JPH0625295B2 - Method for coloring polyester resin - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION "Object of the Invention" (Field of Industrial Application) The present invention relates to a method for coloring a polyester resin. More specifically, the present invention relates to a coloring method excellent in coloring power, uneven coloring, non-aggregating property, etc. in coloring a polyester resin using copper phthalocyanine.

(Prior Art) Conventionally, copper phthalocyanine and / or halogenated copper phthalocyanine pigments have been widely used because of their beautiful color tone, high tinting strength, and various fastnesses. In terms of coloring, there are still unsatisfactory properties.

Polyester resins include unsaturated polyester resins typified by sheet molding compounds and thermoplastic resins (saturated polyester resins) typified by melt spinning. In coloring these resins, there is coloring power and uneven coloring. There is a strong demand for the development of a copper phthalocyanine and / or a halogenated copper phthalocyanine pigment which has a low content of agglomerates, a small amount of agglomerates, and is free from yarn breakage in melt spinning.

One of the drawbacks of copper phthalocyanine or halogenated copper phthalocyanine pigments is the aggregation. When a polyester resin is colored with a copper phthalocyanine or a halogenated copper phthalocyanine pigment, a phenomenon caused by the extremely strong aggregation property, specifically, the pigment particles themselves aggregate in the polyester resin or the compound, and as a result, The obtained colored molded product causes uneven coloring, and only a molded product with extremely low coloring power is obtained. Also, the workability is deteriorated such as clogging of the filter during melt-spinning and yarn breakage caused by resin deterioration and the spinning product. There are drawbacks such as a decrease in coloring power or unevenness.

On the other hand, another major drawback of copper phthalocyanine pigments is
It has the property of exhibiting crystal transition and crystal growth in an aromatic solvent or under high temperature conditions. The polyester resin may be used as a solvent solution or may be subjected to high temperature treatment such as melt spinning, and the copper phthalocyanine pigment may be crystallized to limit its application to coloring the polyester resin.

(Problems to be solved by the invention) When coloring a polyester resin from blue to green, copper phthalocyanine and / or halogenated copper phthalocyanine pigment is used, and it has coloring power, little coloring unevenness, few aggregates, and melting. There has been a demand for an excellent coloring method that does not cause yarn breakage during spinning.

"Structure of the Invention" (Means for Solving the Problem) The present invention relates to 100 parts by weight of copper phthalocyanine and / or halogenated copper phthalocyanine and a copper phthalocyanine represented by the following general formula [I] when coloring a polyester resin. This is a coloring method using 0.5 to 30 parts by weight of the derivative.

General formula [I](In the formula, CuPc is a copper phthalocyanine residue, and X is a halogen source.
Child, A is group- (CH₂)_k-,-CH₂NH (CH₂) -,-CH₂NHCO (CH₂)
-,-SO₂NH (CH₂) -, (However, R₁, R_TwoIs al
Kill group or R₁And R_TwoAnd contains at least a nitrogen atom
Indicates a 6-membered ring. ), M is 0 to 10, n is 1 to 8, and k is 1
2 represents an integer of 1 to 4, respectively. ) By the coloring method of the present invention, a uniform coating of polyester resin is achieved.
See that you can get color molded or melt spun
I put it out.

Copper phthalocyanine pigments include β-type copper phthalocyanine (organic solvent stable type), α type copper phthalocyanine (organic solvent unstable type), and various crystal form copper phthalocyanine pigments such as γ type, δ type or ε type. At 280 to 290 ° C., which is the coloring or processing condition of the polyester resin, crystals of β-type copper phthalocyanine may grow, and α-type copper phthalocyanine causes a crystal transition to β-type,
At the same time, β-type crystal growth occurred, resulting in a change in hue and a decrease in coloring power in the molded product and spun product of the polyester resin. The present invention eliminates these drawbacks and provides a good colored molded product or spun product of a polyester resin.

The copper phthalocyanine of the present invention may be of α-type, β-type, or other crystalline form, while the halogenated copper phthalocyanine may be a low-halogenated copper phthalocyanine substituted with 1 or 2 halogen atoms. Examples include highly chlorinated copper phthalocyanine, highly brominated copper phthalocyanine, or a mixture thereof. It is also possible to mix a bluish copper phthalocyanine derivative with a highly halogenated copper phthalocyanine, but when mixed, there is a disadvantage that the hue becomes bluish, so the highly halogenated copper phthalocyanine derivative is a green copper phthalocyanine derivative. Are preferably mixed, and it is advantageous from the viewpoint of hue and sharpness to use a copper phthalocyanine derivative having a hue close to that of each copper phthalocyanine or halogenated copper phthalocyanine as much as possible.

Group A of the copper phthalocyanine derivative represented by the general formula [I]
Is -CH ₂ -,-(CH ₂ ) ₂ -,-CH ₂ NH (CH ₂ ) ₄ -,-CH ₂ NHCOCH _{2
-, - CH 2 NHCO (CH} 2) 4 -, - SO 2 NHCH 2 -, - SO 2 NH (CH 2) 4 - , and the like. The group X represents a bromine atom and / or a chlorine atom, and the total number of these substituents is 0-12. 0
When it is mixed with green highly halogenated copper phthalocyanine, the amount thereof is preferably reduced. In general, the halogenated copper phthalocyanine having a total number of 11 to 12 has severe manufacturing conditions and is likely to generate a by-product. Therefore, the halogenated copper phthalocyanine having a total number of 5 to 10 is converted into a green highly halogenated copper phthalocyanine. Mixing is practically advantageous. Also, with the same number of substituents, the bromine-substituted derivative becomes yellowish green compared to chlorine. It should be noted that the number of substituents in the synthesized copper phthalocyanine derivative is an average number of those, since some of them are generally mixed when actually measured.

The copper phthalocyanine derivative of the general formula [I] and the copper phthalocyanine or the halogenated copper phthalocyanine can be mixed in the form of a dry powder, a press cake or a slurry, and both of them can be dissolved or suspended in concentrated sulfuric acid separately or together. Pigmentation and mixing can also be carried out simultaneously by making the pigment cloudy and pouring it into water, or mechanically milling with crude copper phthalocyanine or crude highly halogenated copper phthalocyanine. It is also possible to separately prepare copper phthalocyanine or a halogenated copper phthalocyanine and a copper phthalocyanine derivative and add them at the time of coloring and molding the resin. In addition, the mixed copper phthalocyanine or halogenated copper phthalocyanine pigment composition may be processed by dry color, paste color, liquid color or masterbatch processing conventionally known to improve the workability and dispersion of the polyester resin. Advantageously, it is a pigment.

Regarding the copper phthalocyanine or halogenated copper phthalocyanine composition, 0.5 to 30 parts by weight or less than 0.5 parts by weight of the copper phthalocyanine derivative represented by the general formula [I] is mixed with 100 parts by weight of copper phthalocyanine or halogenated copper phthalocyanine. Does not show the effect of suppressing the aggregation of pigment particles and the growth and transition of crystals.
When the amount is more than 0 parts by weight, problems such as solvent resistance and unclear hue occur, so 0.5 to 30 parts by weight, preferably 5 to 15 parts by weight is mixed.

In the present invention, the reason why it is excellent in non-crystallinity and non-aggregation property is not necessarily clear, but the copper phthalocyanine derivative represented by the general formula [I] has an alkyl group or the like bonded to it, as is clear from the chemical structure. It is presumed that the presence of a tertiary amino group having an increased basicity as a result of the presence thereof causes an interaction with the polyester resin that is the substance to be dispersed.

According to experiments by the present inventors, the following general formula [II] [X] _m -CuPc- [A-NHR ₁ ] _n (where CuPc, X, A, m, n and R ₁ in the formula [II] are represented by the formula The addition of a copper phthalocyanine derivative having a secondary amino group represented by the same formula (I)) to the polyester resin was insufficient for improving the crystallinity and the aggregation property.

The present invention will be described below with reference to examples. In the examples, "part" means "part by weight" and "%" means "% by weight".

Production Example 1 5 parts of diethylamine was added to a water slurry containing 10 parts of bis- (chloromethyl) copper phthalocyanine, and the mixture was stirred at 70 ° C. for 5 hours, the pigment dye was filtered off, washed with water and dried to give the copper phthalocyanine derivative shown below. Got

Production Example 2 4 parts of piperidine was added to an aqueous slurry containing 10 parts of bis- (chloromethyl) -octachlorocopper phthalocyanine, and 1
The mixture was stirred at 00 ° C. for 4 hours, the pigment dye was filtered off, washed with water and dried to obtain a copper phthalocyanine derivative shown below.

Production Examples 3 to 9 Various copper phthalocyanine derivatives were produced according to the above production examples and shown in Table 1.

Examples 1 to 9 Using the copper phthalocyanine composition having the composition shown in Table 1, unsaturated polyester resins and melt-spinning colorants were prepared at the following compounding ratios.

[Colorant for unsaturated polyester resin for molding]

Copper phthalocyanine pigment composition 10 parts, titanium oxide 50 parts and unsaturated polyester resin (obtained with maleic anhydride, phthalic anhydride and diethylene glycol)
Coloring agent of the present invention 1-
(I) to 9- (I) were obtained.

[Coloring agent for melt spinning]

Liquid polyester resin (liquid polyester consisting of adipic acid and 1,3-butylene glycol (trade name: ADEKA SAIZER P-300, manufactured by ADEKA ARGUS CHEMICAL))
70 parts and 30 parts of the copper phthalocyanine pigment composition were kneaded with a three-roll mill to form the colorants 1- (II) to 9- (II) of the present invention.
Got

[Coloring of unsaturated polyester resin for molding 1- (I) to 9
-(I)] An unsaturated polyester resin composition for molding 100 having the following composition
5 parts of each of the colorants 1- (I) to 9- (I) of the present invention was added to each part to adjust the sheet molding compound, and the glass fibers were sufficiently impregnated, covered with a polyethylene film, and aged at 40 ° C. for 2 days. Then, it was colored and molded in a mold (size-15 cm in length, 15 cm in width, 0.8 cm in thickness) at 140 ° C. for 3 minutes under a press pressure of 100 kg / cm ² . As a result of examining the coloring unevenness, the coloring power and the change in hue of the obtained colored molded product, it was found that the colored molded product was uniformly colored, and the decrease in the coloring power and the change in hue were not observed. Also,
The molded product was good, with no deterioration in mechanical strength or chemical resistance.

(Unsaturated Polyester Resin Composition for Molding) Thermosetting unsaturated polyester resin Polymer 9607 (Takeda Pharmaceutical Co., Ltd.) 50 parts Polymer 6819 (Takeda Pharmaceutical Co., Ltd.) 20 parts Calcium carbonate (Nitto Powder Co., Ltd.) ) 100 parts Zinc stearate 2 parts Magnesium oxide 1 part t-Butyl peroxybenzoate 1 part Low shrinkage imparting agent (Polymer 9965) 30 parts Polyethylene powder (FLOWSEN UF-80, Iron and Chemicals Co., Ltd.) 5 parts or more composition To 25% by weight of glass fiber.

[Coloring of saturated polyester resin 1- (II) to 9- (I
I)] 100 parts of polyethylene terephthalate resin having an intrinsic viscosity value (IV value) of 0.70 (trade name: Velvet EFG-6, manufactured by Kanebo Gosei Co., Ltd.) is added to 100 parts of the colorant 1- (II) to 9- (II) of the present invention.
Was quantitatively supplied, and spinning was carried out at 290 ° C. with a spinning machine having a 40 μ5 layer filter.

The obtained fiber was cut with a microtome (PR50 type rotary type, Yamato Koki Kogyo Co., Ltd.), and the result of measuring agglomerates of 10 μ or more using a microscope showed that no agglomerates were observed at all, and after 3 days of operation The rise in filter pressure and the yarn breakage resistance were also good.

Further, the addition amount of the colorants 1- (II) to 9- (II) of the present invention was increased to 7 parts, but the agglomerates and the workability under a microscope were good.

The above results are shown in Table 2.

Comparative Examples 1 to 6 When copper phthalocyanine or halogenated copper phthalocyanine pigments shown in Table 3 below were used and the same operation as in Example was carried out, the unsaturated polyester resin for molding was colored unevenly and colored. Insufficient power, a large amount of aggregates in coloring the saturated polyester resin, and a high pressure increase in the filter (see Table 4), which are Examples of the present invention 1- (I) to 9- (I) and 1- (II) -9- (I
It was clearly worse than I).

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Claims (1)

[Claims] 1. When coloring a polyester resin, copper is used.
Phthalocyanine and / or copper halide phthalocyanine
100 parts by weight of nin and copper represented by the following general formula [I]
Use 0.5 to 30 parts by weight of phthalocyanine derivative
And a coloring method. General formula [I](In the formula, CuPc is a copper phthalocyanine residue, and X is a halogen.
Atom, A is a group-(CH_Two)_k-,-CH_TwoNH (CH
_Two) -,-CH_TwoNHCO (CH_Two) -,-SO_Two
NH (CH_Two) Represents − (where R₁, R_TwoIs al
Kill group or R₁And R_TwoAnd contains at least a nitrogen atom
Indicates a 6-membered ring. ), M is 0-10, n is 1-8, k is 1
~ 2 represents an integer of 1 to 4. )