JP2001207063A - Crystalline resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a crystalline resin composition having good mechanical properties, exterior appearance and surface gloss, and enough lightfastness and capable of being colored clearly without detriment to the inherent properties of the resin. SOLUTION: This crystalline resin composition comprises a thermoplastic resin having crystallinity and one or more cationic surfactants selected from the group consisting of (a) an aliphatic amine salt or its quaternary ammonium salt, (b) an aromatic quaternary ammonium salt, (c) a heterocyclic quaternary ammonium salt and (d) a quaternary phosphonium salt and nigrosine or a black dye obtained by blending the cationic surfactant and the nigrosine.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a crystalline resin composition having good appearance and surface gloss.

[0002]

2. Description of the Related Art Thermoplastic resins, which have excellent mechanical and chemical properties, are widely used in plastic moldings in the field of parts such as automobiles and electric and electronic products. In the field of engineering plastics, demand is increasing. Also, by blending fibrous reinforcing material with thermoplastic resin,
Attempts have been made to improve heat resistance and chemical resistance, and to provide mechanical properties tailored to various applications, so as to be suitable for a wide range of industrial uses. Particularly in recent years, in the fields of automobiles, bicycles, and the like, there has been a remarkable movement to replace components that have conventionally used metals with fiber-reinforced thermoplastic resins due to problems of weight reduction, rationalization of processes, and corrosion.

[0003] The coloring of the thermoplastic resin has a decorative effect,
Black coloring is the most important in the industry for the purpose of color-coding effect, improvement of light resistance of molded products, protection and concealment of contents, and the like. Conventionally, for black coloring of a thermoplastic resin, coloring with various inorganic pigments and organic dyes and pigments such as carbon black, black metal-containing dye, azine-based dye and perinone black has been attempted.

[0004] Specific examples of such attempts include molding compounds in which a polyamide resin is colored with carbon black and nigrosine (Japanese Patent Publication No. 60-43379), and polyamide resins are colored with carbon black and copper phthalocyanine pigment. Molding composition (Japanese Patent Application Laid-Open No. 60-22655)
No. 1), a molding composition in which unsaturated polyester resin is colored with aniline black and solvent blue (Japanese Patent Publication No. 46524/1994), and a resin composition for a coloring master in which carbon black is added to a polycarbonate resin (Japanese Patent Publication No. JP-A-61-236854), and a plastic molding composition obtained by adding carbon black and titanium oxide to a thermoplastic resin (JP-A-5-186633).

Examples of the fiber-reinforced colored thermoplastic resin include thermoplastic resin compositions comprising a thermoplastic resin, a modified polyolefin, a fibrous reinforcing material and carbon black (JP-A-3-50263), and polyamides. Glass fiber reinforced black polyamide resin composition comprising resin, surface treated glass fiber and azine dye
JP-A-128479), a reinforced polycarbonate resin composition comprising a polycarbonate resin, glass fiber and carbon black (JP-A-6-212069).

[0006] In the coloring of the above-mentioned fiber-reinforced crystalline resin, since the fibrous reinforcing material is present in the resin, the colorant (eg, black pigment) is sufficiently and uniformly distributed in the resin even after kneading for a long time. Is difficult to disperse. In particular, during molding, there has been a problem that the fiber reinforcing material emerges on the surface of the molded product and the gloss and appearance of the colored molded product are impaired. In addition, these conventional crystalline resin compositions are not always good in appearance and surface gloss, and there is room for improvement.

[0007] The present invention has been made in view of the above-mentioned problems in the prior art, and has as its object the purpose of the present invention is to provide a vivid coloration without impairing the properties of the original thermoplastic resin, It is an object of the present invention to provide a crystalline resin composition which has good appearance and surface gloss, shows sufficient light resistance, and has good mechanical properties.

[0008]

The crystalline resin composition of the present invention that achieves the above object comprises, in a thermoplastic resin having crystallinity, one selected from the group consisting of the following (a) to (d):
Alternatively, it comprises two or more cationic surfactants and nigrosine (claim 1).

Further, the crystalline resin composition of the present invention is a crystalline resin composition comprising a thermoplastic resin having crystallinity and a black dye, wherein the black dye has the following (a) to (a). A black dye obtained by mixing nigrosine with one or more cationic surfactants selected from the group consisting of d) (claim 3). (A) aliphatic amine salt or quaternary ammonium salt thereof (b) aromatic quaternary ammonium salt (c) heterocyclic quaternary ammonium salt (d) quaternary phosphonium salt

The present inventors have made it possible to incorporate one or more cationic surfactants and nigrosine into a thermoplastic resin having crystallinity, or to produce one or more cationic surfactants. By containing the black dye obtained by mixing the activator and nigrosine, the appearance is good, the surface gloss is excellent, and it is uniformly and sharply colored black,
It was found that a molded product with almost no discoloration and discoloration was obtained, and it was found that the molding process could be performed smoothly without impairing the fluidity of the thermoplastic resin, and the present invention was completed. In addition,
The use of the above black dye is preferable because a mixture of nigrosine and a cationic surfactant can be uniformly contained in a thermoplastic resin having crystallinity.

This crystalline resin composition is compared with the above-mentioned crystalline resin composition containing no cationic surfactant and nigrosine or the above-mentioned black dye or crystalline resin (a crystalline resin containing no other components). The crystallization temperature is lower by about 10 ° C. or more (for example, about 10 to 20 ° C.) (claims 2 and 4).

That is, as a method for lowering the crystallization temperature of a crystalline thermoplastic resin, there is provided a method in which one or more cationic surfactants and nigrosine are contained in the crystalline thermoplastic resin. Alternatively, a method may be used in which a black dye obtained by mixing one or more of the above cationic surfactants and nigrosine is contained.

Further, the above-mentioned crystalline resin composition may contain a fibrous reinforcing material.

[0014]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Nigrosine contained in the crystalline resin composition of the present invention and nigrosine used as a raw material of the black dye contained in the crystalline resin composition of the present invention include CO
C. LOR INDEX I. SOLVENT BLA
CK 5 and C.I. I. Black azine-based condensation mixtures such as those described as SOLVENBLACK 7 can be used. The synthesis involves, for example, converting aniline, aniline hydrochloride and nitrobenzene in the presence of iron chloride.
Oxidation and dehydration condensation can be performed at a reaction temperature of 160 to 180 ° C. Nigrosine is produced as a mixture of various different compounds depending on the reaction conditions, the charged raw materials, the charged ratio, and the like. For example, the following formula (I) or (I
It is presumed to be a mixture of various triphenazine oxazines represented by I) and phenazine azine compounds represented by formulas (III) to (VI).

[0015]

Embedded image [In the formulas (I) to (VI), X represents Cl or OH. ]

Commercially available nigrosine includes Spirit Black SB, Spirit Black SSBB, and Spirit Black AB (above, CI Solvent).
Black5); Nigrosine-based SA, Nigrosine-based SAP, Nigrosine-based EE, Nigrosine-based EX, Nigrosine-based EX-BP (above, CIS
solvent black 7) [all are Nigrosine trade names manufactured by Orient Chemical Industries].

It is preferable that the cationic surfactant (a) is a quaternary ammonium salt represented by the following formula (1) or (2).

[0018]

Embedded image [In the formula (1), R ¹ is an alkyl group having 1 to 18 carbon atoms (eg, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, etc.) And R ² and R ³ are each independently (ie, the same or different),
(Hydrogen) or CH ₃ , and Z is an organic acid (eg, formic acid,
Acetic acid, etc.) or inorganic acids (eg, hydrochloric acid, sulfuric acid, etc.). ]

[0019]

Embedded image [In the formula (2), R ⁴ , R ⁵ and R ⁶ are each independently (that is, they may be the same or different), an alkyl group having 1 to 18 carbon atoms (eg, methyl, ethyl, Propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, etc.), and X
Represents Cl, Br or I. ]

The cationic surfactant of the above (b) is preferably an aromatic quaternary ammonium salt represented by the following formula (3) (claim 7).

[0021]

Embedded image [In the formula (3), R ⁷ , R ⁸ and R ⁹ each independently (that is, they may be the same or different) each represent an alkyl group having 1 to 18 carbon atoms, and Y is H (Hydrogen), an alkyl group having 1 to 4 carbon atoms (eg, methyl,
Ethyl, propyl, butyl, etc.), an alkoxyl group having 1 to 4 carbon atoms (for example, methoxy, ethoxy, propoxy, butoxy, etc.), a halogen or a hydroxyl group, and X represents
Indicates Cl, Br or I. ]

The cationic surfactant of the above (c) is an alkylpyridinium salt (the alkyl group is, for example,
It may be alkyl having 1 to 18 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, undecyl, dodecyl, tetradecyl, hexadecyl and octadecyl. ) Or an imidazolium salt (claim 8).

Further, the cationic surfactant (d) is preferably a quaternary phosphonium salt represented by the following formula (4) (claim 9).

[0024]

Embedded image [In the formula (4), R ¹⁰ , R ¹¹ , R ¹² and R ¹³ represent
Each independently (that is, may be the same or different), an alkyl group having 1 to 8 carbon atoms (eg, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, etc.), a benzyl group, Or a substituent (for example, an alkyl group [having 1 to 4 carbon atoms or the like]);
X represents an aryl group (eg, phenyl, naphthyl, etc.) having or not having an alkoxyl group [having 1 to 4 carbon atoms], a halogen, a hydroxyl group, and X is Cl, B
Indicates r or I. ]

The black dye in the present invention is produced by mixing the above-mentioned conventional nigrosine with at least one cationic surfactant selected from the group consisting of (a) to (d). I can do it. As a mixing method, either a wet mixing method or a dry mixing method can be adopted. In the case of wet mixing, the above-mentioned conventional nigrosine and the above-mentioned cationic surfactant are mixed and dispersed in an aqueous or non-aqueous system (organic solvent system) and then taken out to obtain the black dye of the present invention.

The mixing ratio of the conventional nigrosine to the above-mentioned cationic surfactant in the step of producing the black mixed dye in the present invention is preferably 0.1 to 1.5 parts by weight per 1 part by weight of nigrosine. In the crystalline resin composition of the present invention,
The same applies to the mixing ratio between the conventional nigrosine and the above-mentioned cationic surfactant contained therein. If it is less than 0.1, the effect of improving the dispersibility of the thermoplastic resin may be reduced. If it exceeds 1.5, the produced black dye tends to melt and is difficult to take out as crystals. Particularly preferably, it is 0.3 to 1.0 part by weight. The black dye according to the present invention has an increased solubility in an organic solvent as the amount of the cationic surfactant with respect to the raw material nigrosine increases, whereby the dispersibility and / or compatibility with the thermoplastic resin in the compounding and molding steps. Is considered to be improved.

The amount of the black dye (or the conventional nigrosine and the above-mentioned cationic surfactant) used in the crystalline resin composition of the present invention is, for example, 0.1 to 20% by weight based on 100% by weight of the thermoplastic resin. can do. Preferably it is 1 to 10% by weight.

As the crystalline resin in the present invention, a thermoplastic resin having crystallinity is preferable. For example,
Examples include polyamide resin, polyethylene resin, polypropylene resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polyphenylene sulfide resin, and polyether ether ketone resin. These thermoplastic resins can be used alone or in combination of two or more. Preferred are one or more synthetic resins selected from the group consisting of polyamide resins, polyethylene terephthalate resins, polybutylene terephthalate resins, and polyphenylene sulfide resins (claim 10). Further, a copolymer or a mixture mainly composed of these polymers; a thermoplastic resin in which an elastomer such as rubber or a rubber-like resin is blended with them; or a polymer alloy containing 10% by weight or more of these thermoplastic resins is also included. Can be used.

The fibrous reinforcing material that can be used in the crystalline resin composition of the present invention is not particularly limited, and those that can be used as a conventional synthetic resin reinforcing material can be appropriately used depending on the application and purpose. Examples of such a fibrous reinforcing material include glass fiber, carbon fiber, and various organic fibers. For example, in the case of glass fiber, the content is preferably 5 to 120% by weight based on 100% by weight of the crystalline thermoplastic resin. If it is less than 5% by weight, a sufficient glass fiber reinforcing effect may not be obtained, and
If it exceeds 300, the moldability tends to decrease. It is preferably from 10 to 60% by weight, particularly preferably from 20 to 50% by weight.

The crystalline resin composition of the present invention may contain various additives as required. Such additives include, for example, color assistants, dispersants, fillers, stabilizers, plasticizers, modifiers, ultraviolet absorbers or light stabilizers, antioxidants, antibacterial and antifungal agents, antistatic agents , A flame retardant, an inorganic filler, and an elastomer for improving impact resistance.

As the auxiliary colorant, for example, a small amount of an inorganic pigment, an organic pigment, an organic dye, or the like can be used to enhance coloring power, improve heat resistance and light resistance, or adjust color tone.

Examples of the modifier include silicon compounds such as amino-modified silicone oil and alkyl-modified silicone oil.

Examples of UV absorbers or light stabilizers include:
Examples include benzotriazole-based compounds, benzophenone-based compounds, salicylate-based compounds, cyanoacrylate-based compounds, benzoate-based compounds, oxalate-based compounds, hindered amine-based compounds, and nickel complex salts.

Examples of the antioxidant include phenol compounds, phosphorus compounds, sulfur compounds and thioether compounds.

Examples of the antibacterial / fungicide include 2- (4 ′
-Thiazolyl) benzimidazole, 10,10'-oxybisphenoxyarsine, N- (fluorodichloromethylthio) phthalimide and bis (2-pyridylthio-1-oxide) zinc.

Examples of flame retardants include halogen-containing compounds such as tetrabromobisphenol A derivatives, hexabromodiphenyl ether and tetrabromophthalic anhydride; phosphorus compounds such as triphenyl phosphate, triphenyl phosphite, red phosphorus and ammonium polyphosphate. Nitrogen-containing compounds such as urea and guanidine;
And silicon-containing compounds such as silicon oil, organic silane and aluminum silicate; and antimony compounds such as antimony trioxide and antimony phosphate.

Examples of the inorganic filler include glass flake, glass beads, silica, quartz, amorphous silicic acid, talc, magnesium carbonate, calcium carbonate, alumina, metal powder, kaolin, calcium silicate, mica and wollastonite. Is mentioned.

The crystalline resin composition of the present invention can be obtained by blending raw materials by any blending method. Usually, it is preferable to homogenize these components as much as possible. Specifically, for example, all the raw materials are mixed and homogenized in a blender such as a blender, a kneader Banbury mixer, a roll, and an extruder to obtain a crystalline resin composition, or a part of the raw materials is mixed. , The remaining components are added, and the mixture is further mixed and homogenized to obtain a crystalline resin composition. Alternatively, the raw materials previously dry-blended may be melt-kneaded with a heated extruder, homogenized, extruded into a wire, and then cut into a desired length to obtain colored granules (colored pellets).

The masterbatch of the crystalline resin composition of the present invention can be obtained by any method. For example, after mixing the powder or pellets and the colorant of the thermoplastic resin as the base of the masterbatch with a mixer such as a tumbler or a super mixer, the mixture is heated and melted by an extruder, a batch kneader or a roll kneader or the like. It can be obtained by pelletizing or coarsening. Further, for example, a masterbatch can be obtained by adding a colorant to a thermoplastic resin for a masterbatch still in a molten state after the synthesis and removing the solvent.

The molding of the crystalline resin composition of the present invention can be carried out by various procedures usually carried out. For example, it can be performed by molding colored pellets with a processing machine such as an extruder, an injection molding machine, and a roll mill. In addition, pellets or powder of thermoplastic resin, pulverized colorant, and various additives as necessary, mixed in a suitable mixer,
The mixture can be formed by molding using a processing machine. Further, for example, a coloring agent may be added to a monomer containing an appropriate polymerization catalyst, and the mixture may be polymerized to form a desired thermoplastic resin by an appropriate method. As a molding method, any commonly used molding method such as injection molding, extrusion molding, compression molding, blow molding, vacuum molding, injection blow molding, rotational molding, calendar molding, and solution casting can be adopted.

The crystalline resin composition of the present invention essentially comprises a thermoplastic resin having crystallinity, and a group consisting of the above (a) to (d) contained in the thermoplastic resin. One or more selected cationic surfactants and nigrosine, or a black dye obtained by mixing the cationic surfactant and nigrosine, or essentially having crystallinity Thermoplastic resin,
Further, it can be composed of the cationic surfactant, nigrosine and a fibrous reinforcing material, or the black dye and a fibrous reinforcing material. In any case, the composition may contain a substance which does not affect the basic properties of the present invention, for example, one or more of the above-mentioned additives and the like.

[0042]

The crystalline resin composition of the present invention has a lower crystallization temperature of 10 ° C. or more, so that the molding temperature can be lowered and the amount of shrinkage of the molded product is reduced. In addition, it is easy to put the product into practical use for strict requirements for dimensional accuracy. In addition, the cooling and solidification time can be shortened, and the equipment cost for the heating device can be reduced, so that a large-sized product can be formed with relatively small equipment. Further, as the characteristics of the molded product, the appearance and surface gloss are good, the light resistance is excellent, the color change with time is extremely small, and the mechanical properties are also good. Therefore, it is most suitable for high-grade molding materials.

[0043]

Next, the present invention will be described in detail with reference to examples, but it is needless to say that the present invention is not limited to these examples. In the following description, “parts by weight” is replaced by “parts”.
Abbreviated.

Production Examples 1 and 2 relate to the production of the black dye of the present invention by mixing a cationic surfactant with conventional nigrosine.

[0045]Production Example 1  Benzyl tributyl ammonium chloride (Lion
Disperse 15g in 500g water
The spirit black AB (orientated
45 g of Nigrosine manufactured by Gaku Kogyo Co., Ltd. was added. This
Was heated to 80 ° C. and stirred for 3 hours. So
After that, the reaction product is collected by filtration, and the collected product is washed with water and dried.
As a result, 56 g of a black mixed dye (93% yield) was obtained.
Was.

[0046]Production Example 2  Benzyl tributyl ammonium chloride in Production Example 1
Ride to benzyl methyl dilauryl ammonium chloride
Except for changing to the id, the same treatment as in Production Example 1
A synthetic dye was obtained.

The following Examples 1 to 5 and Comparative Examples 1 to 3
Relates to a black polyamide resin composition containing no fibrous reinforcing material.

[0048]Example 1  Polyamide resin (trade name: Zyte, manufactured by Dupont)
l 101L-NC10) 1000 g and obtained in Production Example 1.
Put 30 g of black dye in a stainless steel tumbler,
Stir well for 0 minutes.

The mixture was melted and mixed at 270 ° C. using a vent type extruder (trade name: E30SV, manufactured by Enpla Sangyo) to prepare colored pellets (2 mmφ × 2 mm) by a conventional method. Vacuum dried at 120 ° C. for 6 hours.

The melting point and crystallization temperature of the pellet were determined by JI
In accordance with SK7121, measurement was performed using a differential scanning calorimeter (DSC6100 manufactured by Seiko Instruments Inc.) under the following conditions.

That is, the above-mentioned colored pellets were cut in accordance with the container, placed evenly and uniformly in the container, and the lid of the container was placed and fixed. The temperature was raised from room temperature to 300 ° C. at 20 ° C./min, kept at 300 ° C. for 3 minutes, cooled to room temperature at 10 ° C./min, and the DSC curve at that time was recorded to obtain a melting peak temperature (melting point). Crystallization peak temperature (crystallization temperature)
I asked.

Table 1 shows the melting points and crystallization temperatures measured by DSC.

[0053]Example 2  The black dye obtained in Production Example 1 was replaced with the black dye obtained in Production Example 2.
Coloring is carried out in the same manner as in Example 1 except that
A pellet (2 mmφ × 2 mm) was obtained.

Table 1 shows the melting points and crystallization temperatures of the colored pellets determined by DSC in the same manner as in Example 1.

[0055]Example 3  Polyamide resin (trade name: Zyte, manufactured by Dupont)
l 101L-NC10) 1000g and spirit bra
AB (product of Nigrosin manufactured by Orient Chemical Co., Ltd.)
Name) 20g and triphenylbenzylphosphonium chlora
Put 10g of Id in a stainless steel tumbler for 20 minutes
Stir well.

This mixture was melt-mixed at 270 ° C. using a vent type extruder (trade name: E30SV, manufactured by Enpla Sangyo Co., Ltd.), and colored pellets (2 mmφ × 2 mm) were obtained by a conventional method.
Was prepared, and the obtained pellets were vacuum-dried at 120 ° C. for 6 hours.

Table 1 shows the melting point and crystallization temperature of this colored pellet determined by DSC in the same manner as in Example 1.

[0058]Examples 4 and 5  Spirit black AB and triphenylbenzyl phospho
The nickel chloride and nigrosine and potassium shown in Table 1 were used.
The procedure was the same as in Example 3, except that the thione-based surfactant was used instead.
Color pellets (2mmφ × 2mm)
I got

Table 1 shows the melting point and crystallization temperature of this colored pellet determined by DSC in the same manner as in Example 1.

[0060]Comparative Example 1  Spirit black was used instead of the black dye obtained in Production Example 1.
AB (trade name of Nigrosine manufactured by Orient Chemical Co., Ltd.)
The same procedure as in Example 1 was repeated except that only
(2 mmφ × 2 mm).

Table 1 shows the melting point and crystallization temperature of this colored pellet determined by DSC in the same manner as in Example 1.

[0062]Comparative Example 2  Spirit Black AB (Orient Chemical Co., Ltd.
Except for replacing Glossin's trade name) with carbon black.
A colorant obtained by treating in the same manner as in Production Example 1 was obtained in Production Example 1.
Treated in the same manner as in Example 1 except that the black dye was used instead of
Thus, a colored pellet (2 mmφ × 2 mm) was obtained.

Table 1 shows the melting point and crystallization temperature of this colored pellet determined by DSC in the same manner as in Example 1.

[0064]Comparative Example 3  Instead of the black dye obtained in Production Example 1, benzyl tributyl
Ammonium chloride (product name: BT, manufactured by Lion Corporation)
The same processing as in Example 1 was performed except that only BAC) was used.
A colored pellet (2 mmφ × 2 mm) was obtained.

Table 1 shows the melting point and crystallization temperature of this colored pellet determined by DSC in the same manner as in Example 1.

[0066]

[Table 1] In Table 1, crystallization temperature difference = (crystallization temperature of resin composition of Examples or Comparative Examples) − (crystallization temperature of polyamide resin only), and crystallization temperature of polyamide resin alone is 23.
0.0 ° C.

Examples 6 to 10 and Comparative Examples 10 and 11 relate to black polyamide resin compositions reinforced by containing glass fibers.

[0068]Example 6  Fiber reinforced polyamide resin (manufactured by Dupont)
70G-33L) 500 g and the black dye 1 obtained in Production Example 1
5 g into a stainless steel tumbler and stir well for 1 hour.
Stirred.

The mixture was melted and mixed at 300 ° C. using a vented extruder (trade name: E30SV, manufactured by Enpla Sangyo Co., Ltd.) to produce colored pellets by a conventional method, and the obtained pellets were heated at 120 ° C. for 6 hours. Vacuum dried. After drying, the pellets were molded by an ordinary method at 280 to 300 ° C. using an injection molding machine (trade name: KM50-C, manufactured by Kawaguchi Iron & Steel Co., Ltd.) to prepare a test plate. Bluish black molded plate [48 × 86 × 3 (m
m)] was obtained.

[0070]Example 7  The black dye obtained in Production Example 1 was replaced with the black dye obtained in Production Example 2.
The same processing as in Example 6 except that
A clear and vivid black molded plate [48 x 86 x 3 (mm)] was obtained.
Was done.

[0071]Example 8  Fiber reinforced polyamide resin (manufactured by Dupont)
70G-33L) 500g and Spirit Black AB
(Trade name of Nigrosine manufactured by Orient Chemical Industries) 10
g and 5 g of triphenylbenzylphosphonium chloride
Into a stainless steel tumbler and stir well for one hour.
Was.

This mixture was melted and mixed at 300 ° C. using a vented extruder (trade name: E30SV, manufactured by Enpla Sangyo Co., Ltd.) to prepare colored pellets by a conventional method, and the obtained pellets were heated at 120 ° C. for 6 hours. Vacuum dried. After drying, the pellets were molded by an ordinary method at 280 to 300 ° C. using an injection molding machine (trade name: KM50-C, manufactured by Kawaguchi Iron & Steel Co., Ltd.) to prepare a test plate. Bluish black molded plate [48 × 86 × 3 (m
m)] was obtained.

[0073]Examples 9 and 10  Spirit black AB and triphenylbenzyl phospho
Nigrosine and cation shown in Table 2
Same as Example 8 except that each was replaced by a surfactant
By processing, uniform clear color black molding respectively
A plate [48 × 86 × 3 (mm)] was obtained.

[0074]

[Table 2]

[0075]Comparative Example 4  Spirit Black A in place of the black dye obtained in Production Example 1
B (trade name of Nigrosine manufactured by Orient Chemical Co., Ltd.)
Except for using, it was processed and molded in the same manner as in Example 6.
, Black molded plate with insufficient surface gloss [48 × 86 × 3
(Mm)].

[0076]Comparative Example 5  Using carbon black in place of the black dye obtained in Production Example 1
When processed and molded in the same manner as in Example 6 except that
Black molded plate with poor surface gloss [48 x 86 x 3 (m
m)] was obtained.

Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat II (reference) C08L 81/02 C08L 81/02 F term (reference) 4J002 AA011 BB031 BB121 CF061 CF071 CH091 CL001 CN011 EN136 EU046 EU116 EU137 EU237 EW176 FD010 FD040 FD050 FD070 FD097 FD130 FD180 FD316

Claims (10)

[Claims] 1. A crystalline thermoplastic resin comprising one or more cationic surfactants selected from the group consisting of the following (a) to (d) and nigrosine. Crystalline resin composition. (A) aliphatic amine salt or quaternary ammonium salt thereof (b) aromatic quaternary ammonium salt (c) heterocyclic quaternary ammonium salt (d) quaternary phosphonium salt 2. The crystalline resin composition according to claim 1, wherein the crystallization temperature is lower by about 10 ° C. or more than the crystalline resin or the crystalline resin composition containing no cationic surfactant and nigrosine. 3. A crystalline resin composition containing a black dye in a thermoplastic resin having crystallinity, wherein the black dye is selected from the group consisting of the following (a) to (d): 1
Alternatively, a crystalline resin composition is a black dye obtained by mixing two or more cationic surfactants and nigrosine. (A) aliphatic amine salt or quaternary ammonium salt thereof (b) aromatic quaternary ammonium salt (c) heterocyclic quaternary ammonium salt (d) quaternary phosphonium salt 4. The crystalline resin composition according to claim 3, wherein the crystallization temperature is lower by about 10 ° C. or more than the crystalline resin containing no black dye or the crystalline resin composition. 5. The method according to claim 1, further comprising a fibrous reinforcing material.
Or the crystalline resin composition according to 4. 6. The crystallinity according to claim 1, wherein the cationic surfactant (a) is a quaternary ammonium salt represented by the following formula (1) or (2). Resin composition. Embedded image [In the formula (1), R ¹ represents an alkyl group having 1 to 18 carbon atoms, and R ² and R ³ each independently represent H or CH
_And Z represents an organic acid or an inorganic acid. ] [In the formula (2), R ⁴ , R ⁵ and R ⁶ each independently represent an alkyl group having 1 to 18 carbon atoms;
Indicates 1, Br or I. ] 7. The crystallinity according to claim 1, wherein the cationic surfactant (b) is an aromatic quaternary ammonium salt represented by the following formula (3). Resin composition. Embedded image [In the formula (3), R ⁷ , R ⁸ and R ⁹ each independently represent an alkyl group having 1 to 18 carbon atoms, and Y is H,
X represents an alkyl group, an alkoxyl group, a halogen or a hydroxyl group having 1 to 4 carbon atoms, and X represents Cl, Br or I. ] 8. The crystalline resin composition according to claim 1, wherein the cationic surfactant (c) is an alkylpyridinium salt or an imidazolium salt. 9. The method according to claim 1, wherein the cationic surfactant (d) is a quaternary phosphonium salt represented by the following formula (4). Crystalline resin composition. Embedded image [In the formula (4), R ¹⁰ , R ¹¹ , R ¹² and R ¹³ represent
Each independently represents an alkyl group having 1 to 8 carbon atoms, a benzyl group, or an aryl group having or not having a substituent, and X represents Cl, Br or I. ] 10. The thermoplastic resin having crystallinity is one or more synthetic resins selected from the group consisting of polyamide resin, polyethylene terephthalate resin, polybutylene terephthalate resin and polyphenylene sulfide resin. 10. The crystalline resin composition according to 3, 4, 5, 6, 7, 8, or 9.