 10 or more carbon atoms of the component
An amide is a higher fatty acid having a linear chain having 10 or more carbon atoms.
Means amide compounds derived from aliphatic amines
However, preferred specific examples are stearamide, ethylene
Bis-stearamide, methylene bis-stearamide,
Tylene bis lauroamide, palmitamide, oley
Acid amide and the like, a more preferred specific example is ethylene
Bis-stearamide, methylene bis-stearamide,
Tylene bis lauroamide. Next, the method for producing the resin composition of the present invention will be described.
For the compounding of the stabilizer, the oxymethylene copolymer and
Each component of (A) to (F) is an oxymethylene copolymer 1
(A) sterically hindered phenol 0.1 wt.
01 to 5 parts by weight, preferably 0.01 to 1 part by weight
(B) Amine-substituted triazine compound 0.01 to 7% by weight
Parts, preferably 0.1 to 1 part by weight and (C) alkali gold
Hydroxides of the genus or alkaline earth metals, or inorganic acids
Metals represented by the group consisting of salts or alkoxides
0.001 to 5 parts by weight of at least one compound is preferably used.
Or from 0.001 to 3 parts by weight and (D) carbon number 10
Alkali metal or alkaline earth gold of 36 fatty acids
Genus salt 0.001-5 parts by weight, preferably 0.01-3
Part by weight and (E) a polyhydric alcohol having 2 to 10 carbon atoms
And higher fatty acids having 22 to 32 carbon atoms
At least one fatty acid ester of polyhydric alcohol
To 5 parts by weight, preferably 0.01 to 3 parts by weight and / or
Or (F) higher fatty acids having a long chain of 10 or more carbon atoms.
One or more types of amides, 0.01 to 5 parts by weight, preferably 0.0
Although 1 to 3 weight can be blended, preferably, (A) and
(B), (C), (D), (E) and (F)
Combine. In addition, regarding the compounding amount of each component,
If less, the stabilizing effect is insufficient and too much
In such a case, gas is generated during molding and the appearance of the molded product is poor.
Not good. The above (A) to (E) and / or (F)
Component and oxymethylene copolymer prior to stabilization by heat melting
Chi, blender, mixing device such as Henschel mixer
Is a preferred method. Premix
If dry, wet, emulsion, suspension
Then, it can be implemented. Wet, emulsion, suspension
Is water, methanol, aceto
Benzene, toluene, cyclohexane, etc.
It is prepared by adding other known solvents. [0027] The resin composition manufacturing method of the present invention comprises
One requirement, the melt stabilization treatment, is (A)-(E) and
And / or oxymethylene containing component (F)
The polymer resin mixture is separated from the melting point temperature of the copolymer by
In the temperature range up to 00 ° C higher,
Using a continuous melting and kneading apparatus such as
Degas from the vent port under reduced pressure.
It is characterized in that the melt stabilization process is performed while not being performed. Melting
The kneading temperature is 10 ° C or more to 90 ° C or more from the melting point.
The temperature is preferably in the range of 15 ° C. or higher to 65 ° C. or higher than the melting point.
A degree range is more preferred. Decompression degree is 0.01mmHg ~ 5
The range of 00 mmHg is preferable, and 0.01 mmHg to 2 mm
The range of 00 mmHg is more preferable, and 0.01 mmHg
The range of 範 囲 100 mmHg is most preferred. Continuous melt kneading
Preferred for the extruder is an extruder. That is, vent
Degassing of decomposed formalin and impurities under reduced pressure
A single or twin screw extruder that can remove
Preferably, a single-shaft or twin-shaft pusher with two or more vents
It is more preferable to use two or more vent ports.
It is a twin-screw extruder having the above. That is, the preferred
A preferred embodiment is an oxymethylene compound containing a predetermined stabilizer.
In heating and melting the copolymer at a predetermined temperature, an extruder
Is a method of degassing at a predetermined degree of reduced pressure from the vent port of
More preferred embodiments have two or more vents.
It is a method of degassing at a constant decompression degree, more preferable
Uses a twin-screw extruder and uses two or more vents
This is a method of degassing at a constant degree of reduced pressure. As the type of the twin-screw extruder, two screws are used.
Screws rotate in the same direction and different directions, screw grooves
Deep, shallow, and even screw configurations
Is a normal forward screw type screw and has a kneading effect
Screw type screw, Knee Dain
Incorporates glock to improve degassing effect
A wide variety of products, such as those with seal rings
Exists, but basically achieves a good dispersion of the stabilizer
Oxymethylene copolymer
Anything that does not impair the stability due to thermal deterioration
It may be a displacement extruder. However good
The best thing is that the two screws rotate in the same direction, and
It has a screw with a deep groove. If the melt-kneading temperature is lower than the melting point,
If the melting is insufficient and the melting point is 100 ° C or higher,
This results in thermal degradation of the simethylene copolymer. The degree of pressure reduction is
Degassing becomes insufficient at pressures higher than, and sufficient thermal stability improvement
No effect. Degas from the vent under reduced pressure.
If not performed, sufficient thermal stability improvement effect cannot be obtained.
No. In addition, a method of connecting and using two extruders,
Are JP-B-58-11450, JP-B-61-52.
No. 850, a mixture of an extruder and a surface renewal type
The method of connecting and using joint machines further enhances the effects of the present invention.
It is effective for. In addition, the resin composition of the present invention
Other stabilizers, fillers, pigments, lubricants, plastics as desired
Additives such as chemicals, ultraviolet absorbers, flame retardants, flame retardant aids,
Other components such as other resins and elastomers are appropriately compounded
obtain. Examples of fillers include glass beads, wollast
Knight, mica, talc, kaolin, silicon dioxide, clay
ー, asbestos, silica, diatomaceous earth, graphite,
Mineral filler, glass fiber represented by molybdenum disulfide
Fiber, milled fiber, potassium titanate fiber, boron
Represented by inorganic fibers such as fibers, carbon fibers and aramid fibers
Organic fiber. The oxymethylene copolymer resin group of the present invention
The method for producing the product is as follows:
Each component of (E) and / or (F) is blended and
Using a continuous melt-kneading device such as an extruder with a vent port
Degas from the vent port under reduced pressure.
It is characterized by performing a stabilization process.
To color pigments such as titanium oxide and titanium oxide
Providing the copolymer resin composition having excellent thermal stability
I do. The effects of the present invention are (A) to (E) and / or
The effect of the stabilizer of each component (F) is due to the continuous melting of the extruder etc.
Degas from the vent port under reduced pressure using a kneading device.
Higher synergistically by performing melt stabilization treatment
It is considered that the result was obtained. That is, this effect is simply
In addition, the stabilizers (A) to (E) and / or (F) are used.
The present invention also uses a conventional stabilizer to
Even if the stabilization process is performed,
Not. The present invention is described below with reference examples, examples, and comparative examples.
The bright resin composition will be described. EXAMPLES Reference Example 1 97.5 parts by weight of trioxane and ethylene oxide as a comonomer
2.5 parts by weight of styrene with boron triborate etherate as catalyst
And methylal as a chain transfer agent,
Polymerization is carried out in a twin-screw kneader with
Was. After the end of the polymerization, a small amount of triphenylphosphine
After deactivating the catalyst with a zen solution, pulverize
A copolymer was obtained. p-chloroform (added with α-pinene
In addition, the intrinsic viscosity at 60 ° C. is 1.4 dl / g.
Was. Reference Example 2 95.5 parts by weight of trioxane and 1,3 as a comonomer
4.5 parts by weight of dioxolane in boron triboride ether
Using methyl as a catalyst and methylal as a chain transfer agent
In a two-axis kneader with paddles that engage with each other
Polymerization was performed. After the polymerization is completed, a small amount of tributylamine
After deactivating the catalyst with a solution
A copolymer was obtained. p-chloroform (added with α-pinene
In addition, the intrinsic viscosity at 60 ° C. is 1.46 dl / g.
there were. Example 1 100% by weight of the oxymethylene copolymer produced in Reference Example 1
In the part, triethylene glycol-bis [3- (3-t-
Butyl-5-methyl-4-hydroxyphenyl) propyl
Onate] (Sterically hindered phenol by Ciba-Geigy)
Leganox 245) 0.2 parts by weight,
Melamine 0.1 parts by weight, magnesium hydroxide 0.05
Parts by weight and 0.05 parts by weight of calcium stearate
0.1 parts by weight of behenic acid monoglyceride and ethylene
Add 0.1 parts by weight of bis-stearamide,
Premixing was performed with a shell mixer. After this vent
Cylinder temperature 2 using a twin screw extruder with one mouth
Resin composition melt-kneaded at 00 ° C and pelletized
Was manufactured. At this time, the pressure was reduced by 150 mmHg from the vent port.
Degassed below. The thermal stability evaluation of the resin composition
Heat stability and former
The measurement was performed by measuring the amount of generated phosphorus. Wearing resin composition
The thermal stability evaluation for color pigments
After mixing 0.3 parts by weight of black, remelt with a twin screw extruder
Kneaded, stable heat retention using the obtained black colored pellets
And measuring the amount of formalin generated during molding
evaluated. The results are shown in Table 1. The retention heat stability
The measurement of the amount of formalin generated during molding is performed as follows.
Was. -Stable heat stability: Injection molding with 75 ton mold clamping force
Cylinder temperature 240 ° C, molding cycle 30
And set the time until silver occurs on the test piece.
It was measured.・ Amount of formalin generated during molding: 25 ton mold clamping pressure
Cylinder temperature 190 ° C, gold
Set the mold temperature to 65 ° C and the molding cycle to 15 seconds,
1.5 g of molded articles were injection molded. Take out the molded product
Immediately put in a gas-tight container,
The outgassed gas was recovered and its formalin amount was measured. Example 2 Example 1 is different from Example 1 in that the vent ports of the extruder are added to two places,
Degassing under reduced pressure of 150 mmHg
Except that Example 1 was repeated. The results are shown in Table 1. Example 3 In Example 1, the vent port of the extruder was expanded to three places,
Degas under reduced pressure of 150 mmHg from the outlet
Example 1 was repeated except for the above. The results are shown in Table 1.
Was. Comparative Example 1 Example 1 was degassed under reduced pressure from the vent of the extruder.
Example 1 was repeated except that none was present. The results are shown in Table 1.
did. Example 4 Using the oxymethylene copolymer produced in Reference Example 2,
Example 1 was repeated. The results are shown in Table 1. Example 5 Using the oxymethylene copolymer produced in Reference Example 2,
Example 2 was repeated. The results are shown in Table 1. Example 6 Using the oxymethylene copolymer produced in Reference Example 2,
Example 3 was repeated. The results are shown in Table 1. Comparative Example 2 Using the oxymethylene copolymer produced in Reference Example 2,
Comparative Example 1 was repeated. The results are shown in Table 1. Examples 7-9 Examples without the use of ethylene bis stearamide
Steps 1 to 3 were repeated. The results are shown in Table 2. Comparative Example 3 Comparative Example Without Using Ethylenebisstearamide
1 was repeated. The results are shown in Table 2. Examples 10 to 12 Example 1 without using behenic acid monoglyceride
〜3 was repeated. The results are shown in Table 2. Comparative Example 4 Comparative Example 1 without using behenic acid monoglyceride
Was repeated. The results are shown in Table 2. Comparative Examples 5-8 Behenic acid monoglyceride and ethylene bisstearo
Examples 1 to 3 (Comparative Examples 5 to 7) without using an amide
And Comparative Example 1 (corresponding to Comparative Example 8) are repeated.
Was. The results are shown in Table 3. [Table 1] [Table 2] [Table 3]

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-5-156118 (JP, A) European Patent Application Publication 289142 (EP, A2) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 59/00-59/04

Claims (1)

(57) [Claim 1] When stabilizing an oxymethylene copolymer, (A) 0.01 to 5 parts by weight of a sterically hindered phenol is added to 100 parts by weight of the oxymethylene copolymer. Parts of (B) 0.01 to 7 parts by weight of an amine-substituted triazine compound and (C) a metal-containing compound represented by the group consisting of an alkali metal or alkaline earth metal hydroxide or inorganic acid salt or alkoxide. 0.001 for at least one
To 5 parts by weight, (D) an aliphatic alkali metal having 10 to 36 carbon atoms, or 0.001 to 5 parts by weight of an alkaline earth metal salt and (E) a polyhydric alcohol having 2 to 10 carbon atoms and carbon At least one fatty acid ester of a polyhydric alcohol derived from a higher fatty acid having a number of 10 to 32;
And / or (F) 0.01 to 5.0 parts by weight of at least one kind of higher fatty acid amide having a long chain of 10 or more carbon atoms. Performing melt stabilization treatment while degassing from the vent port under reduced pressure using a continuous melt kneading device such as an extruder having a vent port in a temperature range from the melting point temperature of the coalescence to a temperature higher by 100 ° C. It said method for producing a copolymer resin composition having improved thermal stability with respect to color pigments.