JPS5918750A - Resinous dispersing agent for coloring abs and as resin and method for using the same - Google Patents

Abstract

PURPOSE:To color an ABS or AS resin uniformly with improved dispersibility of a dye or pigment without deteriorating the characteristics of the colored resin, by dispersing a styrene-acrylonitrile copolymer in the ABS or AS resin. CONSTITUTION:100pts.wt. ABS or AS resin is melt kneaded with 0.05-5.0pts.wt., preferably 0.25-1.0pts.wt., styrene-acrylonitrile copolymer having 1,000-10,000 number-average molecular weight, usually 3.5-1.0 ratio between the weight- average and number-average molecular weights, 20-60mol% content of acrylonitrile and 200-40,000 cP melt viscosity at 200 deg.C as a dispersing agent and 0.01-1.5pts.wt. pigment, e.g. potassium sulfide. The ratio between the dispersing agent and the pigment is (1/1)-(1/6) for an inorganic pigment and (6/1)-(1/1) for an organic pigment.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a resinous dispersant for coloring ABS or As resin, and a method for coloring ABS or As resin using the resinous dispersant.

ABS and As resins are used in various electrical and electrical equipment, automobile parts, and miscellaneous goods because of their well-balanced physical properties, good moldability, and good appearance of molded products. I'm talking. Furthermore, ABS and As resins are often used in colored products in which various dyes and pigments (hereinafter simply referred to as pigments) are dispersed in order to increase the commercial value of molded products. However, if the pigment is simply melted and mixed into the resin, the pigment will coagulate in the resin, resulting in poor appearance of the finished product and a decrease in colorability, resulting in a problem that the commercial value of the product will be impaired. To solve this problem, metallic soaps, higher fatty acids, known surfactants, and the like are added as dispersants for pigments during melt mixing, and some effects have been achieved. In addition to dispersion performance, this dispersant is required to be stable under processing conditions and not to impair the physical properties of the resin, and so far no one has been found that fully satisfies the requirements. However, even the metal soaps that are used in large quantities have insufficient dispersing performance, and it has been hoped that a more easily palatable dispersant would appear.

The present inventor has conducted extensive studies to develop a dispersant for coloring ABS or As resin that does not have the above-mentioned drawbacks, and as a result has arrived at the present invention.

That is, the present invention has a number average molecular weight of 1,000 to 10,00.
A resinous dispersant for coloring ABS and As resins consisting of a styrene-acrylonitrile copolymer [AI of 0.0 and 0.0 and 0.0% for coloring ABS and As resins, and for coloring ABS and As resins with the coloring dispersants. Suitable resins include ABS resin and As resin, or resin compositions containing these as main components, and are compliant with ASTM D-1788.68 and ASTI, 'ID-1, respectively.
431.67 may be used.

The coloring dispersant used in the present invention is obtained by copolymerizing acrylonide and styrene (other polymerizable monomers may be added within a range that does not impair performance) using the known low molecular weight polymerization method described below. You can get it. The content of acrylonitrile in the copolymer is 20 to 60 mol%, more preferably 30 to 50 mol%. Other third weight substances that may be added include, for example, methyl methacrylate-1., vinyl acetate, etc., and the amount thereof is preferably 30 mol % or less based on the total copolymer. If the ratio of acrylonitrile and styrene is outside the above range, the appearance of products with insufficient compatibility with ABS or As resin will be impaired. Dispersant [The molecular weight of AI can be measured by Kölpermeation chromatography, and the number average molecular weight in terms of polystyrene is usually 1,000 to 10,000, and further 2
,000 to 8,000. The weight average molecular weight is preferably 1,500 to 85,000, more preferably 8,000 to 28,000, and the ratio (iφ) of the weight average molecular weight to the number average molecular weight is usually 35 to 1.
．． 0 and more preferably 30 to 15. If the number average molecular weight is less than 1,000, the resin's hardness and tip will decrease.
If it is less than 0.000, the acceptability of the @ material becomes poor and a uniform dispersion cannot be obtained. Also, if the 1.1 luy/M is 3.5 or more, low molecular weight substances that reduce the properties of the resin will inevitably be included, which is not preferable. In addition, the resinous dispersant [Al has a melt viscosity of 200 to 4 at 200°C.
0,000OCPS and 1,000~10,000OC
I like that it's PS.

If the melt viscosity is less than 2000 PS, pigment receptivity will be poor, and if it is more than 40,0 OOCPS, the ABS or As resin will deteriorate.

The resinous dispersant can be used for anionopolymerization using an alkali (or alkaline earth metal alkyl) as a catalyst, or for polymerization using a polymerization initiator in a solvent with a high chain transfer constant such as 1-luene, xylene, or cumene. It can be produced by coradical polymerization.Rancal polymerization initiators include peroxide-based initiators such as benozoyl peroxide, lauroyl peroxide, and dicumyl peroxide, and azo-based initiators such as abhisisobutyronitrile and azohisvaleronitrile. An initiator can be used.Moreover, in radical polymerization, it is also possible to control the molecular weight by using a chain transfer agent based on mercaptan, such as lauryl mercaptan.An example of the production method is as follows. Stirring blade, thermometer 9 dropping funnel.

1 in an 11-capacity reaction vessel equipped with a cooling tube and a nitrogen introduction tube.
- 180 g of toluene was charged, stirred and heated under a nitrogen atmosphere, and at the boiling point of toluene, 130 g (127 mol) of styrene, 45 g (0.85 mol) of acrylonitrile, 7 g of lauryl mercaptan, and 7 g of asohyscliff tyronitrile were added.
A mixed solution of g was added dropwise over 4 hours. After the dropwise addition was completed, the reaction solution was kept below the boiling point for another 4 hours to complete the reaction.

After the reaction was completed, the solvent was distilled off to obtain 179 g of styrene/acrylonyl copolymer. Its softening point is 115°
According to C (ring and ball method), its number average molecular weight M is 2,700 miles, and 1,000 molecules NM♂ is 6,400, and the ratio (k/Mnl)
is 24, and the melt viscosity at 200°C is 2.80
It was 00PS.

The pigment used in the present invention may be one that does not undergo significant deterioration or change even if treated for several hours at the processing temperature of the ABS or As resin to be colored, such as cadmium sulfide, iron oxide,
Chromium oxide, ultramarine.

Inorganic pigments such as Kobal I-Blue, Carfosi Flac, and titanium dioxide, phthalocyanine-based, quinacridone-based, naphthol-based, azo-based, and anthraquinone-based pigments.

Examples include organic dyes and pigments such as dioxazine-based and berylene-perinone-based dyes and pigments, and mixtures thereof.

Resinous dispersant [The ratio of AI to 100 parts by weight of ABS or As resin is 0.05 to 50 parts by weight, more preferably 01 to 20 parts by weight, most preferably 0.25 to 1.
It is 0 parts by weight. If it is less than 0.05 parts by weight, the dispersibility of the pigment will be insufficient, and if it is more than 5 parts by weight, the impact strength and heat resistance of the final molded product will decrease.

The proportion of the pigment to be used is 0.05 to 1.5 parts by weight, preferably 0.1 to 10 parts by weight, per 100 parts by weight of the 8Bs or As resin.
Parts by weight. The ratio of resinous dispersant (AI) to pigment (dispersant/pigment) is 1/1 to 1/6 for inorganic pigments and 6/1 to 1/2 for organic dyes and pigments.

The method of coloring ABS or As resin with a pigment using the resinous dispersant [AI includes a method of mixing and melting three components at once,
A method using a processed pigment in which a pigment and a dispersant are mixed (for example, published patent publication No. 54-80831) or a method using a processed pigment in which a pigment and a dispersant are mixed
A method using a so-called masterbatch that is dispersed in BS or As resin at a high concentration (for example, the method described in Japanese Patent Application Publication No. 1983-1999)
58955. 52-58956), but there is no particular limitation. Generally, pigments and resinous dispersants [Al are mixed in a Henschel mixer or a Banbury mixer-1 extruder.

Processed pigments are prepared by triblend or melt friend at 50 to 250°C, preferably 70 to 150°C using a mixer such as a two-roll mixer, and then the processed pigments are mixed into A, BS, etc.
Or use As resin and a mixer such as an extruder to
Preferably, a method of kneading at 150 to 250°C is used. Furthermore, a so-called masterbatch is prepared by dispersing the resinous dispersant and pigment in ABS or As resin at a high concentration, and then this masterbatch is dispersed in ABS or As resin using a mixer such as an extruder. I'll tell you how. From the viewpoint of uniform dispersion of the pigment, the Masterno (edge) method is more preferable.

In the present invention, in addition to the plasticizers, oxidizing agents, ultraviolet absorbers, and antistatic agents that are normally employed when processing resins, spreading aids (for example, fluid It is also possible to add paraffin, wax-in-wax, etc.).

The ABS or ΔASS resin coloring external dispersant of the present invention has extremely excellent T-co dyeing and pigment dispersion ability, and has excellent compatibility with ABS or As resin, so that the resin can be colored uniformly. Furthermore, since it has almost the same chemical structure as the base resin to be added, it is possible to obtain an excellent colored ABS or As resin without impairing the physical properties of the colored resin.

Next, Examples and Comparative Examples will be described to explain the present invention in more detail, but the present invention is not limited thereto.

Example-1 Phthalocyaninofno L; -100 overlapping parts Tostyrene-acrylonitrile copolymer (styrene-acrylonitrile, molar ratio 15:1, number average molecular weight 2,700, softening point 11
Melt viscosity at 5°C and 1200'C: 2,800CPS
) 2ooN parts were mixed in a Henschel mixer to prepare a processed pigment. ABS resin (Mitsubishi Monsando Tuflex TFX-410, Melt Intex 10 g,
0.75 parts by weight of the processed pigment and part by weight of liquid paraffin were added to 100 parts by weight (100 parts by weight) of the processed pigment, mixed in a drum-type blender, cross-extruded in an extruder (temperature 210 C), and then pelletized. In order to judge the surface condition and pigment dispersion degree in the pellet, the pellet was pressed for 3 minutes at 200"C and 100φ using a pressure molding machine to a thickness of 10".
A 0μ film was produced. Visually check the surface condition at a magnification of 1
The determination was made by observing the number of coarse pigment particles (particles with a particle size of 20 μm or more) using an optical microscope with a magnification of 50 times.

The results are shown in Table 1.

Example-2 Phthalocyanine Fluorine 20 Weight 100 parts by weight of the styrene-acrylonitrile copolymer described in Example-i was kneaded in the same manner as in Example-1 to prepare a processed pigment. Example 1: 06 parts by weight of the processed pigment and 100 parts by weight of ABS resin
A colored ABS resin was prepared by mixing and extruding in the same manner as above. The surface condition and pigment dispersion degree are shown in Table 1.

Example-3 100 parts of ABs m fat, 25 parts by weight of phthalocyanin, 25 parts by weight of Flu, 50 parts by weight of the styrene-acryliconi-1-lyl copolymer described in Example-1, and 1 part by weight of liquid paraffin.
Add the weight part, fred with a drum-type printer, and use an extruder! 1 (extrusion temperature: 200°C) and pelletized by extrusion into a string to obtain a masterbatch. 175 parts by weight of the masterbatch and 899 parts by weight of AB were mixed in a drum-type printer, and the mixture was similarly extruded into pellets using an extruder.

The surface condition and pigment dispersion degree are shown in Table 1.

Example-4 Styrene-acrylonitrile molar ratio t, 5:1.
Number average molecular weight 8,500, softening point 128°C, 200°
In C, the same procedure as in Example 1 was carried out using the copolymer as a dispersant. The results are shown in Table 1.

Example 5 The same procedure as in Example 1 was conducted using As resin (Estyrene As-41 manufactured by Nippon Steel Chemical Co., Ltd., Nulto Intex 1.5) as the resin to be colored. The results are shown in Table 1.

Example 6 A processed pigment was prepared in the same manner as in Example 2 from 100 parts by weight of red iron and 50 parts by weight of the styrene-acrylonitrile copolymer described in Example 1. Mix 0.15 parts by weight of the processed pigment and 100 parts by weight of ABS resin in the same manner as in Example-1,
Extruded into pellets. The results are shown in Table 1.

Comparative Example-1 Styrene/acrylonitrile molar ratio 1.5:1 number average molecular weight 15,000. Softening point 160°C, 200°C
A processed pigment was prepared in the same manner as in Example-1 using a styrene-acrylonitrile copolymer with a solution M viscosity of 60,0000PS, and then ABS resin (Tafrenox TFX
-410). The surface condition and pigment dispersion degree are shown in Table 1.

Comparative Example 2 In Example 1, instead of the styrene/acrylonide 1-nor copolymer dispersant, Styrene O'J comer (number average molecular weight 1,200, softening point 94C, melt viscosity at 200°C 2000PS) was used.

Comparative Example 3 In Example 1, 7J lesium stearate was used instead of the styrene/acrylonide 1-nor copolymer.

Comparative Example-4/4BS [100 parts by weight of fat, 25 parts by weight of phthalocyanine filler-0, and 1 part by weight of liquid paraffin 0]
1. Transfer to a drum-type printer and extruder (
2] υ cross-wire extrusion by 0°C), pereino by Tshi)
- Changed t2.

MA 1) Surface condition The bleeding condition and other conditions on the surface were observed with a second glance, and judged in the following three stages.

2) Pigment dispersion: Judgment was made based on the number of coarse pigment particles of 20p or larger observed in one field of view using an optical microscope with a magnification of 150 times.

-,355-

Claims (1)

[Scope of Claims] 1) ABS consisting of styrene/acrylonyl 1-lyl copolymer [A+] having a number average molecular weight of 1,000 to 10,000
Or a resinous dispersant for coloring As resin. 2) Styrene/acryloni-1-lyl copolymer [A] Melt viscosity at 200'C is 200 to 40,0000
ABS or A according to claim 1 which is PS
sResinous dispersant for resin coloring. 3) ABS″i! or As resin coloring according to claim 1 or 2, wherein the content of acrylonitrile 1-lyl in the styrene-acrylonitrile copolymer [A] is 20 to 60 mol%. 4) ABS or As resin, number average molecular weight of 1,000 to 10, 0.05 to 5 parts by weight per 100 parts by weight of the resin.
,000 styrene acryloni!・Ryl copolymer [A
], and a method of using a resinous dispersant for coloring ABS or As resin, which is characterized by uniformly mixing and dispersing dye and/''!, or pigment. 5) ABS or AS resin 100 500 parts by weight
0.05 to 10 parts by weight or less of pigments and/or dyes
ABS according to claim 4, wherein 0 parts by weight of copolymer [A] is uniformly mixed and dispersed to obtain a masterbatch, and then the masterbatch is uniformly mixed and dispersed in ABS or As resin. and a method of using a resinous dispersant for coloring As resin.