JP3074864B2 - Coloring material and resin composition containing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coloring material comprising a crosslinkable resin colored by a dye and a pigment, and dispersing the coloring material in a thermoplastic resin to form a resin material. An object of the present invention is to provide a thermoplastic resin composition having a beautiful fine spot pattern having a cloth texture and giving a molded article having a decorative feeling.

[0002]

2. Description of the Related Art Various methods have heretofore been attempted for the purpose of imparting a dot pattern such as a stone pattern or a cloth pattern to a thermoplastic resin molded product. As one of the methods, a spot pattern is formed on the surface of a molded product by melting and kneading several kinds of thermoplastic resins colored in different hues and molding them in an unevenly colored state before they are uniformly kneaded. There is a way to make it happen. However, kneading properties are improved in recent screw-type injection molding machines, hollow molding machines, and the like, and it is difficult to obtain a spot pattern by uneven kneading on the surface of a resin molded product using such a molding machine. Further, when mixing and dispersing different colored synthetic resin particles having a high softening temperature, the temperature range in the resin melt-kneading step is limited, and further, due to an unexpected temperature rise during kneading, the colored resin particles soften, It is difficult to obtain a stable pattern because the speckle pattern on the surface of the molded article flows.

[0003] Therefore, as a method of applying a spotted pattern such as stone-grain or cloth-grain to the surface of a molded article without giving various problems to the physical properties of the molded article, hitherto, such as print coating, hot stamping, sinking, etc. Surface painting is used in various areas. However, since all of these techniques involve surface treatment as secondary processing, the production cost is high, and the ground pattern inside the molded product is easily exposed due to external damage, and there is a risk of abrasion and discoloration. It had various disadvantages.

Further, as a method of using a fibrous substance, Japanese Patent Application Laid-Open No. 51-123248 discloses a thermoplastic resin having a fine speckle pattern by uniformly dispersing cellulosic colored fibers in the thermoplastic resin. Although the composition is described, in this method, since the fibers emerge in the form of lint on the surface of the colored molded product, it is difficult to form a fine spot pattern, and the decorative feeling such as stone-grain tone and cloth-grain tone is sufficiently reproduced. It is difficult.

[0005]

SUMMARY OF THE INVENTION In view of such circumstances, reproducibility can be easily achieved with ordinary extrusion molding machines and injection molding machines without the need for expensive secondary processing or work on molds and molding machines. It gives spot patterns such as stone-grain tone and cloth-grain tone well, improves molding temperature range and improves reproducibility failure due to unexpected temperature rise during molding and kneading property difference of molding machine. The emergence of a thermoplastic resin composition that allows adaptation is strongly desired.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to obtain a thermoplastic resin composition which gives a spot pattern easily and with good reproducibility. A thermoplastic resin composition which, when dispersed in a resin, easily gives a molded article having a spot pattern such as a stone-grain tone, a cloth-grain tone or the like which is reproducible by ordinary extrusion molding or injection molding without the above-mentioned various disadvantages It was found that a product was obtained, and the present invention was completed.

That is, the present invention is a coloring material comprising a specific crosslinkable resin (A) and a dye / pigment (B) described below, and a thermoplastic resin composition or a coloring material containing the coloring material. It is intended to provide a thermoplastic resin molded product.

The crosslinkable resin (A) used in the present invention is selected from an epoxy group, a maleic anhydride group and an oxazoline group.
That the reactivity of the thermoplastic resin having a substituent (C) with functional groups that react therewith, i.e. carboxyl groups, reactive hydroxyl, low molecular compounds having two or more mercapto groups and (D) (obtained known as cross-linking agent) a crosslinkable resins obtained by.

The thermoplastic resin (C) having a reactive substituent has a main chain of polyethylene, polypropylene, polystyrene, EVA resin, AS resin, ABS
Resins, acrylic resins and the like can be mentioned, and among them, polystyrene is preferable.

As the reactive substituent, an oxazoline group is particularly preferable among the above. The low-molecular compound (D) used as a crosslinking agent is not particularly limited as long as it has two or more functional groups selected from a carboxyl group, a hydroxyl group, and a mercapto group in the molecule. Compounds having a melting point of 200 ° C. or less are preferred. Furthermore, polyvalent carboxylic acids having high reactivity with oxazoline groups, such as citric acid, tartaric acid, malic acid, malonic acid, succinic acid, and maleic acid, are preferred.

The dye / pigment (B) is not particularly limited.
Various dyes and pigments can be used, and among them, pigments are preferable, and any of known organic pigments, inorganic pigments, extender pigments and the like can be used. For example, azo-based, anthraquinone-based, thioindigo-based, perylene-based, perinone-based, quinacridone-based, phthalocyanine-based, dioxazine-based, isoindolinone-based organic pigments, carbon black, titanium oxide, red iron oxide, ultramarine, graphite, Other examples include inorganic pigments such as calcined pigments, and extender pigments such as tankar, barium sulfate, and talc. These may be used alone or in combination of two or more.

As the thermoplastic resin used in the present invention, for example, polystyrene, polypropylene, polyethylene, A
Examples include S resin, ABS resin, acrylic resin, and vinyl chloride resin, and among them, polystyrene, polypropylene, and ABS resin are preferable.

It should be noted that the coloring material according to the present invention is:
As such, it is effective for general use as a coloring material, and can be used, for example, for coloring thermosetting resins and for producing paints. As a basic matter for obtaining a molded product having a beautiful spot pattern according to the present invention, first, a coloring material obtained by coloring a crosslinkable resin with a dye or pigment is prepared.

That is, the method for producing a coloring material according to the present invention includes, for example,
The thermoplastic resin having a reactive group, the dye / pigment, and the crosslinking agent are preliminarily mixed, and the mixture is melt-kneaded by a kneader or a screw-type extruder that can be heated, crosslinked and hardened, and further pulverized and granulated. Classification is performed as necessary to obtain a granular color material of a desired size. In the case of an extruder, the crosslinking agent may be supplied from a side feeder. In addition, the product is taken out by opening the head without using the die portion.

The particle size of the coloring material of the present invention is determined by the size of the molded product,
The appropriate value range varies depending on the wall thickness, molding method, etc.
When a molded article for daily necessities by injection molding, blow molding, press molding or the like is used, the thickness is suitably about 10 μm to 3 mm, and preferably about 0.1 to 2 mm.

Here, the ratio of the reactive group bonded to the thermoplastic resin is about 0.5 to 10% by weight. Especially, in order to perform a stable crosslinking reaction, 1 to 5% by weight is preferable. In addition, the color material can freely change the hue and concentration by selecting the dye and pigment.
1 to 10% by weight. If the amount of the crosslinking agent is too large, the crosslinking does not proceed, so that usually 0.05 to 2% by weight is preferable.

The coloring material thus prepared is infusible and insoluble in itself, and is mixed with a thermoplastic resin and other coloring agents and additives, and is directly supplied to a molding machine for molding.
Alternatively, after melt-kneading with a screw-type extruder to form pellets, the pellets are formed by a molding machine. Thereby, a beautiful molded product having a fine spot pattern on the surface of the molded product can be obtained. The addition ratio of the coloring material to the molding resin is not particularly limited, but is preferably 0.1 to 10% by weight.

In the composition of the present invention, various additives such as a surfactant, a dispersant, an antistatic agent,
Antioxidants, ultraviolet absorbers, metal soaps, polyethylene waxes and the like can be added. Of course, the same applies to the molded product of the present invention.

[0019]

The present invention will be described more specifically with reference to the following examples and comparative examples. All parts and percentages in the examples are on a weight basis.

Example 1 (Preparation of Coloring Material) Epoxros®, an oxazoline-based reactive polymer
PS-1005 (product name of Nippon Shokubai Chemical Co., Ltd., styrene-based compatibilizer, containing 5% by weight of oxazoline), 2 parts of titanium oxide, organic violet pigment No. 1 Violet DV-2 (No. 1) 3 parts of Kasei Kogyo Co., Ltd.) were added, and premixed for 3 minutes with a Henschel mixer. Next, this mixture is 30 mmφ
It was fed to a twin screw vent extruder. The temperature is 21
The temperature was set to 0 ° C., and citric acid as a cross-linking agent was introduced from the vent of the extruder using a side feeder. The amount of citric acid was set to 1 part with respect to 100 parts of RPS-1005. The ejected material was collected from the head from which the dice had been removed, and a 16 mesh pass, 42 mesh on (0.35
〜1 mm) to prepare a coloring material (I).

Example 2 (Preparation of Coloring Material) For 100 parts of Epocros RPS-1005, 1 part of red pattern 100ED (product name of Toda Kogyo Co., Ltd.) and 1 part of Asahi Yellow 5950S (product name of Asahi Nippon Sangyo Co., Ltd.) 1 Parts, 0.1 parts of carbon black, 200
After kneading for 15 minutes in a pressure kneader at a temperature of 0.5 ° C., 0.5 part of maleic acid was added as a crosslinking agent, and the mixture was further kneaded for 5 minutes.
At the time of hardening and forming into granules, it was taken out and subjected to a classification of 10 mesh pass and 42 mesh on (0.35 to 1.68 mm) to prepare a coloring material (II).

Example 3 (Preparation of coloring material) Reseda GP-50 which is an epoxy-modified polystyrene
0 parts (product name of Toa Gosei Chemical Industry Co., Ltd.) and 0.1 parts of red stalk NYR-60N (product name of Titanium Industry Co., Ltd.) were mixed with 0.3 parts of titanium oxide, and the same as in Example 1. Extrusion granulation was performed by the method described above to prepare a coloring material (III). However, here, 2 parts of glycerin was used as the crosslinking agent.

Example 4 (Preparation of Coloring Material) Reseda, a modified maleic anhydride acrylic styrene
GP-400 (product name of Toa Gosei Co., Ltd.) 10
To 0 parts, 0.5 part of cyanine blue # 5050 (product name of Dainippon Ink and Chemicals, Inc.) is blended,
Extrusion granulation was performed in the same manner as in Reference Example to prepare a coloring material (IV). However, here, 5 parts of glycerin and 0.5 part of sodium acetate were used as the crosslinking agent.

Example 5 1 part of the coloring material (I) obtained in Example 1, polypropylene J-
After mixing 100 parts of 109G (product name of Ube Industries, Ltd.), 1 part of titanium oxide and 0.4 parts of magnesium stearate with a tumble mixer for 3 minutes, the mixture was melted at 230 ° C. using a 40 mmφ single screw vent extruder. The mixture was kneaded and pelletized to obtain a colored thermoplastic resin composition.
The pellets were molded at 230 ° C. using a 75-ton screw injection molding machine as a molding material. The surface of the obtained molded product had a beautiful stone grain with a purple spot pattern on a white background.

Examples 6 to 9 In the same manner as in Example 5, molded articles of various compositions were prepared using the coloring materials (I) to (IV) and any pigments and resins. The composition, appearance and surface condition of the molded product are shown in Table 1 together with Example 5. The resins used in these examples are as follows.

PP: polypropylene (product of Ube Industries, Ltd., brand name J-109G) PS: polystyrene (product of Dainippon Ink and Chemicals, brand name CR-3500) ABS: ABS resin (product of Nippon Synthetic Rubber Co., Ltd.
Brand name: JSR10) AS: AS resin (Mitsubishi Kasei Polytech Co., Ltd., brand name: SAN-A)

[0027]

[Table 1] Comparative Example 1 A composition obtained by melt-kneading a polyester resin and a pigment was finely pulverized to prepare a colored chip. polypropylene
1 part of this colored chip for 100 parts, titanium oxide
1 part, 0.4 part of magnesium stearate
230 ° C directly by 75 ton screw type injection molding machine
Molded. On the surface of the obtained molded article, there was a defect that delamination occurred.

Comparative Example 2 Ceramic-based colored chip, diamond chip DM-1
No. 8 (Dia Kogyo Co., Ltd., 1 part) and 100 parts of polystyrene (GPPS) were mixed and molded in the same manner as in Comparative Example 1. On the surface of the obtained molded product, the shape of the colored chip was distorted and color bleeding was observed due to the separation of the pigment, and the decorativeness was poor.

[0029]

By using the coloring material or the thermoplastic resin composition of the present invention, a resin molded product having a spot pattern such as stone-grain or cloth-grain tone, which has been a great difficulty so far, can be easily reproduced. Can be obtained, and also has the following advantages.

Since the crosslinked coloring material does not melt at the molding temperature of the thermoplastic resin, it can be used at a wide range of molding temperatures and can be applied to various resins. Because there is little effect on the pattern due to fluctuations in molding temperature,
There is no problem in case of unexpected temperature rise.

The reproducibility of the molded product is high because it is not due to intentional poor dispersion which is difficult to control. By simply mixing and dispersing uniformly with a usual extrusion molding machine or injection molding machine, a stone-grained or cloth-grained pattern can be easily provided.

There is no need for secondary processing. The effect on the physical properties as in the case of mixing different resins is small. Because you can change the color of the spots and the ground arbitrarily,
Extremely decorative.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-3-200841 (JP, A) JP-A-51-123247 (JP, A) JP-A-3-210350 (JP, A) JP-A-50- 44247 (JP, A) JP-A-58-154737 (JP, A) JP-A-54-94537 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 1/00-101 / 16 C08K 3/00-13/08

Claims (5)

(57) [Claims] 1. An epoxy group and maleic anhydride in a molecule.
Having a reactive substituent selected from oxazoline and oxazoline groups
Carboxy which reacts with the thermoplastic resin (C) in the molecule
A functional group selected from a xyl group, a hydroxyl group, and a mercapto group.
Obtained by reacting a low molecular compound (D) having two or more
A coloring material comprising a crosslinkable resin (A) and a dye / pigment (B). 2. The coloring material according to claim 1, wherein the particle size is in a range of 10 μm to 3 mm. 3. The crosslinking resin (A) is obtained by reacting a resin (C1) having an oxazoline group with a compound (D) having two or more functional groups selected from a carboxyl group, a hydroxyl group and a mercapto group in a molecule. The coloring material according to claim 1 or 2, which is obtained by the following. 4. A thermoplastic resin and 0.1 to 1 with respect to the thermoplastic resin.
0 wt% of claim 1, 2 or the thermoplastic resin composition containing a coloring material according 3. 5. The method of claim 1, 2 or thermoplastic resin molded product containing a coloring material 3 described.