CN106947211A - Polyacetal resin granular composition and polyacetal resin composite - Google Patents

Polyacetal resin granular composition and polyacetal resin composite Download PDF

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CN106947211A
CN106947211A CN201611136170.8A CN201611136170A CN106947211A CN 106947211 A CN106947211 A CN 106947211A CN 201611136170 A CN201611136170 A CN 201611136170A CN 106947211 A CN106947211 A CN 106947211A
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polyacetal resin
granular composition
acid
resin granular
nitrogen
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CN106947211B (en
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近藤知宏
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Asahi Kasei Corp
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Asahi Kasei Kogyo KK
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/101—Esters; Ether-esters of monocarboxylic acids
    • C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C08K5/134—Phenols containing ester groups
    • C08K5/1345—Carboxylic esters of phenolcarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/22—Compounds containing nitrogen bound to another nitrogen atom
    • C08K5/24—Derivatives of hydrazine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
    • C08K5/31—Guanidine; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C08K5/34922—Melamine; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The present invention relates to polyacetal resin granular composition and polyacetal resin composite.Obtain the polyacetal resin granular composition of a kind of coloring that can suppress nitrogen-containing compound and excellent in uniformity, and by adding the polyacetal resin granular composition, obtain a kind of high-purity, performance can also be played consistently in long-term production and production stability is excellent, heat endurance is high and by shaping after formed body release formaldehyde the considerably less polyacetal resin composite of amount.A kind of polyacetal resin granular composition, it, which contains at least one (A) antioxidant and at least one (B) intramolecular, has the nitrogen-containing compound of two or more nitrogen-atoms.

Description

Polyacetal resin granular composition and polyacetal resin composite
Technical field
The present invention relates to polyacetal resin granular composition and polyacetal resin composite.
Background technology
The processability and productivity ratio of polyacetal resin are excellent, thus with can be shaped by melt injection, melting extrusion The various manufacturing process such as shaping efficiently produce the product of desired shape or the advantage of part.
On the other hand, all the time, make polyacetal resin melt during, in order to prevent by heat or oxygen cause it is bad Change, coordinate the various additives such as antioxidant, heat stabilizer, then carry out melting mixing etc., thus manufacture polyacetal resin group Compound.The polyacetal resin be widely used in Material for electrical/electroniuse use field, automotive field, other various industrial materials fields, In food packaging applications, part Material Field.
As described above, all the time using the polyacetal resin composite for being combined with various additives, but in addition, There are problems that additive itself dust from flying,.In view of described problem, it is proposed that by adding containing calcium stearate Plus agent composition is a granulated into graininess, the technology in defined thermoplastic resin is then coupled to (for example, with reference to patent document 1)。
Suppress the technology (example of coloring caused by calcium stearate using by heat during resin melting in addition, it is also proposed Such as, referring to patent document 2).
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 8-333477 publications
Patent document 2：No. 5206093 publications of Japanese Patent No.
The content of the invention
Invent problem to be solved
However, in above-mentioned patent document 1 and 2, the suppression of coloring on nitrogen-containing compound is not referred to or on production The polyacetal resin group that high-purity, production stability are excellent and yield of formaldehyde of formed body after shaping is few The technology of compound, has room for improvement at the aspect.
Therefore, it is an object of the present invention to provide suppressing the coloring of nitrogen-containing compound and the polyacetals of excellent in uniformity Resin particulate additive, and containing the polyacetal resin granular composition, high-purity, in long-term production Performance can also be played consistently and production stability is excellent, heat endurance is high and by shaping after formed body release first The considerably less polyacetal resin composite of the amount of aldehyde.
The means used to solve the problem
The present inventor etc. has made intensive studies to above-mentioned problem of the prior art, as a result finds：By using with spy The nitrogen-containing compound and antioxidant of fixed structure, obtain that the coloring of nitrogen-containing compound, the polyacetals of excellent in uniformity can be suppressed Resin granular composition, by using the polyacetal resin granular composition, can provide high-purity, even in length Performance can also be played consistently in phase production and production stability is excellent, heat endurance is high and by shaping after formed body The few polyacetal resin composite of the formaldehyde amount of release, so as to complete the present invention.
That is, the present invention is as described below.
[1] a kind of polyacetal resin granular composition, it contains
At least one (A) antioxidant and
At least one (B) intramolecular has the nitrogen-containing compound of two or more nitrogen-atoms.
[2] polyacetal resin granular composition as described described in [1], wherein,
The pine dress apparent specific gravity of the polyacetal resin granular composition is more than 0.3 and less than 0.8.
[3] polyacetal resin granular composition as described described in [1] or [2], wherein,
The average grain diameter of the polyacetal resin granular composition is more than 100 μm and below 2mm.
[4] polyacetal resin granular composition as described described in any one of [1] to [3], wherein,
The fusing point of (A) antioxidant is more than 30 DEG C.
[5] polyacetal resin granular composition as described described in any one of [1] to [4], wherein,
Polyacetal resin granular composition also contains (C) fatty acid ester.
[6] polyacetal resin granular composition as described described in any one of [1] to [5], wherein,
(B) it is selected from by glyoxaline compound, amino triazine that intramolecular, which has the nitrogen-containing compound of two or more nitrogen-atoms, At least one in the group that class compound, triazole class compounds and hydrazide kind compound are constituted.
[7] polyacetal resin granular composition as described described in any one of [1] to [5], wherein,
(A) content of antioxidant is more than 20 mass %.
[8] polyacetal resin granular composition as described described in any one of [1] to [7], wherein,
Polyacetal resin granular composition also contains (D) thermoplastic polymer.
[9] polyacetal resin granular composition as described described in any one of [1] to [8], wherein,
Polyacetal resin granular composition also contains (E) inorganic filler.
[10] a kind of polyacetal resin composite, it contains
Polyacetal resin described in any one of [1] to [9] with granular composition and
Polyacetal resin.
[11] polyacetal resin composite as described described in [10], wherein,
Relative to the mass parts of polyacetal resin 100, the polyacetal resin composite contains the mass parts of 0.1 mass parts~10 Any one of [1] to [9] described in polyacetal resin granular composition.
[12] a kind of manufacture method of polyacetal resin composite, it is the polyacetal resin combination described in [11] The manufacture method of thing, wherein, the manufacture method includes
By the process of the polyacetal resin and the polyacetal resin with granular composition melting mixing.
[13] manufacture method of polyacetal resin composite as described described in [12], wherein, the manufacture method bag Include
By the polyacetal resin mass parts of mass parts of granular composition 0.1~50 and the mass of polyacetal resin 100 Part melting mixing and formed masterbatch process and
The process for further carrying out melting mixing to polyacetal resin after masterbatch is formed.
Invention effect
According to the present invention it is possible to obtain that the coloring of nitrogen-containing compound, and the polyacetals tree of excellent in uniformity can be suppressed Fat granular composition.
In addition, by adding the polyacetal resin granular composition, high-purity can be obtained, even in long-term production Middle performance can also be played consistently and production stability is excellent, heat endurance is high and by shaping after formed body release The considerably less polyacetal resin composite of the amount of formaldehyde.
Embodiment
Hereinafter, the mode (hereinafter referred to as " present embodiment ") for implementing the present invention is explained.This following reality It is the illustration for illustrating the present invention to apply mode, it is not intended to limit the invention to following content.The present invention can be in its main points In the range of appropriate deformation and implement.
[polyacetal resin granular composition]
The polyacetal resin of present embodiment is contained with granular composition
Selected from (A) antioxidant at least one and
There is at least one of the nitrogen-containing compound of two or more nitrogen-atoms selected from (B) intramolecular.
((A) antioxidant)
The polyacetal resin granular composition of present embodiment contains at least one (A) antioxidant.
(A) fusing point of antioxidant is preferably more than 30 DEG C, more preferably more than 40 DEG C, more preferably 50 DEG C with On.
It is more than 30 DEG C by fusing point, the melting when preserving summer can be prevented, can be obtained well as additive Treatability.
As (A) antioxidant, from the viewpoint of being readily available, preferred hindered phenol anti-oxidants.
As (A) antioxidant, following material is not limited to, can be enumerated for example：3- (3 ', 5 '-di-t-butyl -4 '-hydroxyl Phenyl) propionic acid n-octadecane base ester, 3- (- 4 '-hydroxy phenyl of 3 '-methyl -5- tert-butyl groups) propionic acid n-octadecane base ester, 3- (3 ', 5 '-di-t-butyl -4 '-hydroxy phenyl) propionic acid n-tetradecane base ester, double (3- (3, the 5- di-t-butyl -4- hydroxyls of 1,6- hexylene glycols Phenyl) propionic ester), BDO double (3- (3,5- di-tert-butyl-hydroxy phenyl) propionic ester), the double (3- (3- of triethylene glycol The tert-butyl group -5- methyl -4- hydroxy phenyls) propionic ester), four (methylene -3- (3 ', 5 '-di-t-butyl -4 '-hydroxy phenyl) propionic acid Ester) methane, double (2- (3- (3- tertiary butyl-4-hydroxy -5- aminomethyl phenyls) propionyloxy) -1, the 1- dimethyl ethyls) -2 of 3,9-, 4,8,10- tetra- oxaspiro (5.5) hendecanes, N, the N '-methylene of bis- -3- (3 ', 5 '-di-tert-butyl-hydroxy phenyl) propiono six Base diamines, N, N '-bis- -3- (3 '-methyl -5 '-tert-butyl-hydroxy phenyl) propiono tetra-methylenedimine, N, N '-bis--(3- (3,5- di-tert-butyl-hydroxy phenyl) propiono) hydrazine, N- salicyls-N '-salicylidene hydrazine, 3- (N- salicyls) ammonia Base -1,2,4- triazoles, N, N '-bis- (2- (3- (3,5- dibutyl -4- hydroxy phenyls) propionyloxy) ethyl) oxamides etc..
In the hindered phenol anti-oxidants, particularly from the viewpoint of being readily available, the preferably double (3- of triethylene glycol (the 3- tert-butyl group -5- methyl -4- hydroxy phenyls) propionic ester), four (methylene -3- (3 ', 5 '-di-t-butyl -4 '-hydroxy phenyl) Propionic ester) methane, 3- (3,5- di-tert-butyl-hydroxy phenyl) propionic acid stearyl ester.
It should be noted that antioxidant can be used alone only one kind, it can also be applied in combination two or more.
The polyacetal resin of present embodiment is preferably 20 matter with the content of (A) antioxidant in granular composition Measure more than %, more preferably more than 30 mass %, further preferred more than 40 mass %.
By for more than 20 mass %, can effectively suppress the coloring of (B) nitrogen-containing compound described later.
((B) intramolecular has the nitrogen-containing compound of two or more nitrogen-atoms)
The polyacetal resin granular composition of present embodiment, which contains at least one (B) intramolecular, has two or more The nitrogen-containing compound of nitrogen-atoms.
There is the nitrogen-containing compound of two or more nitrogen-atoms as (B) intramolecular, following material is not limited to, example can be enumerated Such as：Amino triazines, glyoxaline compound, amides compound, carbamide compounds, hydrazide kind compound, guanidine Compound, triazole class compounds etc..
(B) there is intramolecular the nitrogen-containing compound of two or more nitrogen-atoms can be used alone only one kind, can also be used in combination It is two or more.
As amino triazines, following material is not limited to, can be enumerated for example：(1) dicyandiamide, (2) amino take Cocondensation for triazine, (3) amino substitution triazine and formaldehyde etc..
Replace triazine as (2) amino, be not limited to following material, can enumerate for example：Guanamines (2,4- diaminourea equal three Piperazine), melamine (2,4,6- tri-amino-p-triazine), N- melamine-butyls, N phenyl melamine, N, N- diphenyl trimerizations Cyanamide, N, N- diallyl melamines, N, N ', N "-triphenyl melamine, N- melamine methylols, N, N '-dihydroxy first Base melamine, N, N ', N "-trimethylol melamine, benzoguanamine (2,4- diaminourea -6- phenyl s-triazine), 2,4- diaminos Base -6- methyl s-triazine, 2,4- diaminourea -6- butyl s-triazine, 2,4- diaminourea -6- benzyloxies s-triazine, 2,4- diaminourea - 6- butoxy s-triazine, 2,4- diaminourea -6- cyclohexyl s-triazine, 2,4- diaminourea -6- chloro-s-triazines, 2,4- diaminourea -6- Sulfydryl s-triazine, 2,4- dihydroxy -6- amino s-triazine (ammelide), 2- hydroxyl -4,6- diaminourea s-triazine (ammeline), N, N ', N '-four cyano ethyl benzoguanamine etc..
Replace triazine and the cocondensation of formaldehyde as (3) amino, be not limited to following material, such as melamine can be enumerated Amine-for-aldehyde condensation polymer etc..
In these compounds, preferably dicyandiamide, melamine and melamine-formaldehyde condensation products.
As glyoxaline compound, following material is not limited to, can be enumerated for example：Imidazoles, 1- methylimidazoles, 2- methyl miaows Azoles, 1,2- methylimidazoles, 2- phenylimidazoles etc..
As amides compound, following material is not limited to, can be enumerated for example：Polyamide 6, polyamide 66, gather oneself two Acyl m-xylene diamine (polyamide MXD6), dimer acid polyamide, polyamide 12,6/66/610/12 quarternary copolymerized polyamide, 6/ 66/610 ternary polymerization polyamide, 6/12 copolyamide etc..
As carbamide compounds, following material is not limited to, can be enumerated for example：Biuret, biruea, ethylidene-urea, Asia Alkylidene urea such as propyl group urea etc..In these compounds, preferred ethylidene-urea.
As hydrazide kind compound, following material is not limited to, can be enumerated for example：3,9- double (2- carboxy ethyls) -2,4, The hydrazides of 8,10- tetra- oxaspiro [5.5] hendecane two, the hydrazides of 1,3,5- tri- (3- carboxypropyls) isocyanuric acid ester three etc.；(methyl) Polymer-type hydrazide compound such as homopolymer or copolymer of acrylic acid hydrazides etc..
In these compounds, dihydrazide compound is preferably used.The hydrazides of more preferably 1,12- dodecanedioic acids two, the last of the ten Heavenly stems two The aliphatic dihydrazide compound such as acid dihydrazide, adipic dihydrazide；1,8- naphthalene dihydrazi, 2,6- naphthalenes dihydrazi, The aromatic series dihydrazide compound such as terephthaldehyde's acid dihydrazide.
As guanidine compound, following material is not limited to, can be enumerated for example：Glycocyamine, guanidine quinoline (グ ア ノ リ Application), Glycocyamidine, oxalyl guanidine, kreatinin, imino group urazole, malonylguanidine, the mesoxalyl guanidine (ジ of メ ソ キ サ リ グ ア bis- Application) etc..
As triazole class compounds, following material is not limited to, can be enumerated for example：2- (2 '-hydroxyl -5 '-aminomethyl phenyl) BTA, 2- (2 '-hydroxyl -3 ', 5 '-di-tert-butyl-phenyl) BTA, 2- (2 '-hydroxyl -3 ', 5 '-two tert-amyl benzenes Base) BTA, 2- (2 '-hydroxyl -3 ', 5 '-diisoamyl phenyl) BTA etc. have hydroxyl and alkyl (preferably C1-6Alkane Base) substituted aryl benzotriazole；The tools such as 2- [2 '-hydroxyl -3 ', 5 '-bis- (alpha, alpha-dimethylbenzyl) phenyl] BTA There is the benzotriazole of hydroxyl and aralkyl or alkyl substituted aryl；2- (2 '-hydroxyl -4 '-octyloxyphenyl) BTA etc. With hydroxyl and alkoxy (preferably C1-12Alkoxy) substituted aryl benzotriazole.As benzotriazole compound, on Preferably there is hydroxyl and C in stating3-6Alkyl replaces C6-10The benzotriazole of aryl (particularly phenyl), and with hydroxyl and C6-10Aryl-C1-6Alkyl (particularly phenyl C1-4Alkyl) substituted aryl benzotriazole.
(characteristic of polyacetal resin granular composition)
The polyacetal resin granular composition of present embodiment has to polyacetal resin due to for graininess High production rate is so as to improving the addition concentration in polyamide.
Here, " graininess " refers to that pine dress apparent specific gravity, the proportion i.e. under the nature comprising gases such as air are More than 0.3 powder and average grain diameter is more than 100 μm of powder.
The polyacetal resin of present embodiment is preferably pine dress apparent specific gravity, i.e. comprising air etc. with granular composition The powder that proportion under the nature of gas is more than 0.3.
Thus, it is possible to when forming the conevying efficiency when being transported in loaded on regulation container, polyacetals being handled The excellent polyacetal resin granular composition of Targets, powder handling.
Pine dress apparent specific gravity more preferably more than 0.4, further preferred more than 0.45.
On the upper limit, in the case where the usage amount of polyacetal resin granular composition is few, apparent specific gravity is filled from pine For less than 0.8 when weigh or quantitative feeder precision improve from the viewpoint of, preferably less than 0.8.
Pine dress apparent specific gravity can utilize (the thin close Krona company manufacture in river of powder tester：Powder tester model PT- E), it is measured using the canister of 100mL volumes.Specifically, can be by the method described in embodiment described later To determine.
The polyacetal resin granular composition of present embodiment can fill pine apparent ratio by controlling traffic condition Control again in above-mentioned number range.
It is preferred that the average grain diameter of the polyacetal resin granular composition of present embodiment be more than 100 μm and 2mm with Under.
When average grain diameter is more than 100 μm, it can also obtain good when manufacture polyacetal resin composite for a long time Production stability.Furthermore it is possible to prevent the generation that the powder in additive hopper is remained, treatability is excellent.
By the way that for below 2mm, following effect can be obtained：Do not need the excessive time can be with polyacetal resin equably Mixing, the free degree of processing conditions is high.
From the uniformity and suppression bunching of the polyacetal resin granular composition in polyacetal resin composite particle From the viewpoint of foreign matter in urea formaldehyde composition grain, average grain diameter more preferably below 1.5mm, further preferred 1.0mm with Under.
In addition, from the viewpoint of performance can play consistently and improve production stability, more preferably more than 200 μm, Further preferred more than 400 μm.
The average grain diameter of the polyacetal resin granular composition of present embodiment can be by embodiment described later The method of record is determined.
((C) fatty acid ester)
The polyacetal resin granular composition of present embodiment can also contain (C) fatty acid ester.
As (C) fatty acid ester, following material is not limited to, can be enumerated for example：Glycerol monopalmitate, the palm of glycerine two Acid esters, tripalmitin, glyceryl monostearate, glycerol distearate, glycerol tristearate, glycerine list behenic acid Ester, the behenate of glycerine two, glycerol tri-docosanoic acid ester, glycerine list montanate, the montanate of glycerine two, the montanic acid of glycerine three Ester, pentaerythritol monopalmitate, pentaerythrite dipalmitate, pentaerythrite tripalmitate, the palmitic acid of pentaerythrite four Ester, pentaerythritol monostearate, pentaerythritol stearic acid ester 2, pentaerythrite tristearate, the stearic acid of pentaerythrite four Ester, pentaerythrite list behenate, the behenate of pentaerythrite two, pentaerythrite tribehenin acid esters, the behenic acid of pentaerythrite four Ester, pentaerythrite list montanate, the montanate of pentaerythrite two, the montanate of pentaerythrite three, the montanic acid of pentaerythrite four Ester, sorbitan-monopalmityl ester, anhydrosorbitol dipalmitate, anhydrosorbitol tripalmitate, dehydration Sorbitan monostearate, sorbitandistearate, anhydrosorbitol tristearate, anhydrosorbitol Single behenate, the behenate of anhydrosorbitol two, anhydrosorbitol tribehenin acid esters, anhydrosorbitol list montanic acid Ester, the montanate of anhydrosorbitol two, the montanate of anhydrosorbitol three, sorbitan monopalmitate, D-sorbite Dipalmitate, D-sorbite tripalmitate, sorbitan monostearate, sorbitan distearte, D-sorbite Tristearate, D-sorbite list behenate, the behenate of D-sorbite two, D-sorbite tribehenin acid esters, D-sorbite Single montanate, the montanate of D-sorbite two, the montanate of D-sorbite three etc..
Alternatively, it is also possible to using the fatty acid ester compound that hydroxyl is enclosed using boric acid etc., be not limited to following material, The borate of such as fatty acid monoglyceride can be enumerated.
Alternatively, it is also possible to using the ester of alcohol and dicarboxylic acids, as the alcohol, enumerate：Methanol, ethanol, propyl alcohol, just Butanol, isobutanol, the tert-butyl alcohol, n-amyl alcohol, 2- amylalcohols, n-heptanol, n-octyl alcohol, n-nonyl alcohol, laruyl alcohol, myristyl alcohol, cetanol, Saturation/the unsaturated alcohol such as stearyl alcohol, docosyl alcohol, as the dicarboxylic acids, can be enumerated：Oxalic acid, malonic acid, butanedioic acid, penta Diacid, adipic acid, pimelic acid, suberic acid, azelaic acid, decanedioic acid, heneicosanedioic acid, Ba Laxi acid, maleic acid, fumaric acid, penta Enedioic acid etc..The ester of these alcohol and dicarboxylic acids can be monoesters or diester.
((D) thermoplastic polymer)
The polyacetal resin granular composition of present embodiment can also contain (D) thermoplastic polymer.
It is used as (D) thermoplastic polymer, preferably polyacetals, polyamide-based resin, polyolefin resin.
((E) inorganic filler)
The polyacetal resin granular composition of present embodiment can also contain (E) inorganic filler.As inorganic Class filler, is not limited to following material, can enumerate for example：The threadiness reinforcing agent such as glass fibre, carbon fiber；Glass microballoon, carbon Sour calcium, talcum, clay etc..
Particularly from the viewpoint of the easy degree, price obtained, preferably talc, clay, calcium carbonate.
(other additives)
The polyacetal resin granular composition of present embodiment can contain existing known various additives.
Formic acid agent for capturing, various stabilizers, such as weather-proof (light) stabilizer, releasing agent can be for example used alone or in combination Deng.
Formic acid agent for capturing is not limited to following material, can enumerated for example for that can catch the additive of formic acid：Alkali metal or Hydroxide, inorganic acid salt, carboxylate and alkoxide of alkaline-earth metal etc..
As the hydroxide of alkali metal or alkaline-earth metal, inorganic acid salt, carboxylate and alkoxide, following material is not limited to, It can enumerate for example：The hydroxide of sodium, potassium, magnesium, calcium or barium etc., the carbonate of the metal, phosphate, silicate, boric acid Salt, carboxylate.The carboxylic acid of the carboxylate is saturation or unsaturated aliphatic carboxylic acid with 10~36 carbon atoms etc., these Carboxylic acid can be replaced with hydroxyl.As representative examples of saturated aliphatic carboxylic, it can enumerate：It is capric acid, laurate, myristic acid, palmitic acid, hard Resin acid, arachidic acid, behenic acid, lignoceric acid, cerinic acid, montanic acid, melissic acid, ceroplastic scid.Unsaturated aliphatic carboxylic acid It can enumerate：Undecenoic acid, oleic acid, elaidic acid, cetoleic acid, erucic acid, brassidic acid, sorbic acid, linoleic acid, leukotrienes, flower Raw tetraenoic acid, propiolic acid, stearolic acid etc..In addition, as alkoxide, methoxide, ethylate of above-mentioned metal etc. can be enumerated.
As weather-proof (light) stabilizer, it can enumerate：(1) benzotriazole material, (2) oxanilide class material and (3) Hindered amines material is used as preferred material.
As (1) the benzotriazole material, following material is not limited to, can be enumerated for example：2- (2 '-hydroxyl- 5 '-methylphenyl) BTA, 2- (2 '-hydroxyl -3,5- di-t-butyl-phenyl) BTA, 2- (2 '-hydroxyls -3,5- bis- Isopentyl-phenyl) BTA, 2- [2 '-hydroxyl -3,5- double (alpha, alpha-dimethylbenzyl) phenyl] -2H- BTAs, 2- (2 '-hydroxyl -4 '-octyloxyphenyl) BTA etc., preferably 2- [double (alpha, alpha-dimethylbenzyl) benzene of 2 '-hydroxyl -3,5- Base] -2H- BTAs, 2- (2 '-hydroxyl -3,5- di-t-butyl-phenyl) BTA.
As (2) the oxanilide class material, following material is not limited to, can be enumerated for example：2- ethyoxyls -2 ' - Ethyloxanilide, -2 '-ethyloxanilide of the 2- ethyoxyl -5- tert-butyl groups, 2- -3 '-dodecyls of ethyoxyl oxalyl two Aniline etc..
Only one kind can be each used alone in these materials, can also be applied in combination two or more.
As (3) the hindered amines material, following material is not limited to, can be enumerated for example：4- acetoxyl groups -2,2, 6,6- tetramethyl piperidines, 4- stearoyl-oxies -2,2,6,6- tetramethyl piperidines, 4- acryloxies -2,2,6,6- tetramethyl piperazines Pyridine, 4- (phenylacetyl epoxide) -2,2,6,6- tetramethyl piperidines, 4- benzoyloxys -2,2,6,6- tetramethyl piperidines, 4- methoxies Base -2,2, the stearic epoxide -2,2 of 6,6- tetramethyl piperidines, 4-, 6,6- tetramethyl piperidines, 4- cyclohexyloxies -2,2,6,6- tetramethyls Piperidines, 4- benzyloxies -2,2,6,6- tetramethyl piperidines, 4- phenoxy groups -2,2,6,6- tetramethyl piperidines, 4- (ethylcarbamoyls Epoxide) -2,2,6,6- tetramethyl piperidines, 4- (cyclohexyl carboxyamide epoxide) -2,2,6,6- tetramethyl piperidines, 4- (phenylaminos Base formyloxy) -2, double (2,2,6, the 6- tetramethyl -4- piperidyls) esters of 2,6,6- tetramethyl piperidines, carbonic acid, oxalic acid it is double (2,2, 6,6- tetramethyl -4- piperidyls) ester, double (2,2,6, the 6- tetramethyl -4- piperidyls) esters of malonic acid, decanedioic acid double (2,2,6,6- Tetramethyl -4- piperidyls) ester, double (2,2,6, the 6- tetramethyl -4- piperidyls) esters of adipic acid, terephthalic acid (TPA) double (2,2,6,6- Tetramethyl -4- piperidyls) ester, 1,2- double (2,2,6,6- tetramethyl -4- piperidines epoxide) ethane, α, α '-bis- (2,2,6,6- tetramethyls Base -4- piperidines epoxide) paraxylene, Toluene-2,4-diisocyanate, it is double (2,2,6, the 6- tetramethyl -4- piperidyls) esters of 4- diamino acids, six sub- Methyl isophthalic acid, 6- diamino acids double (2,2,6,6- tetramethyl -4- piperidyls) ester, benzene -1,3,5- tricarboxylic acids three (2,2,6,6- tetra- Methyl -4- piperidyls) ester, benzene -1,3, preferably 4- tricarboxylic acids three (2,2,6,6- tetramethyl -4- piperidyls) ester etc., decanedioic acid Double (2,2,6,6- tetramethyl -4- piperidyls) esters.Only one kind can be each used alone in above-mentioned hindered amines material, can also group Close using two or more.In addition, the group of more preferably above-mentioned benzotriazole material, oxanilide class material and hindered amines material Close.
As releasing agent, it can enumerate：Ester, the ester of alcohol and dicarboxylic acids, silicone oil of alcohol and alcohol and aliphatic acid etc..
As alcohol, following material is not limited to, for example, has monohydric alcohol, polyalcohol, as monohydric alcohol, following material is not limited to, It can enumerate for example：Octanol (Le of ability Network チ Le ア Le U one), n-octyl alcohol (Le of power プ リ Le ア Le U one), nonyl alcohol, decyl alcohol, ten One alkanol, laruyl alcohol, tridecanol, myristyl alcohol, pentadecanol, cetanol, heptadecanol, stearyl alcohol, oleyl alcohol, nonadecane Alcohol, eicosanol, docosyl alcohol, ceryl alcohol, melissyl alcohol, 2- hexyl decyl alcohols, 2- octyldodecanols, 2- decyls tetradecanol, synthesis Aliphatic alcohol (Le of bis- リ Application ア Le Us of ユ one) etc..
As polyalcohol, be not limited to following material, the polyalcohol for example containing 2~6 carbon atoms can be enumerated, it is specific and Speech can be enumerated：It is ethylene glycol, diethylene glycol, triethylene glycol, propane diols, DPG, butanediol, pentanediol, hexylene glycol, sweet Oil, two glycerine, triglycerin, threitol, antierythrite, pentaerythrite, arabite, ribitol, xylitol, sorbierite, mistake Water D-sorbite, D-sorbite, mannitol etc..
As alcohol and the ester of aliphatic acid, it can enumerate：Palmitic acid, stearic acid, behenyl are preferably selected from fatty acid cpds The fat of aliphatic acid and the polyalcohol in glycerine, pentaerythrite, anhydrosorbitol, D-sorbite in acid, montanic acid Acid esters.
The hydroxyl of these fatty acid ester compounds can contain, can also not contain, and fatty acid ester compound not carried out Limitation.The ester of alcohol and aliphatic acid can be monoesters or diester, three esters.Furthermore it is possible to close hydroxyl with boric acid etc..
As preferred fatty acid ester, following material is not limited to, can be enumerated for example：Glycerol monopalmitate, glycerine two Palmitate, tripalmitin, glyceryl monostearate, glycerol distearate, glycerol tristearate, glycerine list mountain Yu acid esters, the behenate of glycerine two, glycerol tri-docosanoic acid ester, glycerine list montanate, the montanate of glycerine two, the lignite of glycerine three Acid esters, pentaerythritol monopalmitate, pentaerythrite dipalmitate, pentaerythrite tripalmitate, the palm of pentaerythrite four Acid esters, pentaerythritol monostearate, pentaerythritol stearic acid ester 2, pentaerythrite tristearate, pentaerythrite four are stearic Acid esters, pentaerythrite list behenate, the behenate of pentaerythrite two, pentaerythrite tribehenin acid esters, the behenyl of pentaerythrite four Acid esters, pentaerythrite list montanate, the montanate of pentaerythrite two, the montanate of pentaerythrite three, the lignite of pentaerythrite four Acid esters, sorbitan-monopalmityl ester, anhydrosorbitol dipalmitate, anhydrosorbitol tripalmitate, mistake Water sorbitan monostearate, sorbitandistearate, anhydrosorbitol tristearate, Sorbitan Alcohol list behenate, the behenate of anhydrosorbitol two, anhydrosorbitol tribehenin acid esters, anhydrosorbitol list lignite Acid esters, the montanate of anhydrosorbitol two, the montanate of anhydrosorbitol three, sorbitan monopalmitate, sorbose Alcohol dipalmitate, D-sorbite tripalmitate, sorbitan monostearate, sorbitan distearte, sorbose Alcohol tristearate, D-sorbite list behenate, the behenate of D-sorbite two, D-sorbite tribehenin acid esters, sorbose Alcohol list montanate, the montanate of D-sorbite two, the montanate of D-sorbite three etc..
In addition, as the fatty acid ester compound that hydroxyl is enclosed with boric acid etc., being not limited to following material, example can be enumerated Such as the borate of fatty acid monoglyceride.
On alcohol and the ester of dicarboxylic acids, as alcohol, it can use：Methanol, ethanol, propyl alcohol, n-butanol, isobutanol, uncle Butanol, n-amyl alcohol, 2- amylalcohols, n-heptanol, n-octyl alcohol, n-nonyl alcohol, laruyl alcohol, myristyl alcohol, cetanol, stearyl alcohol, docosyl alcohol Etc. saturation/unsaturated alcohol, as the dicarboxylic acids, it can use：Oxalic acid, malonic acid, butanedioic acid, glutaric acid, adipic acid, heptan Diacid, suberic acid, azelaic acid, decanedioic acid, heneicosanedioic acid, Ba Laxi acid, maleic acid, fumaric acid, glutaconate etc., these alcohol Ester with dicarboxylic acids can be monoesters or diester.
[polyacetal resin composite]
The polyacetal resin composite of present embodiment contains the polyacetal resin graininess of above-mentioned present embodiment Composition and
Polyacetal resin.
(polyacetal resin)
As the polyacetal resin used in the polyacetal resin composite of present embodiment, it can enumerate：By formaldehyde, Substantially by oxymethylene units-(CH obtained from the homopolymerization of the cyclic oligomer such as metaformaldehyde or four polyformaldehyde2O)-structure Into polyoxymethylene homopolymer；Or by formaldehyde and/or metaformaldehyde with cyclic ether and/or cyclic formals, added with 1 matter Obtained from measuring more than ppm and the copolymerization of the cyclic formals of below 500 mass ppm hindered phenol anti-oxidants, with By oxymethylene units-(CH2O the random knot inserted with the oxygen alkylidene unit represented by following formulas (1) in the chain of)-composition Polyoxymethylene copolymer of structure etc..
R in formula (1)1And R2It is each independent, it is hydrogen atom, alkyl or aryl, they can be the same or different.N is 2~6 integer.
Also branch's polyoxymethylene copolymer of molecule chain component is included in polyoxymethylene copolymer, with containing 50 matter Measure the polyoxymethylene block copolymer of the variety classes composition block of more than % oxymethylene repeat units.
It should be noted that the insertion rate of the above-mentioned oxygen alkylidene unit in polyoxymethylene copolymer, sub- relative to oxygen 100 moles of methyl group unit, preferably more than 0.01 mole and less than 50 moles, more preferably more than 0.03 mole and 20 moles with Under scope.As the oxygen alkylidene unit, it can enumerate for example：More oxygen ethylene unit, oxygen propylene unit, oxygen tetramethylene Unit, oxygen butylidene unit, oxygen phenyl-ethylene unit etc..In these oxygen alkylidene units, from the poly- of raising present embodiment From the viewpoint of the physical property of acetal resin composition, preferably more oxygen ethylene unit-[(CH2)2O]-, oxygen tetramethylene unit- [(CH2)4O]-。
The content of polyacetal resin granular composition in the polyacetal resin composite of present embodiment, relative to The mass parts of the mass parts of polyacetal resin 100 preferably 0.01 mass parts~10.
The mass parts of more preferably 0.1 mass parts~8, the mass parts of more preferably 0.1 mass parts~6.
The content of polyacetal resin granular composition is more than 0.01 mass parts, it is hereby achieved that high thermal stability Effect, below for 10 mass parts, thus keep polymer mechanical strength.
[manufacture method of polyacetal resin composite]
The polyacetal resin composite of present embodiment can be by by the polyacetal resin graininess of present embodiment Composition is manufactured with polyacetal resin melting mixing.
Melting mixing can use the kneading machines such as extruder, heating roller, kneader, Banbury mixer to implement, from life From the viewpoint of yield, the mixing of extruder is particularly preferably utilized.
Melting temperature, according to the preferred processing temperature of base resin, is 140 DEG C~260 DEG C as substantially standard Scope, preferably 180 DEG C~230 DEG C of scope.
The polyacetal resin of present embodiment is graininess with granular composition, therefore, it is possible to not reduce productivity ratio In the case of improve the addition concentration in polyacetal resin.Utilize the feature, the polyacetal resin composite of present embodiment Manufacture method in, relative to the mass parts of polyacetal resin 100, use the polyacetal resin mass parts of granular composition 0.1 ~50 mass parts simultaneously form masterbatch, in addition, by that can obtain polyacetal resin and the masterbatch melting mixing as target Polyacetal resin composite.
The additive package and when carrying out multiple melting mixing in polyacetal resin, it is possible to cause the bad of polyacetal resin Change or the deterioration of additive, polyacetal resin can not caused by having used the masterbatch of polyacetal resin granular composition The polyacetal resin composite of high-purity is obtained in the case of deterioration or the deterioration of additive.
, can further additive package, and suppress the formaldehyde generation of the formed body after shaping by forming masterbatch Amount.
Embodiment
Hereinafter, enumerate specific embodiment and comparative example explains present embodiment, but present embodiment is not limited to Following embodiment.
The assay method of various characteristics is as follows.
[assay method of characteristic]
(measure of (1) pine dress apparent specific gravity)
Using powder tester, (the thin close Krona company in river manufactures：Powder tester model PT-E) and 100mL volumes gold Category container is determined.
(measure of (2) average grain diameter)
Average grain diameter is determined in the following manner：Pacify in micro electromagnetic vibrating scalper (manufacture of cylinder well Physicochemical apparatus) Dress sieve aperture is respectively that 1700 μm, 1000 μm, 710 μm, 500 μm, 355 μm, 250 μm, 150 μm, 106 μm and 46 μm of screen cloth is gone forward side by side The row screening of 30 minutes, average grain diameter is used as using 50% particle diameter of weight build-up size distribution.
(evaluation of (3) uniformity)
<The evaluation of the uniformity of polyacetal resin granular composition>
Polythene Bag is provided with height 3m, the pipe of diameter 15cm polyvinyl chloride.
Make to weigh the 1kg polyacetal resins granular composition in another Polythene Bag from top quickly to fall Under.
The random institute that 1.00mg is each weighed from ten positions, ten positions at middle part and ten positions of bottom on top The polyacetal resin granular composition accumulated in the Polythene Bag under the pipe of polyvinyl chloride is stated, and uses Mitsubishi's analytical technology The blood urea/nitrogen analyzer TN-2100H of manufacture is determined.
The percentage of the relative standard deviation of the numerical value of 30 nitrogen analysis is calculated respectively.
It is evaluated as：The smaller expression uniformity of value is higher.
During more than 10%, it is judged as：Deviation is big, uniformity is insufficient.
<The evaluation of the uniformity of polyacetal resin composite particle>
The blood urea/nitrogen analyzer TN-2100H manufactured using Mitsubishi's analytical technology, respectively to since operation, i.e. resin is from extrusion The die section of machine start extrusion 10 minutes after, operation start 1 hour after, after 2 hours, after 3 hours, at the end of polyacetal resin Composition grain 10mg has carried out each 10 measure in each time.
It is each to carry out 10 measure, calculate the percentage of the relative standard deviation of the numerical value of nitrogen analysis.
It is evaluated as：The smaller expression uniformity of value is higher.
During more than 10%, it is judged as：Deviation is big, uniformity is insufficient.
(measure of the foreign matter in (4) polyacetal resin composite particle)
For polyacetal resin composite particle 3kg, the particle containing foreign matter has been sorted by visual observation.
Then, to every 1 particle, the size of foreign matter contained in the particle containing foreign matter with vernier caliper measurement.
Then, the pressurization of 5 minutes has been carried out to 100g particles at 200 DEG C, under 10MPa pressure, 10 have been made 30cm × 30cm × about 1.2mm matrix band, confirms containing foreign matter by visual observation, and is commented according to following benchmark Valency.
There is a situation where more than 1.0mm foreign matter：×
Foreign matter in the absence of more than 1.0mm, there is a situation where foreign matters of the 0.3mm less than 1.0mm：△
Foreign matter in the absence of more than 0.3mm, there is foreign matter less than 0.3mm in the case of, number is counted, added up to For more than 30 situations：○
Situation other than the above：◎
(the formaldehyde yield of (5) polyacetal resin composite particle)
The formaldehyde yield of polyacetal resin composite particle is determined in the following manner.
20.00g polyacetal resin composite particles are fitted into valvular Tedlar (registration mark) bag of tool, fully Nitrogen displacement is carried out.Then, 5.00L nitrogen is sealing into Tedlar (registration mark) bag.Then, by Tedlar (registrations Trade mark) bag be placed in inside top have with the baking oven of the sample tap of outside insertion, the sampling bag is connected into sampling Mouthful, then it placed at 80 DEG C 3 hours.
Then, DNPH (DNPH) filter cylinder (power-ト リ Star ジ) is connected to the sample tap, opens sampling bag Valve, 4.00L polyacetal resin composites is passed through in DNPH filter cylinders.
Acetonitrile liquid is passed through with certain speed in DNPH filter cylinders, and formaldehyde is recovered in 10mL volumetric flasks.
Then, 10mL is settled to water, and is sufficiently mixed.
The mixed liquor is assigned in bottle, the HPLC manufactured using Shimadzu manufacturing company, using DNPH titers as Titer, using water/acetonitrile (52/48) as separating liquid, is quantified with flow 1mL/ minutes, 40 DEG C of column temperature, is measured with ppm The formaldehyde that the polyacetal resin composite particle of unit mass is produced is determined.
Determination of the upper limit is below 15ppm, and O.D. (can not determine) is designated as the sample more than determination of the upper limit.
After being started 10 minutes with operation, operation start 1 hour after, after 2 hours, after 3 hours, at the end of particle surveyed It is fixed, describe maximum therein.
[raw material of polyacetal resin granular composition]
((A) antioxidant)
A-1：Four [methylene -3- (3,5 '-di-t-butyl -4 '-hydroxy-phenylpropionic acid ester)] methane
120 DEG C of fusing point
A-2：Triethylene glycol is double [3- (the 3- tert-butyl group -5- methyl -4- hydroxy phenyls) propionic ester]
77 DEG C of fusing point
A-3：3- (3,5- di-tert-butyl-hydroxy phenyl) propionic acid stearyl ester
53 DEG C of fusing point
((B) nitrogen-containing compound)
B-1：Melamine
B-2：Benzoguanamine
B-3：Adipic dihydrazide
B-4：2- tolimidazoles
B-5：Sebacic dihydrazide
B-6：The hydrazides of dodecanedioic acid two
((C) fatty acid ester)
C-1：Glycol distearate
C-2：Stearyl stearate
((D) thermoplastic polymer)
D-1：Polyacetals
D-2：Polyamide 66
((E) fatty acid metal salts)
E-1：Distearyl acid calcium
E-2：Two -12 hydroxy stearic acid calcium
((F) inorganic filler)
F-1：Talcum
F-2：Calcium carbonate
[manufacture method (I) of polyacetal resin granular composition]
The equidirectional double screw extruder that screw diameter is 30mm is used.Screw configuration is all set to whole type, and The die head of the outlet of resin is adjusted to open state.
Selection regulation raw material, has manufactured polyacetal resin using double screw extruder and has been combined with graininess from above-mentioned raw materials Thing.
Specifically, raw material is loaded into double screw extruder, do not make integrally fused state~particle completely it is constant it is big, Directly by running under conditions of between the state of extruder.It is controlled in the following manner in operation：Raw material melts once turning into Increase additivated inlet amount when melting state, then on the contrary, reducing inlet amount when raw material turns into the state not melted completely.
Confirm the state of polyacetal resin granular composition discharged from the outlet of double screw extruder, simultaneously will The barrel temperature of extruder be set as 80 DEG C, rotation number be set as 30rpm.
By resulting polyacetal resin with granular composition load by 10 mesh sieves upper, 35 mesh sieves downside it is overlapping and Into sieve in, make its high vibration and sieved.
The particle remained on 10 mesh sieves is fallen on 35 mesh sieves by being crushed.
The raw material supply side of extruder will be suitably back to by the fine powder of 35 mesh sieves, be recycled.
On barrel temperature, confirm the particle of discharge, suitable control is carried out in the range of 60 DEG C~100 DEG C.
[manufacture method (II) of polyacetal resin granular composition]
In 110mL screwed pipe, the raw material of 30g polyacetal resin granular compositions is added, in sheathing formula resistance Heated on heating stirrer, while being stirred with spatula.
In stirring, confirm that the particle diameter of additive becomes big by visual observation, particle turns into graininess.
The operation is suitably repeated.
[polyacetal resin A manufacture method]
By with 80 DEG C can be adjusted to by the polymerizer of the twin-screw self-cleaning type of the chuck of thermal medium.
Then, in the polymerizer with 12kg/ hours continuously addition metaformaldehyde, with 414.6g/ hours (relative to Metaformaldehyde 1mol is 4.2 moles of %) 1,3- dioxolane is continuously added as comonomer, relative to metaformaldehyde Using 6.8g/ hours, continuously addition dimethoxym ethane was used as chain-transferring agent to 1mol.
In addition, continuously adding using 38g/ hours the boron trifluoride di-n-butyl ether network as polymerization catalyst in polymerizer The mass % of compound 1 cyclohexane solution is simultaneously polymerize.
The form of polymerization is polymerisation in bulk.
By in the powder input aqueous solution of triethylamine 0.1% for the Copolyacetal discharged by polymerizer, it is polymerize The inactivation of catalyst.
The Copolyacetal after inactivation is filtered with centrifugal separator, is dried after washing at 140 DEG C, has obtained thick Polyacetal resin.
Relative to the thick mass parts of polyacetal resin 100, using tetramethyl formic acid aqueous ammonium as quaternary ammonium compound, and press The amount conversion mixing 20ppm of nitrogen-atoms, is then supplied to the double-screw type extruder with exhaust outlet.
Extruder design temperature be 200 DEG C, the residence time in extruder be to have carried out polyacetals under conditions of 5 minutes The decomposition of the unstable terminal part of resin.
Unstable terminal part be decomposed after Copolyacetal exhaust outlet vacuum be 20 supports (Torr) under conditions of Volatile ingredient is removed, is extruded by extruder die head with strands shape, and is granulated, so as to obtain polyacetal resin A.
[manufacture method of polyacetal resin composite]
By the polyacetal resin manufactured as described above and polyacetal resin granular composition or additive, according to as follows State the composition shown in Tables 1 and 2, load 36L stainless steel vapor tight tank so that total amount reaches about 18kg, use Tumbler mini TMC-36S, is mixed 15 minutes, so as to obtain mixture.
The mixture is set to fall into the hopper that double screw extruder thereunder at 2 meters is set.
Double screw extruder using be set as 200 DEG C, L/D=30, double screw extruder with 30mm exhaust outlets.
By main feed mouthful supply mixture, melting mixing is carried out with screw speed 100rpm, polyacetals tree is resulting in Oil/fat composition.
(embodiment 1~12)
According to above-mentioned " manufacture method (I) of polyacetal resin granular composition ", the group according to table 1 below Into having manufactured polyacetal resin granular composition, and various evaluations are carried out.
Evaluation result is as shown in table 1.
(embodiment 13,14)
According to above-mentioned " manufacture method (II) of polyacetal resin granular composition ", according to table 1 below Composition has manufactured polyacetal resin granular composition, and has carried out various evaluations.
Evaluation result is as shown in table 1.
(comparative example 1~12)
According to the composition shown in table 2 below, raw material is fitted into Polythene Bag and hand operated mixing is carried out, addition has been manufactured Agent, and carried out various evaluations.
Evaluation result is as shown in table 2.
(embodiment 15)
In addition to 10 mesh sieves are replaced with into 5 mesh sieves, polyacetal resin use has been manufactured in the same manner as in example 6 Granular composition, and carried out various evaluations.
Evaluation result is as shown in table 1.
(embodiment 16)
In addition to 10 mesh sieves are replaced with into 5 mesh sieves, polyacetal resin use has been manufactured in mode same as Example 7 Granular composition, and carried out various evaluations.
Evaluation result is as shown in table 1.
(embodiment 17~30)
Graininess is respectively prepared with granular composition in the polyacetal resin manufactured by above-mentioned (embodiment 1~16) Sample K-1~K-16, using the material shown in these samples and Table 3 below, has manufactured polyacetal resin composite.
Evaluation result is as shown in table 3.
(comparative example 13~24)
Additive samples P-1~P-12 is respectively prepared in the additive manufactured by above-mentioned (comparative example 1~12), is used Material shown in these samples and table 4 below, has manufactured polyacetal resin composite.Evaluation result is as shown in table 4.
Industrial applicability
The polyacetal resin composite of polyacetal resin composite granular composition of the present invention has been used as electricity In the sub- Material Field of gas-to-electric, automotive field, other various industrial materials fields, food packaging applications, part Material Field Material, with industrial applicability.

Claims (13)

1. a kind of polyacetal resin granular composition, it contains
At least one (A) antioxidant and
At least one (B) intramolecular has the nitrogen-containing compound of two or more nitrogen-atoms.
2. polyacetal resin granular composition as claimed in claim 1, wherein,
The pine dress apparent specific gravity of the polyacetal resin granular composition is more than 0.3 and less than 0.8.
3. polyacetal resin granular composition as claimed in claim 1 or 2, wherein,
The average grain diameter of the polyacetal resin granular composition is more than 100 μm and below 2mm.
4. polyacetal resin granular composition as claimed any one in claims 1 to 3, wherein,
The fusing point of (A) antioxidant is more than 30 DEG C.
5. the polyacetal resin granular composition as any one of Claims 1-4, wherein,
Polyacetal resin granular composition also contains (C) fatty acid ester.
6. the polyacetal resin granular composition as any one of claim 1 to 5, wherein,
(B) it is selected from by glyoxaline compound, amino triazine class that intramolecular, which has the nitrogen-containing compound of two or more nitrogen-atoms, At least one in the group that compound, triazole class compounds and hydrazide kind compound are constituted.
7. the polyacetal resin granular composition as any one of claim 1 to 5, wherein,
(A) content of antioxidant is more than 20 mass %.
8. the polyacetal resin granular composition as any one of claim 1 to 7, wherein,
Polyacetal resin granular composition also contains (D) thermoplastic polymer.
9. the polyacetal resin granular composition as any one of claim 1 to 8, wherein,
Polyacetal resin granular composition also contains (E) inorganic filler.
10. a kind of polyacetal resin composite, it contains
Polyacetal resin granular composition and polyacetal resin any one of claim 1 to 9.
11. polyacetal resin composite as claimed in claim 10, wherein,
Relative to the mass parts of polyacetal resin 100, the polyacetal resin composite contains the power of the mass parts of 0.1 mass parts~10 Profit requires the polyacetal resin granular composition any one of 1 to 9.
12. a kind of manufacture method of polyacetal resin composite, it is the polyacetal resin composite described in claim 11 Manufacture method, wherein, the manufacture method includes
By the process of the polyacetal resin and the polyacetal resin with granular composition melting mixing.
13. the manufacture method of polyacetal resin composite as claimed in claim 12, wherein, the manufacture method includes
The mass parts of mass parts of polyacetal resin granular composition 0.1~50 and the mass parts of polyacetal resin 100 are melted Melt mixing and formed masterbatch process and
The process for further carrying out melting mixing to polyacetal resin after masterbatch is formed.
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