JP2005226020A - Masterbatch resin composition for coloring polyoxymethylene resin and colored polyoxymethylene resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a masterbatch resin composition for coloring a polyoxymethylene resin that has less uneven coloring and superior heat stability, and reduces generation of gaseous formaldehyde, and to obtain a colored polyoxymethylene resin composition using the same. <P>SOLUTION: This masterbatch resin composition comprise (D) a hindered phenol antioxidant with a molecular weight of ≥400 of 0.01-10 pts.wt. and (E) an aliphatic acid metal salt of 0.01-5 pts.wt. on the basis of the total of 100 pts.wt. of (A) a polyoxymethylene resin of 99-0 wt%, (B) a quatercopolymer of nylon 6/66/610/12 of 0.5-60 wt% and (C) a colorant of 0.5-40 wt% selected from an inorganic pigment, an organic pigment and an extender. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a masterbatch resin composition for coloring a polyoxymethylene resin with little color unevenness during coloring, excellent thermal stability, and reduced generation of formaldehyde gas, and a colored polyoxymethylene resin composition using the same It is about things.

  Since polyoxymethylene resin has excellent strength characteristics, fatigue characteristics, electrical characteristics, and the like, it has been widely used in many fields such as electric parts, office equipment parts, and building materials.

  However, polyoxymethylene resins are easy to cause decomposition from the end of the copolymer component and decomposition with main chain cleavage by auto-oxidation due to their structure. Furthermore, as a result of these decomposition, irritating formaldehyde gas Therefore, there is a problem that the working environment is polluted and the thermal stability is greatly impaired.

  In addition, when a colorant typified by carbon black or titanium oxide is added to the polyoxymethylene resin for the purpose of coloring, the decomposition thereof is particularly accelerated, and the thermal stability of the polyoxymethylene resin is greatly impaired. Therefore, it is also known that it is difficult to use as a plastic material.

  Furthermore, it is generally known that coloring with a coloring masterbatch is not sufficient in dispersibility of the colorant in the polyoxymethylene resin, and color unevenness is likely to occur, resulting in problems in appearance characteristics. Yes.

  As a technique for improving the dispersibility of the colorant with respect to the polyoxymethylene resin, a method using a long-chain alkyl primary alcohol is known (for example, see Patent Document 1). According to this method, Although the dispersibility is improved to some extent, the decomposition of the polyoxymethylene resin is not suppressed, and the improvement of the thermal stability is insufficient.

  Further, as a technique for improving the thermal stability of polyoxymethylene resin, sterically hindered phenol is an essential component, amine-substituted triazine compound, alkali or alkaline earth metal hydroxide, inorganic acid salt, carboxylate salt and At least one selected from the group consisting of alkoxides, fatty acid esters of polyhydric alcohols derived from polyhydric alcohols having 2 to 10 carbon atoms and higher fatty acids having 22 to 32 carbon atoms, and having 10 or more carbon atoms A method of adding one or more combinations of higher fatty acid amides is known (for example, see Patent Document 2). A masterbatch resin composition for coloring a polyoxymethylene resin produced by applying this method has a heat Although stability is improved, the improvement effect is still inadequate, and formaldehyde generated during molding Not yet been enough improvement regarding the effect of suppressing Dehidogasu was circumstances. In addition, the coloring unevenness has not been sufficiently improved, and the appearance characteristics of the molded product have a problem.

Furthermore, it is attempted to absorb the generated formaldehyde gas by suppressing the form deposit during the molding process by making the formaldehyde scavenger present when the molding process is performed. A polyamide resin (for example, see Patent Document 3) is known, but even if this formaldehyde scavenger is applied to a masterbatch resin composition for coloring a polyoxymethylene resin, it has not been improved sufficiently. there were.
Japanese Patent Laid-Open No. 7-53773 (2nd page) JP 7-331028 A (second page) Japanese Patent Laid-Open No. 4-77528 (page 2)

  The present invention has been achieved as a result of studying the solution of the problems in the prior art described above as an issue.

  Accordingly, an object of the present invention is to provide a masterbatch resin composition for coloring a polyoxymethylene resin with little color unevenness during coloring, excellent thermal stability, and reduced generation of formaldehyde gas, and a colored polymer using the same. The object is to provide an oxymethylene resin composition.

In order to achieve the above object, according to the present invention,
(A) 99 to 0% by weight of polyoxymethylene resin;
(B) polyamide 6/66/610/12 quaternary copolymer 0.5 to 60% by weight;
(C) For a total of 100 parts by weight consisting of 0.5 to 40% by weight of one or more colorants selected from inorganic, organic and extender pigments,
(D) 0.01 to 10 parts by weight of a hindered phenol antioxidant having a molecular weight of 400 or more (E) 0.01 to 5 parts by weight of a metal salt of a saturated fatty acid,
And further (F) 0-3 parts by weight of an ultraviolet absorber, if desired
(G) 0 to 6 parts by weight of a hindered amine stabilizer,
(H) A masterbatch resin composition for coloring a polyoxymethylene resin containing 0 to 20 parts by weight of a dispersion aid is provided.

In the masterbatch resin composition for coloring the polyoxymethylene resin of the present invention,
The polyoxymethylene resin is an oxymethylene copolymer composed of repeating units represented by the following general formula (I), and that the metal salt of the (E) saturated fatty acid is an alkaline earth metal salt, All are mentioned as preferable conditions.

(In the formula, R ₁ and R ₂ are an inert substituent selected from hydrogen, a lower alkyl group and a halogen-substituted lower alkyl group, n is an integer of 0 to 5, and 70 to 99.9 of repeating units. Mole% is n = 0.)
The colored polyoxymethylene resin composition of the present invention is characterized by comprising the above-mentioned masterbatch resin composition for coloring a polyoxymethylene resin and (b) a polyoxymethylene resin. The mixing weight ratio of component (b) is preferably 1: 5 to 100, and the colorant content in the colored polyoxymethylene resin composition is substantially 0.05 to 2%. Preferably there is.

  According to the present invention, as described below, a masterbatch resin composition for coloring a polyoxymethylene resin with less color unevenness during coloring, excellent thermal stability, and reduced generation of formaldehyde gas, and The used colored polyoxymethylene resin composition can be obtained.

  Hereinafter, the present invention will be described in detail.

  The (A) polyoxymethylene resin used in the present invention will be described.

  The polyoxymethylene resin in the present invention can be used as either a homopolymer or a copolymer, but in the present invention, in particular, an oxymethylene copolymer composed of a repeating unit represented by the following general formula (I), that is, mainly composed of oxymethylene units, Preference is given to using oxymethylene copolymers containing oxyalkylene units having 2 to 8 adjacent carbon atoms in the main chain, for example oxymethylene copolymers copolymerized with trioxane with a cyclic ether component.

(In the formula, R ₁ and R ₂ are an inert substituent selected from hydrogen, a lower alkyl group and a halogen-substituted lower alkyl group, n is an integer of 0 to 5, and 70 to 99.9 of repeating units. Mole% is n = 0.)

As an example of a typical method for producing an oxymethylene copolymer, a high purity trioxane and a copolymer component such as ethylene oxide or 1,3-dioxolane are introduced into an organic solvent such as cyclohexane, and boron trifluoride diethyl ether complex is prepared. A method of producing by cationic polymerization using a Lewis acid catalyst such as deactivation of the catalyst and stabilizing the end groups, or trioxane into a self-cleaning stirrer without using any solvent. Examples thereof include a method in which a copolymer component and a catalyst are introduced and bulk polymerization is performed, and then an unstable terminal is further decomposed and removed.

  The cyclic ether copolymerized with trioxane in the present invention includes ethylene oxide, propylene oxide, 1,3-dioxolane, 1,3-dioxane, 1,3-dioxepane, 1,3,5-trioxepane, 1,3,6- Examples thereof include glycidyl ether compounds such as trioxocane, phenyl glycidyl ether, and 1,4-butanediol diglycidyl ether. These cyclic ethers can be used alone or in combination of two or more.

  The (B) polyamide 6/66/610/12 quaternary copolymer used in the present invention is a copolymer obtained by copolymerization of a salt of a dicarboxylic acid and a diamine, ω-aminocarboxylic acid or lactam. And a copolyamide having structural units composed of polyamide 6, polyamide 66, polyamide 610, and polyamide 12. The composition of the copolyamide can have various ratios, and any ratio may be used in the present invention. However, the copolyamide preferably has a melting point from the viewpoint of compatibility with the polyoxymethylene resin and dispersibility. Is a composition which becomes the range of 50-200 degreeC, Most preferably, it is 80-170 degreeC.

  The amount of the (B) polyamide 6/66/610/12 quaternary copolymer added is in the range of 0.5 to 60% by weight of the entire master batch composition for coloring the polyoxymethylene resin. Preferably it is the range of 0.5-40 weight%, More preferably, it is the range of 0.5-30 weight%. If the amount added is less than 0.5% by weight, the formaldehyde scavenging effect is not sufficient, and if it exceeds 60.0% by weight, not only is it uneconomical as a colored masterbatch, but also the color change becomes large and bleeding on the product surface occurs. Since the possibility of a phenomenon increases, it is not preferable.

  As the colorant (C) used in the present invention, inorganic pigments such as cadmium sulfate, cadmium selenide, ultramarine, titanium dioxide, iron oxide, chromate, carbon black, azo, anthraquinone, phthalocyanine, quinacridone Organic pigments such as calcium carbonate, barium sulfate, talc, clay, and silica, and organic pigments such as calcium, isoindolinone, dioxane, berylene, quinophthalone, and belinone. Among these, those that do not decompose or discolor during the molding process of the polyoxymethylene resin are preferable. These colorants are used alone or in combination of two or more selected from the above.

  The addition amount of the (C) colorant is in the range of 0.5 to 40% by weight of the entire master batch composition for coloring the polyoxymethylene resin. Preferably it is 2 to 30 weight%, More preferably, it is the range of 4 to 20 weight%. When the addition amount is less than 0.5% by weight, the amount of the masterbatch resin composition for coloring necessary for coloring the polyoxymethylene resin becomes excessive, which is uneconomical. When the addition amount exceeds 40% by weight Is not preferable because it causes a decrease in fluidity during melt kneading and poor dispersion.

  Specific examples of the (D) hindered phenol antioxidant used in the present invention include triethylene glycol-bis (3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate), pentaerythris Lityl-tetrakis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate), 2,2-thio-diethylenebis (3- (3,5-di-tert-butyl-4-hydroxy) Phenyl) propionate), N, N-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamide), 1,3,5-trimethyl-2,4,6-tris (3 5-di-t-butyl-4-hydroxybenzyl) benzene, 1,6-hexanediol-bis (3- (3,5-di-t-butyl-4-hydroxyphenyl) pro Onato), tris (3,5-di -t- butyl-4-hydroxybenzyl) compounds such as isocyanurate. Among these antioxidants, those having a molecular weight of 400 or more are preferable, and these may be used alone or in combination of two or more.

  The addition amount of the (D) hindered phenol antioxidant is (A) polyoxymethylene resin, (B) polyamide 6/66/610/12 quaternary copolymer, and (C) total amount of colorant of 100 weight. 0.01 to 10.0 parts by weight, particularly preferably 0.01 to 5.0 parts by weight with respect to parts. If the addition amount is less than 0.01 parts by weight, the effect of thermal stability is not sufficient, and if it exceeds 10.0 parts by weight, coloring due to heat becomes severe, which is not preferable.

  The metal in the metal salt of (E) saturated fatty acid used in the present invention is preferably an alkaline earth metal, specifically, calcium stearate, magnesium stearate, calcium behenate, magnesium behenate, or 12-hydroxymagnesium stearate. , 12-hydroxy calcium stearate and the like. These fatty acid metal salts may be used alone or in combination of two or more.

  The addition amount of the metal salt of (E) saturated fatty acid is (A) polyoxymethylene resin, (B) polyamide 6/66/610/12 quaternary copolymer, and (C) 100 parts by weight of the colorant. The range is 0.01 to 5 parts by weight. If the amount added is less than 0.01 parts by weight, the effect of reducing formaldehyde is not sufficient, and if the amount added exceeds 5 parts by weight, the color change of the masterbatch resin composition for coloring the polyoxymethylene resin becomes large and the commercial value is lowered. This is not preferable.

  As the ultraviolet absorber (F) used as an optional component in the present invention, 2- (2′-hydroxy-3 ′, 5′-bis (α, α-dimethylbenzyl) phenyl) -2H-benzotriazole, 2- Benzotriazole ultraviolet absorbers such as (3,5-di-t-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (4,6-diphenyl-1,3,5-triazine-2 -Il) -5-((hexyl) oxy) -phenol includes triazine ultraviolet absorbers, benzophenone ultraviolet absorbers, and the like.

  The amount of the (F) ultraviolet absorber added is 100 parts by weight based on the total amount of (A) polyoxymethylene resin, (B) polyamide 6/66/610/12 quaternary copolymer, and (C) colorant. The range is 0 to 3 parts by weight, and preferably 0.01 to 2.0 parts by weight. When the added amount exceeds 3 parts by weight, it is economically disadvantageous and undesirably causes problems such as deterioration of mechanical properties of the polyoxymethylene resin and mold contamination.

  Examples of the (G) hindered amine stabilizer used as an optional component in the present invention include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and bis (1,2,2,6,6-pentamethyl). -4-piperidinyl) sebacate, bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate and the like. Among them, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate is preferably used.

  The amount of the (G) hindered amine stabilizer added is 100 parts by weight based on the total amount of (A) polyoxymethylene resin, (B) polyamide 6/66/610/12 quaternary copolymer, and (C) colorant. In the range of 0 to 6 parts by weight, preferably in the range of 0.01 to 4.0 parts by weight. When the addition amount exceeds 6 parts by weight, the effect of addition reaches saturation, which is not economical and causes problems such as discoloration and mold contamination, which is not preferable.

  (H) Dispersing aid used as an optional component in the present invention includes polyethylene wax, high density polyethylene wax, high molecular weight polyoxyalkylene, amide wax, olefin wax, montan wax, zinc salt of long chain fatty acid, polyvalent Examples include fatty acid esters of alcohol. These dispersing aids may be used alone or in combination of two or more.

  The addition amount of the (H) dispersion aid is based on 100 parts by weight of the total amount of (A) polyoxymethylene resin, (B) polyamide 6/66/610/12 quaternary copolymer, and (C) colorant. The range is from 0 to 20 parts by weight, and particularly preferably 10 parts by weight or less. When the addition amount exceeds 20 parts by weight, it causes a bleeding phenomenon on the product surface and mold surface contamination, which is not preferable.

  In addition, the polyoxymethylene resin coloring masterbatch resin composition produced in the present invention and the colored polyoxymethylene resin composition are filled with mica powder and glass beads as long as the effects of the present invention are not impaired. Agent, glass fiber, carbon fiber, ceramic fiber, fibrous reinforcing agent such as aramid fiber, release agent such as ethylene bisstearylamide, metal soap, fatty acid ester, molybdenum disulfide, polytetrafluoroethylene, silicone oil, Additives such as lubricants such as hydrocarbon oils, elastomers such as thermoplastic polyurethane, hydrolysis resistance improvers, nucleating agents, plasticizers, adhesion aids and the like can be optionally contained.

  As a method for producing a masterbatch resin composition for coloring a polyoxymethylene resin in the present invention, a continuous melt-kneading apparatus such as an extruder having a vent port is used to vent at a temperature of 170 ° C. to 250 ° C. under reduced pressure. It is preferable to carry out degassing from the mouth. Moreover, the melt kneading method of each additive component is not particularly limited, and it is preferable to carry out the conditions under which the colorant is uniformly dispersed.

  The colored polyoxymethylene resin composition of the present invention can be obtained by mixing a predetermined amount of the polyoxymethylene resin coloring masterbatch of the present invention and a polyoxymethylene resin, followed by injection molding, extrusion molding, blow molding or the like. The mixing weight ratio of the polyoxymethylene resin coloring masterbatch resin composition: polyoxymethylene resin can be arbitrarily implemented in the range of 1: 5-100. Among these, it is preferable to implement in the range of 1: 10-80. When the mixing ratio is less than 1: 5, the proportion of the colored master batch composition increases, which is uneconomical and undesirable. A mixing ratio exceeding 1: 100 is not preferred because poor dispersion of the colored master batch composition tends to occur and color unevenness is likely to occur. It is preferable from the viewpoints of economy, colorability, thermal stability and the like that the colorant in the colored polyoxymethylene resin is finally in the range of 0.05 to 2%.

  The colored polyoxymethylene resin composition produced using the master batch resin composition for coloring the polyoxymethylene resin of the present invention has little color unevenness during coloring, excellent thermal stability, and generation of formaldehyde gas. Since it is reduced, it can be used for a wide range of molding applications such as electric / electronic parts, automobile parts, machine parts, and toys.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. In the following Examples and Comparative Examples, a masterbatch resin composition for coloring a polyoxymethylene resin was prepared, and this was mixed with a polyoxymethylene resin at a predetermined mixing ratio, followed by injection molding. A test piece was molded, and the thermal decomposition rate (Kx), coloring color unevenness, generation of mold deposit, and formaldehyde odor were measured for the test piece by the following methods.

[injection molding]:
Using an injection molding machine having a clamping pressure of 60 tons, a cylinder temperature of 200 ° C., a mold temperature of 80 ° C., injection / cooling time = 15/15 seconds, and a square plate of 80 mm × 80 mm × 1 mmt and ASTM No. 1 dumbbell test piece Was injection molded.

[Evaluation of thermal decomposition rate (Kx)]:
Kx means the decomposition rate when left at x ° C. for a certain period of time, and it was cut out from ASTM No. 1 dumbbell prepared by the injection molding using a thermobalance device (TG / DTA200 manufactured by Seiko Electronics Co., Ltd.). A 10 mg sample was allowed to stand at x ° C. for 6 hours in an air atmosphere, and the following formula was obtained.

Kx = (W0−W1) × 100 / W0 (%)
Here, W0 means the sample weight before heating, and W1 means the sample weight after heating.

[Evaluation of coloring color unevenness]:
Using the color computer “SM-5-IS-2B” (manufactured by Suga Test Instruments Co., Ltd.), the color difference (ΔE) between the central portion and the four corners of the 80 mm × 80 mm × 1 mmt square plate is the difference between the maximum value and the minimum value. The color unevenness was judged. The judgment criteria are shown in Table 1.

[Evaluation of mold deposit generation]:
A hot runner type pin gate mold is used in the operation of continuously injection-molding 2000 shots of a JIS No. 4 dumbbell with an injection molding machine at a cylinder temperature of 230 ° C., a mold temperature of 30 ° C., and an injection molding cycle of 10 seconds. The mold surface state after 2000 shots was determined according to the criteria shown in Table 2.

[Evaluation of the amount of formaldehyde generated]:
The 80 mm × 80 mm × 1 mmt square plate obtained by injection molding is left in the room for one week, then cut out and weighed accurately so as to have a weight of 1 g and a surface area of 16 cm ² . The cut-out molded product is put into an Erlenmeyer flask having an internal volume of 1000 ml, and the inside of the flask is purged with nitrogen and sealed. This Erlenmeyer flask was heat-treated in a hot air circulating oven set at 80 ° C. for 5 hours. Immediately after the heat treatment, the amount of formaldehyde in the Erlenmeyer flask was measured using a Kitagawa type formaldehyde detector tube manufactured by Komyo Chemical Co., Ltd.

[Examples 1-20, Comparative Examples 1-9]
[Production of masterbatch resin composition for coloring polyoxymethylene resin]:
(A) Polyoxymethylene resin “Amirasu” S731 (manufactured by Toray Industries, Inc.), (B) Polyamide 6/66/610/12 quaternary copolymer (copolymerization composition 6/66/610/12 = 22/12) / 16/50 (parts by weight)) and (C-1) carbon black (Color Index Generic Name: Pigment Black 7) are charged so that the total corresponds to 100% by weight as shown in Table 3, (D) “Irganox” IR245 [manufactured by Ciba Geigy Specialty, triethylene glycol-bis (3- ( 3-t-butyl-5-methyl-4-hydroxyphenyl) propionate)] (hindered phenol antioxidant) (corresponding to 4 parts by weight), (E) 12-hydroxystearate Was added calcium phosphate 200 g (corresponding to 2 parts by weight), after stirring and mixing for 3 minutes, 200 ° C. using Ikegai biaxial 45mmφ extruder with Iron Works Ltd. vent, melt-extruded at a vent pressure 0.7 kPa. The obtained masterbatch resin composition (MB1) for coloring the polyoxymethylene resin was extruded into a strand shape and pelletized with a cutter. The pellets were dried in a hot air circulating oven at 80 ° C. for 5 hours (used in Examples 1, 2, and 3).

  A master batch resin for coloring a polyoxymethylene resin in the same manner as MB1, except that the blending ratio of the components (A), (B) and (C-1) was changed to 99: 0.5: 0.5. A composition (MB2) was prepared (used in Example 4).

  (A), (B) and (C-1) The mixing ratio of the component was changed to 30:40:30, the component (D) was changed to 10 parts by weight, and the component (E) was changed to 5 parts by weight. A masterbatch resin composition (MB3) for coloring a polyoxymethylene resin was produced in the same manner as in Example 1 (used in Example 5).

  A masterbatch resin composition for coloring a polyoxymethylene resin (MB4) in the same manner as MB1, except that the component (D) is changed to 0.01 parts by weight and the component (E) is changed to 0.01 parts by weight. Was used (used in Example 6).

  A masterbatch resin composition for coloring a polyoxymethylene resin (MB5) was produced in the same manner as MB1 except that the component (D) was changed to 10 parts by weight and the component (E) was changed to 5 parts by weight ( Used in Example 7).

  The blending ratio of the components (A), (B) and (C-1), and the blending amounts of the components (D) and (E) are the same as in MB1, and (F) “Tinuvin” 234 [Ciba Specialty] as an ultraviolet absorber. -100 g (equivalent to 1 part by weight) of 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol], manufactured by Chemicals, was added, and was the same as MB1 A masterbatch resin composition (MB6) for coloring a polyoxymethylene resin was produced by the method described above (used in Example 8).

  The blending ratio of the components (A), (B), and (C-1), and the blending amounts of the components (D) and (E) are the same as MB1, and (G) “Sanol” LS765 as a hindered amine light stabilizer. 100 g (corresponding to 1 part by weight) of [Bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, manufactured by Sankyo Lifetech Co., Ltd.] was added, and polyoxy was treated in the same manner as MB1. A masterbatch resin composition (MB7) for coloring methylene resin was produced (used in Example 9).

  The blending ratio of (A), (B) and (C-1) components and the blending amounts of (D) and (E) components are the same as MB1, and (H) polyethylene wax (manufactured by Clariant Japan Co., Ltd.) , LicowaxPED822) was added in an amount of 1000 g (corresponding to 10 parts by weight), and a polyoxymethylene resin coloring masterbatch resin composition (MB8) was produced in the same manner as MB1 (used in Example 10).

  (C-1) The same as MB1, except that the component carbon black (Color Index Generic Name: Pigment Black 7) is changed to (C-2) Diketoropyrrolopyrrole (Color Index Generic Name: Pigment Red 254) A masterbatch resin composition (MB9) for coloring polyoxymethylene resin was produced by the method (used in Examples 11, 12, and 13).

  (C-1) The same as MB2, except that the component carbon black (Color Index Generic Name: Pigment Black 7) is changed to (C-2) Diketoropyrrolopyrrole (Color Index Generic Name: Pigment Red 254) A masterbatch resin composition (MB10) for coloring a polyoxymethylene resin was produced by the method (used in Example 14).

  (C-1) The same as MB3, except that the component carbon black (Color Index Generic Name: Pigment Black 7) is changed to (C-2) Diketoropyrrolopyrrole (Color Index Generic Name: Pigment Red 254) A masterbatch resin composition (MB11) for coloring polyoxymethylene resin was produced by the method (used in Example 15).

  (C-1) The same as MB4, except that the component carbon black (Color Index Generic Name: Pigment Black 7) is changed to (C-2) Diketoropyrrolopyrrole (Color Index Generic Name: Pigment Red 254) A masterbatch resin composition (MB12) for coloring a polyoxymethylene resin was produced by the method (used in Example 16).

  (C-1) The same as MB5, except that the component carbon black (Color Index Generic Name: Pigment Black 7) is changed to (C-2) Diketoropyrrolopyrrole (Color Index Generic Name: Pigment Red 254) A masterbatch resin composition (MB13) for coloring polyoxymethylene resin was produced by the method (used in Example 17).

  (C-1) The same as MB6, except that the component carbon black (Color Index Generic Name: Pigment Black 7) is changed to (C-2) Diketoropyrrolopyrrole (Color Index Generic Name: Pigment Red 254) A masterbatch resin composition (MB14) for coloring a polyoxymethylene resin was produced by the method (used in Example 18).

  (C-1) The same as MB7, except that the component carbon black (Color Index Generic Name: Pigment Black 7) is changed to (C-2) Diketoropyrrolopyrrole (Color Index Generic Name: Pigment Red 254). A masterbatch resin composition (MB15) for coloring polyoxymethylene resin was produced by the method (used in Example 19).

  (C-1) The same as MB8, except that the component carbon black (Color Index Generic Name: Pigment Black 7) is changed to (C-2) Diketoropyrrolopyrrole (Color Index Generic Name: Pigment Red 254). A masterbatch resin composition (MB16) for coloring a polyoxymethylene resin was produced by the method (used in Example 20).

  (B) Component polyamide 6/66/610/12 quaternary copolymer (copolymerization composition 6/66/610/12 = 22/12/16/50 (parts by weight)) A master batch resin composition (MB17) for coloring a polyoxymethylene resin was produced by the method described above (used in Comparative Example 1).

  (B) Component polyamide 6/66/610/12 Quaternary copolymer (copolymerization composition 6/66/610/12 = 22/12/16/50 (parts by weight)) A master batch resin composition (MB18) for coloring a polyoxymethylene resin was produced by the method described above (used in Comparative Example 2).

  (E) The masterbatch resin composition (MB19) for coloring polyoxymethylene resin was manufactured by the same method as MB1 except not adding the component 12-hydroxy calcium stearate (used in Comparative Example 3).

  (D) Component “Irganox” IR245 [manufactured by Ciba Geigy Specialty, triethylene glycol-bis (3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate)] (hindered phenol antioxidant) A masterbatch resin composition (MB20) for coloring a polyoxymethylene resin was produced in the same manner as MB1 except that the (agent) was not added (used in Comparative Example 4).

  (D) Component “Irganox” IR245 [manufactured by Ciba Geigy Specialty, triethylene glycol-bis (3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate)] (hindered phenol antioxidant) Agent) and (E) component 12-hydroxy master stearate resin composition (MB21) for coloring a polyoxymethylene resin was prepared in the same manner as MB9, except that calcium hydroxystearate was not added (used in Comparative Example 5).

  (B) Component polyamide 6/66/610/12 quaternary copolymer (copolymerization composition 6/66/610/12 = 22/12/16/50 (parts by weight)), and (D) component “Irganox IR245 [manufactured by Ciba Geigy Specialty, triethylene glycol-bis (3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate)] (hindered phenolic antioxidant), and (E) The masterbatch resin composition for coloring a polyoxymethylene resin (MB22) was produced in the same manner as MB1, except that the component 12-calcium hydroxystearate was not added (used in Comparative Example 6).

[Production of colored polyoxymethylene resin composition]
The polyoxymethylene resin “Amirasu” S761 (manufactured by Toray Industries, Inc.) is 1/20 of the master batch resin composition (MB1) for coloring the polyoxymethylene resin obtained by the above method as shown in Table 4. Blended at a weight ratio, 80 × 80 × 1 mmt square plate and ASTM No. 1 dumbbell were prepared by the above-described injection molding, and the mold deposit property was similarly evaluated. (Example 1). From the cut sample of ASTM No. 1 dumbbell prepared by injection molding, the thermal decomposition rate (Kx) was measured for color unevenness and formaldehyde odor with an 80 mm × 80 mm × 1 mm square plate, and the mold deposit property was measured by injection molding of JIS No. 4 dumbbell. It was found that Kx was 15%, coloring color unevenness was 2, mold depositing property was 2, and odor was 2.0 ppm.

  As shown in Table 2, the blending weight ratio of the master batch resin composition for coloring the polyoxymethylene resin (MB1) and the polyoxymethylene resin “Amirasu” S761 (manufactured by Toray Industries, Inc.) was changed to 1/5. A colored polyoxymethylene resin composition was obtained in the same manner as in Example 1 except for the above (Example 2). When the physical properties were measured in the same manner as in Example 1, it was found that Kx was 12%, the coloring color unevenness was 1, the mold depositing property was 2, and the odor was 1.8 ppm.

  As shown in Table 2, the blending weight ratio of the master batch resin composition for coloring the polyoxymethylene resin (MB1) and the polyoxymethylene resin “Amirasu” S761 (manufactured by Toray Industries, Inc.) was changed to 1/100. A colored polyoxymethylene resin composition was obtained in the same manner as in Example 1 except for the above (Example 3). When physical properties were measured in the same manner as in Example 1, it was found that Kx was 21%, coloring color unevenness was 3, mold depositing property was 2, and odor was 2.2 ppm.

  A colored polyoxymethylene resin composition was obtained in the same manner as in Example 2 except that the master batch resin composition (MB1) for coloring the polyoxymethylene resin was changed to (MB2) (Example 4). When physical properties were measured in the same manner as in Example 2, it was found that Kx was 14%, coloring color unevenness was 1, mold depositing property was 2, and odor was 2.0 ppm.

  A colored polyoxymethylene resin composition was obtained in the same manner as in Example 1 except that the master batch resin composition (MB1) for coloring the polyoxymethylene resin was changed to (MB3) (Example 5). When the physical properties were measured in the same manner as in Example 1, it was found that Kx was 13%, the coloring color unevenness was 1, the mold depositing property was 1, and the odor was 1.3 ppm.

  A colored polyoxymethylene resin composition was obtained in the same manner as in Example 1 except that the master batch resin composition (MB1) for coloring the polyoxymethylene resin was changed to (MB4) (Example 6). When the physical properties were measured in the same manner as in Example 1, it was found that Kx was 20%, the coloring color unevenness was 3, the mold depositing property was 2, and the odor was 2.3 ppm.

  A colored polyoxymethylene resin composition was obtained in the same manner as in Example 1 except that the master batch resin composition (MB1) for coloring the polyoxymethylene resin was changed to (MB5) (Example 7). When the physical properties were measured in the same manner as in Example 1, it was found that Kx was 16%, the coloring color unevenness was 2, the mold depositing property was 2, and the odor was 1.9 ppm.

  A colored polyoxymethylene resin composition was obtained in the same manner as in Example 1 except that the master batch resin composition (MB1) for coloring the polyoxymethylene resin was changed to (MB6) (Example 8). When the physical properties were measured in the same manner as in Example 1, it was found that Kx was 15%, coloring color unevenness was 1, mold depositing property was 2, and odor was 1.3 ppm.

  A colored polyoxymethylene resin composition was obtained in the same manner as in Example 1 except that the master batch resin composition for coloring the polyoxymethylene resin (MB1) was changed to (MB7) (Example 9). When physical properties were measured in the same manner as in Example 1, it was found that Kx was 14%, coloring color unevenness was 2, mold depositing property was 1, and odor was 1.2 ppm.

  A colored polyoxymethylene resin composition was obtained in the same manner as in Example 1 except that the master batch resin composition (MB1) for coloring the polyoxymethylene resin was changed to (MB8) (Example 10). When physical properties were measured in the same manner as in Example 1, it was found that Kx was 15%, coloring color unevenness was 1, mold depositing property was 2, and odor was 1.5 ppm.

  A colored polyoxymethylene resin composition was obtained in the same manner as in Example 1 except that the master batch resin composition (MB1) for coloring the polyoxymethylene resin was changed to (MB9) (Example 11). When the physical properties were measured in the same manner as in Example 1, it was found that Kx was 15%, the coloring color unevenness was 2, the mold depositing property was 2, and the odor was 1.9 ppm.

  A colored polyoxymethylene resin composition was obtained in the same manner as in Example 2 except that the master batch resin composition (MB1) for coloring the polyoxymethylene resin was changed to (MB9) (Example 12). When physical properties were measured in the same manner as in Example 1, it was found that Kx was 11%, coloring color unevenness was 1, mold depositing property was 2, and odor was 1.7 ppm.

  A colored polyoxymethylene resin composition was obtained in the same manner as in Example 3 except that the master batch resin composition for coloring the polyoxymethylene resin (MB1) was changed to (MB9) (Example 13). When physical properties were measured in the same manner as in Example 3, it was found that Kx was 21%, coloring color unevenness was 3, mold depositing property was 2, and odor was 2.2 ppm.

  A colored polyoxymethylene resin composition was obtained in the same manner as in Example 2 except that the master batch resin composition (MB1) for coloring the polyoxymethylene resin was changed to (MB10) (Example 14). When physical properties were measured in the same manner as in Example 2, it was found that Kx was 15%, coloring color unevenness was 1, mold depositing property was 2, and odor was 1.9 ppm.

  A colored polyoxymethylene resin composition was obtained in the same manner as in Example 1 except that the master batch resin composition (MB1) for coloring the polyoxymethylene resin was changed to (MB11) (Example 15). When physical properties were measured in the same manner as in Example 1, it was found that Kx was 14%, coloring color unevenness was 1, mold depositing property was 1, and odor was 1.3 ppm.

  A colored polyoxymethylene resin composition was obtained in the same manner as in Example 1 except that the master batch resin composition (MB1) for coloring the polyoxymethylene resin was changed to (MB12) (Example 16). When the physical properties were measured in the same manner as in Example 1, it was found that Kx was 19%, the color unevenness was 3, the mold deposit property was 2, and the odor was 2.3 ppm.

  A colored polyoxymethylene resin composition was obtained in the same manner as in Example 1 except that the master batch resin composition (MB1) for coloring the polyoxymethylene resin was changed to (MB13) (Example 17). When the physical properties were measured in the same manner as in Example 1, it was found that Kx was 15%, the coloring color unevenness was 2, the mold depositing property was 2, and the odor was 1.9 ppm.

  A colored polyoxymethylene resin composition was obtained in the same manner as in Example 1 except that the master batch resin composition (MB1) for coloring the polyoxymethylene resin was changed to (MB14) (Example 18). When physical properties were measured in the same manner as in Example 1, it was found that Kx was 14%, coloring color unevenness was 1, mold depositing property was 2, and odor was 1.2 ppm.

  A colored polyoxymethylene resin composition was obtained in the same manner as in Example 1 except that the master batch resin composition for coloring the polyoxymethylene resin (MB1) was changed to (MB15) (Example 19). When physical properties were measured in the same manner as in Example 1, it was found that Kx was 13%, coloring color unevenness was 2, mold depositing property was 1, and odor was 1.1 ppm.

  A colored polyoxymethylene resin composition was obtained in the same manner as in Example 1 except that the master batch resin composition (MB1) for coloring the polyoxymethylene resin was changed to (MB16) (Example 20). When the physical properties were measured in the same manner as in Example 1, it was found that Kx was 14%, the coloring color unevenness was 1, the mold depositing property was 2, and the odor was 1.4 ppm.

  A colored polyoxymethylene resin composition was obtained in the same manner as in Example 1 except that the master batch resin composition (MB1) for coloring the polyoxymethylene resin was changed to (MB17) (Comparative Example 1). When physical properties were measured in the same manner as in Example 1, it was found that Kx was 40%, coloring color unevenness was 4, mold depositing property was 5, and odor was 21.7 ppm.

  A colored polyoxymethylene resin composition was obtained in the same manner as in Example 1 except that the master batch resin composition (MB1) for coloring the polyoxymethylene resin was changed to (MB18) (Comparative Example 2). When physical properties were measured in the same manner as in Example 1, it was found that Kx was 38%, coloring color unevenness was 4, mold depositing property was 5, and odor was 21.4 ppm.

  A colored polyoxymethylene resin composition was obtained in the same manner as in Example 1 except that the master batch resin composition (MB1) for coloring the polyoxymethylene resin was changed to (MB19) (Comparative Example 3). When physical properties were measured in the same manner as in Example 1, it was found that Kx was 26%, coloring color unevenness was 3, mold depositing property was 3, and odor was 4.2 ppm.

  A colored polyoxymethylene resin composition was obtained in the same manner as in Example 1 except that the master batch resin composition (MB1) for coloring the polyoxymethylene resin was changed to (MB20) (Comparative Example 4). When the physical properties were measured in the same manner as in Example 1, it was found that Kx was 30%, the coloring color unevenness was 2, the mold depositing property was 4, and the odor was 12.2 ppm.

  A colored polyoxymethylene resin composition was obtained in the same manner as in Example 1 except that the master batch resin composition (MB1) for coloring the polyoxymethylene resin was changed to (MB21) (Comparative Example 5). When the physical properties were measured in the same manner as in Example 1, it was found that Kx was 34%, the coloring color unevenness was 3, the mold depositing property was 4, and the odor was very bad at 18.3 ppm.

  A colored polyoxymethylene resin composition was obtained in the same manner as in Example 1 except that the master batch resin composition for coloring the polyoxymethylene resin (MB1) was changed to (MB22) (Comparative Example 6). When the physical properties were measured in the same manner as in Example 1, it was found that Kx was 52%, the coloring color unevenness was 5, the mold depositing property was 5, and the odor was 24.2 ppm.

  The masterbatch resin composition for coloring the polyoxymethylene resin of the present invention, and the colored polyoxymethylene resin composition obtained by mixing the polyoxymethylene resin with the polyoxymethylene resin have little color unevenness during coloring, and are thermally stable. And the generation of formaldehyde gas is reduced, it can be used for a wide range of molding applications such as electric / electronic parts, automobile parts, machine parts, and toys.

Claims (6)

(A) 99 to 0% by weight of polyoxymethylene resin;
(B) polyamide 6/66/610/12 quaternary copolymer 0.5 to 60% by weight;
(C) For a total of 100 parts by weight consisting of 0.5 to 40% by weight of one or more colorants selected from inorganic, organic and extender pigments,
(D) 0.01 to 10 parts by weight of a hindered phenol antioxidant having a molecular weight of 400 or more (E) 0.01 to 5 parts by weight of a metal salt of a saturated fatty acid,
And further (F) 0-3 parts by weight of an ultraviolet absorber, if desired
(G) 0 to 6 parts by weight of a hindered amine stabilizer,
(H) A masterbatch resin composition for coloring a polyoxymethylene resin containing 0 to 20 parts by weight of a dispersion aid. 2. The masterbatch resin composition for coloring a polyoxymethylene resin according to claim 1, wherein the polyoxymethylene resin is an oxymethylene copolymer composed of a repeating unit represented by the following general formula (I).

(In the formula, R ₁ and R ₂ are an inert substituent selected from hydrogen, a lower alkyl group and a halogen-substituted lower alkyl group, n is an integer of 0 to 5, and 70 to 99.9 of repeating units. Mole% is n = 0.) The master batch resin composition for coloring a polyoxymethylene resin according to claim 1 or 2, wherein the metal salt of the (E) saturated fatty acid is an alkaline earth metal salt. A colored polyoxymethylene obtained by mixing (a) a masterbatch resin composition for coloring a polyoxymethylene resin according to any one of claims 1 to 3 and (b) a polyoxymethylene resin. Resin composition. The colored polyoxymethylene resin composition according to claim 4, wherein a mixing weight ratio of the component (a): the component (b) is 1: 5 to 100. The colored polyoxymethylene resin composition according to claim 4, wherein the content of the colorant in the colored polyoxymethylene resin composition is substantially 0.05 to 2%.