Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Processes of preparing a desired or intentional composition...
Reexamination Certificate
2000-06-28
2002-05-28
Sanders, Kriellion A. (Department: 1714)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Processes of preparing a desired or intentional composition...
C524S127000, C524S156000, C524S157000, C524S284000, C544S347000, C544S348000
Reexamination Certificate
active
06395809
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a water-insoluble nigrosine compound, a crystalline resin composition and fiber-reinforced crystalline resin molded product both containing said nigrosine compound, a method for lowering the crystallization temperature of a crystalline resin, a method for improving the to fluidity of a crystalline resin, and a method for improving the surface gloss of a crystalline resin.
2. Description of the Prior Art
Being excellent in mechanical and chemical properties, crystalline resins are widely used for molded plastic products in the field of parts of automobiles, electric and electronic products, etc, and their demand is increasing in the field of engineering plastics.
Crystalline resins are colored for decoration, color identification, improvement of light fastness of molded products, content protection and shading and for other purposes. Traditionally, various inorganic pigments and organic dyes/pigments, such as carbon black, black metal complex dyes, azine dyes and perinone black, have been used for black coloring of crystalline resins.
More specifically, examples of colored crystalline resins include a molding formula comprising a polyamide resin colored with carbon black and nigrosine (Japanese Patent Examined Publication No. 43379/1985); a molding composition comprising a polyamide resin colored with carbon black and a copper phthalocyanine pigment (Japanese Patent Unexamined Publication No. 226551/1985); a molding composition comprising an unsaturated polyester resin colored with aniline black and solvent blue (Japanese Patent Examined Publication No. 46524/1989); a plastic molding composition comprising a thermoplastic resin added with carbon black and titanium oxide (Japanese Patent Unexamined Publication No. 186633/1993); a colored resin composition comprising a thermoplastic resin colored with a red organic pigment, a blue organic pigment and a yellow organic pigment (Japanese Patent Unexamined Publication No. 230278/1993); and a mixed resin of polyethylene terephthalate resin and polybutylene terephthalate resin with carbon black dispersed therein (Japanese Patent Unexamined Publication No. 194825/1993).
However, these conventional colored crystalline resin compositions do not always have good appearance and surface gloss, remaining to require further investigation.
In addition, there have been attempts to improve the heat resistance and chemical resistance of crystalline resins or to confer mechanical characteristics suited for various uses, by formulating a fibrous reinforcing material therein, to meet the requirements of a wide variety of industrial applications. Furthermore, in recent years, there has been a marked trend toward replacement of conventional metal parts of products with fiber-reinforced crystalline resin parts, for the purpose of weight reduction, manufacturing process simplification and corrosion prevention, taking note of the good properties of fiber-reinforced crystalline resins as molding materials.
Examples of such fiber-reinforced colored crystalline resins include the polyamide vehicle element described in Japanese Patent Unexamined Publication No. 246958/1987, which comprises a nylon 66/6 copolymer, glass fiber, an inorganic mineral powder and an azine dye; a polyester resin composition for molding comprising a polybutylene terephthalate having a specific viscosity of not less than 0.35, a reinforcing material and carbon black (Japanese Patent Unexamined Publication No. 117951/1990); a thermoplastic resin composition comprising a thermoplastic resin, a modified polyolefin, a fibrous reinforcing material and carbon black (Japanese Patent Unexamined Publication No. 50263/1991); a glass fiber-reinforced black polyamide resin composition comprising a polyamide resin, surface-treated glass fiber and an azine dye (Japanese Patent Unexamined Publication No. 128479/1994); and a polybutylene terephthalate resin composition reinforced with antistatic fiber comprising a glass fiber-reinforced polybutylene terephthalate resin having a volume specific resistivity of not more than 1×10
10
&OHgr;· cm and carbon black (Japanese Patent Unexamined Publication No. 53610/1996).
However, in coloring a fiber-reinforced crystalline resin, there arises the problem of difficulty in thoroughly and uniformly dispersing a coloring agent (e.g., black pigment) in the resin even by kneading for a long time, because of the presence of a fibrous reinforcing material in the resin. In addition, adding a coloring agent can deteriorate the physical properties in comparison with the original resin before its addition, can considerably reduce the fluidity during molding, and can intensify the warpage deformation of the molded product due to a temperature change during molding. In particular, the flotation of the fibrous reinforcing material on the surface of the molded product poses the problem of deterioration of the gloss, appearance, etc. of the colored molded product.
The present invention was developed in view of the above problems in the prior art. Accordingly, the object of the invention is to provide a nigrosine compound which is capable of vividly coloring a crystalline resin (fiber-reinforced or not), which shows particularly good fluidity during molding of a colored crystalline resin, which is excellent in molding precision for the colored crystalline resin, and which favorably improves the appearance-related properties, such as surface gloss, and surface shape or texture, of the molded product, a crystalline resin composition and fiber-reinforced crystalline resin molded product containing said nigrosine compound, a method for lowering the crystallization temperature of a crystalline resin, a method for improving the fluidity of a crystalline resin, and a method for improving the surface gloss of a crystalline resin.
SUMMARY OF THE INVENTION
(1) The nigrosine compound of the present invention for accomplishing the above object is a water-insoluble nigrosine compound which is a salt of nigrosine with sulfuric acid and/or phosphoric acid.
The term “salt of nigrosine with sulfuric acid and/or phosphoric acid” as used herein refers to a salt of nigrosine (generally hydrochloride) wherein sulfate ions and/or phosphate ions are bound to all or a considerable portion (e.g., not less than 50%, or not less than 70%, and preferably not less than 90%) of the groups capable of binding sulfate ions or phosphate ions. (1-1) The nigrosine compound of Term (1) desirably has a chlorine concentration (i.e., chlorine concentration in nigrosine compound) of not more than 3% by weight.
(1-2) In addition, the nigrosine compound of Term (1) or (1-1) desirably has an iron concentration (i.e., iron concentration in nigrosine compound) of not more than 0.5% by weight.
5 (1-3) In addition, the nigrosine compound of Term (1), (1-1) or (1-2) desirably has a residual aniline concentration (i.e., residual aniline concentration in nigrosine compound) of not more than 0.5% by weight.
(1-4) In addition, the nigrosine compound of Term (1), (1-1), (1-2) or (1-3) desirably has a volume resistivity value of not less than 2.0×10
10
&OHgr;· cm.
(1-5) The nigrosine compound of Term (1), (1-1), (1-2), (1-3) or (1-4) can, for example, be produced by treating nigrosine (generally hydrochloride) with sulfuric acid and/or phosphoric acid. When the nigrosine is a hydrochloride, the treatment of the nigrosine with sulfuric acid and/or phosphoric acid may be such that the chlorine ion constituting the salt in the nigrosine is exchanged with a sulfate ion and/or phosphate ion.
(1-6) Furthermore, the nigrosine compound of Term (1), (1-1), (1-2), (1-3) or (1-4) is desirably a sulfate of nigrosine having a chlorine concentration of not more than 9000 ppm.
20 (2) The crystalline resin composition of the present invention is characterized in that the nigrosine compound of Term (1), (1-1), (1-2), (1-3), (1-4), (1-5) or (1-6) is contained in a crystalline resin.
(2-1) The crystalline resin in the crystalline resin composition o
Hayashi Akihiko
Turuhara Tohru
McGlew and Tuttle , P.C.
Orient Chemical Industries Ltd.
Sanders Kriellion A.
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