JP2000230014A - Polymeric colorant and resin composition containing same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymeric colorant which is excellent in durability, solubility, coloring power, and compatibility in a polyolefin since it has a specified chemical structure. SOLUTION: This colorant has a chemical structure represented by the formula wherein D is an organic colorant residue; X is -O-, -NH- or -NR'- wherein R' is 1-12C alkyl; p and q are each an integer of 0 or higher provided p+q is 1 or higher; and r is an integer of 1 or higher and is prepared by thermally reacting an organic colorant with a graft polymer formed by grafting maleic anhydride onto a polyolefin, preferably polyethylene or polypropylene. Preferably, the organic colorant has a primary or secondary amino group or a hydroxyl group. Preferably, the polymeric colorant has a wt. average mol.wt. of 1,000-100,000, and the content of the organic colorant in the polymeric colorant is 2-80 wt.%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a polymer dye,
More specifically, the present invention relates to a colorant used for coloring a plastic, especially a polyolefin such as polyethylene and polypropylene, that is, a resin colorant.

[0002]

2. Description of the Related Art Pigments and oil-soluble dyes have been used for coloring plastics. However, in the case of pigments, there is an essential problem that the hue is unclear and the coloring power is small, so that a large amount of pigments needs to be added. On the other hand, in the case of oil-soluble dyes, there are problems caused by low molecular weight of dyes such as migration (bleeding property) and contamination of equipment by sublimation. In order to solve the problem of the oil-soluble dye, a method of introducing a polar group or a long-chain alkyl group into the structure of the low-molecular dye was examined, but no sufficient effect was obtained.

On the other hand, in the fields of color toners and ink jets, it has been proposed to polymerize dyes (for example, FrP1, 547, 495;
JP-A-330462, JP-B-7-89238, JP-A-62-119279, JP-A-63-3056
7, JP-A-7-304994, JP-A-10-304994
No. -60344, Japanese Patent No. 2521758, US
P4, 339, and 237. ). However, these are polymers obtained by polymerizing a dye using a polyacrylamide-based or polyacrylester-based resin, and the resulting polymer dye has a high polarity and a high hydrophilicity. The coloring of certain polyolefins suffers from poor durability, solubility, coloring power or compatibility.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a polyolefin having excellent durability, solubility, coloring power and compatibility, and excellent transferability of a dye or contamination of equipment due to sublimation of a dye. An object of the present invention is to provide a polymer dye.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies in view of the above problems, and as a result, have found that polyethylene (hereinafter referred to as “PE”)
) Or polypropylene (hereinafter abbreviated as “PP”), a polymer dye obtained by covalently bonding an organic dye and a polymer obtained by grafting maleic anhydride to a polymer. The inventors have found that bleeding can also be prevented, and have reached the present invention. That is, the gist of the present invention resides in a polymer dye having a structure represented by the following formula (1).

[0006]

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Wherein D is an organic dye residue, X is —O—,
-NH- or -NR'-, R 'represents an alkyl group having 1 to 12 carbon atoms, p and q are each an integer including 0,
r represents an integer. However, the sum of p and q is 1 or more. )

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The polymer dye of the present invention has the structure of the above formula (1), and preferably has the structure of the formula (2).

[0009]

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Wherein R is a hydrogen atom or a methyl group, Z is
Is

[0011]

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Wherein D is an organic dye residue, X is —O—,
-NH- or -NR'-, R 'represents an alkyl group having 1 to 12 carbon atoms, p and q are each an integer of 0 or more,
r represents an integer. However, the sum of p and q is 1 or more. ), And m and n each represent an integer. Here, Z in the expressions (1), (2) and (2) is
Either a block polymer or a random polymer may be used.

The polymer dye of the present invention is a polyolefin,
Preferably, it can be obtained by reacting an organic dye with a graft polymer of maleic anhydride of polyethylene or polypropylene. The maleic anhydride graft polymer of a polyolefin used in the present invention is, for example, a polymer compound schematically represented by the following formula (3). This is accomplished by mixing a polyolefin with a radical generator such as maleic anhydride and benzoyl peroxide, and then mixing 150 to 230
C. and graft-polymerized. For example, "Modic AP" manufactured by Mitsubishi Chemical Corporation, "Umex" manufactured by Sanyo Chemical Co., Ltd., "Polybon" manufactured by BP Co., Ltd.
d ", Mitsui Chemicals'" Admer Qf ", Him
It is commercially available as “Hercoprime G” manufactured by Ont.

The maleic anhydride modification ratio of the polyolefin maleic anhydride graft polymer used in the present invention is represented by the weight of maleic anhydride-derived groups in the polymer.
Usually, it is 0.1 to 50% by weight, preferably 1 to 30% by weight. If the maleic anhydride modification ratio is too small, the number of sites that react with the organic dye is small, and the color may be lightened. On the other hand, if it is too large, the compatibility of the polyolefin may be insufficient.

[0015]

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(In the formula, R represents a hydrogen atom or a methyl group.) As the organic dye used in the present invention, a dye generally used as a water-insoluble disperse dye is used, and a primary amino group is preferably used. And a dye having a secondary amino group or a hydroxyl group. The parent skeleton of the pigment is not particularly limited as long as it has a pigmented structure such as azo, anthraquinone, quinophthalone, perylene, naphthalimide, anthrapyridone, phthalocyanine, quinacridone, diketopyrrolopyrrole, indigo, thioindigo, dioxazine, and thioxanthen. However, non-azo dyes are preferred from the viewpoint of heat resistance and durability. Specific examples of such a dye include the following dyes.

[0017]

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[0018]

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[0019]

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[0020]

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[0021]

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[0022]

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[0023]

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The method of reacting the maleic anhydride graft polymer of polyolefin with the organic dye is as follows: <1> The maleic anhydride graft polymer of polyolefin and the organic dye are usually mixed with a roll mill, kneader, extruder or the like for 180 to 180 minutes. Method of kneading while heating to 250 ° C, <2>
When the organic dye does not have a primary amino group, a secondary amino group or a hydroxyl group, after reacting a polyolefin maleic anhydride graft polymer with an alkylenediamine having 1 to 12 carbon atoms with one amino group , The remaining amino groups,
A method of reacting with an organic dye having a reactive group such as a halogen atom, sulfonyl chloride or triazinyl chloride, and the like. <3> A polyolefin maleic anhydride graft polymer and an organic dye are
If necessary, in a solvent such as aromatics such as toluene, xylene and mesitylene, and amides such as dimethylformamide and N-methylpyrrolidone, the temperature is usually 10
The reaction is carried out by heating at 0 to 250 ° C., preferably 120 to 250 ° C. under normal pressure, usually for 5 to 48 hours. After the completion of the reaction, a method of adding a diluting solvent such as methanol, if necessary, to precipitate the produced polymer dye, and filtering the resultant is preferable.

In the production of the polymer dye of the present invention, the amount of the organic dye to be added is usually 2 to 300 parts by weight, preferably 5 to 150 parts by weight, per 100 parts by weight of the polyolefin maleic anhydride graft polymer. The molecular weight of the organic dye also depends on the amount of maleic anhydride added to the graft polymer.However, the amount of the organic dye added is represented by the weight of the organic dye relative to the weight of maleic anhydride in the maleic anhydride graft polymer of the polyolefin. And usually 1: 0.1 ~
The ratio is 1:10, preferably 1: 1 to 1: 5. If the added amount of the organic dye is too small, the coloring power may be insufficient and the polymer dye may be insufficient.On the other hand, if the added amount is too large, only the organic dye that does not participate in the reaction of the polyolefin with the maleic anhydride graft polymer increases. is there.

When an organic dye having a primary amino group, a secondary amino group or a hydroxyl group is used as an organic dye, these reactive groups react with a maleic anhydride residue to form the following (4) or (5) ).
When an organic dye having a primary amino group is used, it is considered to bond as shown in the following (4), and when an organic dye having a secondary amino group or a hydroxyl group is used, it is thought to be bonded as shown in the following (5).

[0027]

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The weight average molecular weight of the polymer dye thus obtained is usually 1,000 to 100,000, preferably 5,000.
0 to 50,000. If the weight average molecular weight is too small, migration resistance may be insufficient, while if too large, the solubility and compatibility with the resin may be reduced. The proportion of the organic dye in the polymer dye is usually 2 to 80% by weight, preferably 5 to 60% by weight. If the proportion of the organic dye is small, the coloring power is insufficient, and if it is too large, the migration resistance may be insufficient.

The polymer dye thus obtained is usually a resin, preferably a thermoplastic resin, more preferably a polyolefin resin or a vinyl resin, more preferably a polyolefin resin, further preferably LDPE,
PE resin such as LLDPE, PP resin, ethylene-propylene copolymer, ethylene-styrene copolymer, ethylene-based copolymer such as ethylene-butadiene copolymer, PE-based resin such as propylene-based copolymer, or PP-based It is mixed with the resin and used as a colorant for the resin. The amount of the polymer dye to be added to the resin is usually 1 to 50% by weight. The coloring of the resin with the polymer dye may be performed by heating and kneading the polymer dye and the resin by an ordinary method. Alternatively, a masterbatch in which a dye is mixed at a high concentration with a resin may be prepared in advance, and the masterbatch may be added to the resin for coloring.

The polymer dye of the present invention is usually PE or P
It is obtained by covalently bonding an organic dye to a polymer obtained by grafting maleic anhydride onto P. Therefore, it has high compatibility with polyolefins, especially PE and PP,
When added to a resin, the organic dye apparently dissolves in the PE resin or the PP resin, and migration in the resin and bleeding to the resin surface are prevented. In addition, since the structure of the main chain of the dye is similar to that of the polyolefin, it is presumed that the addition of the high-molecular dye hardly causes a decrease in the mechanical strength inherent to the polyolefin.

[0031]

EXAMPLES Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. Parts represent parts by weight.

<Example 1> (Production of high molecular dye) Maleic anhydride grafted polypropylene resin 10 parts (manufactured by Sanyo Chemical Co., Ltd. "Umex 1010" Maleic anhydride content 10% by weight) No. 5 dye 3 parts Add the components to 100 parts of tetramethylbenzene and add
Heated at 00-210 ° C for 48 hours. After cooling to room temperature,
100 parts of methanol was added, the precipitated solid was filtered, washed with 100 parts of methanol, dried, and dried.
Part of a pale red powder was obtained.

(Coloring of Polypropylene Resin) Polypropylene resin 80 parts (“Mitsubishi Polypropylene EA8” manufactured by Nippon Polychem Co., Ltd.) 20 parts of the above polymer dye

After mixing the above components, the mixture was kneaded and extruded at 220 ° C. using an extruder manufactured by Thermoplastics to obtain uniformly colored colored pellets. A 2 mm-thick plate-shaped colored molded product was obtained from the obtained pellet by a press molding machine manufactured by Shinto Metal Co., Ltd. When the bleeding resistance and heat resistance of the obtained molded article were tested under the following conditions, the bleeding resistance was 5th grade for polypropylene resin and 4th grade for vinyl chloride resin, and the bleeding resistance was good. The heat resistance was ΔE2 and the heat resistance was good, and the change in hue of the molded product in any cycle was slight as compared with the reference product.

<Bleed Resistance Test> The resin molded plate containing the polymer dye of the present invention obtained as described above and a white molded plate made of a polypropylene resin containing 0.5% by weight of titanium oxide were overlapped. 100 g with a migration tester manufactured by Toyo Seiki Co., Ltd. at 80 ° C. for 24 hours.
After applying a load of / cm ² , the degree of coloring of the white molded plate made of the polypropylene resin was determined by a gray scale for contamination according to JIS-L-0805, and the bleeding property was evaluated.

Also, instead of a white molded plate made of a polypropylene resin containing 0.5% by weight of titanium oxide, a white molded plate made of a vinyl chloride resin containing 0.5% by weight of titanium oxide was used. The bleeding property was evaluated in a gray scale. Judgment by the gray scale shows that Grade 5 has the least migration of the dye and good bleeding resistance, and Grade 1 has the most migration of the dye and poor bleeding resistance, that is, the bleeding is remarkable.

<Heat Resistance Test> The colored pellets obtained as described above were subjected to an injection molding machine (J
-50EII), a colored plate-like product obtained by molding at a cycle of 220 ° C. for 2 minutes is used as a standard.
The degree of discoloration and fading of each colored plate obtained by molding at each cycle of 0 ° C. × 10 minutes, 280 ° C. × 2 minutes, and 280 ° C. × 10 minutes is determined by colorimetry. (ΔE) and the heat resistance was evaluated. The larger the value of ΔE, the greater the discoloration and discoloration, indicating that the heat resistance of the dye is insufficient.

<Comparative Example 1> In Example 1 (coloring of polypropylene resin), No. 5
A molded article was obtained in the same manner as in Example 1 except that 4 parts of the dye was used. As a result of evaluation in the same manner as in Example 1, the bleeding resistance was first-class for both the polypropylene resin and the vinyl chloride resin, and the bleeding was marked.

Example 2 (Production of Polymeric Dye) Maleic Anhydride Grafted Polyethylene Resin 10 parts (Sanyo Kasei Co., Ltd. “UMEX 2020” Maleic anhydride content 5 wt%) The above No. 16 dye 3 parts

A polymer dye was synthesized using the above components in the same manner as in Example 1. As a result, 11 parts of a blue-green powder were obtained.

(Coloring of Polyethylene Resin) Polyethylene resin 85 parts (“Mitsubishi Polyethylene LL” manufactured by Nippon Polychem Co., Ltd.) 15 parts of the above polymer dye

Using the above components, a blue molded plate was obtained in the same manner as in Example 1. The obtained molded plate was evaluated in the same manner as in Example 1. As a result, the bleeding resistance was 5th grade for polypropylene resin and 4th grade for vinyl chloride resin, and the bleeding resistance was good. The property was as good as ΔE1.

<Comparative Example 2> Instead of the polymer dye used in (Coloring of polyethylene resin) in Example 2, No.
A molded product was obtained in the same manner as in Example 2 except that 3 parts of 16 dyes were used. As a result of the evaluation in the same manner as in Example 1, the bleeding resistance was remarkably bleeding at 2nd grade for the polypropylene resin and 1st grade for the vinyl chloride resin, and the heat resistance was ΔE6. It was remarkable. The results are summarized in Table 1.

[0044]

[Table 1] PP: polypropylene, PVC: vinyl chloride resin

[0045]

According to the present invention, a polymer dye excellent in heat resistance and bleed resistance can be provided. In the resin composition containing the polymer dye of the present invention, a decrease in mechanical strength is suppressed.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) C08L 51/06 C08L 51/06 101/02 101/02 C09B 69/10 C09B 69/10 B F-term (reference ) 4J002 AA001 BB031 BB091 BB101 BB121 BB151 BB202 BB212 BB282 BN052 4J026 AA11 AA12 AA13 AC01 BA35 BA38 DB15 EA09 EA10 GA01 GA09 4J100 AA02P AA03P AK32P AL41R AM39R AM47Q BA02H BA02Q BA02R BA03H BA03Q BA03R BA04Q BA11Q BA11R BA16R BA20H BA20Q BA20R BA28H BA28Q BA28R BA29H BA29Q BA29R BA34H BA34Q BA34R BA40H BA40Q BA40R BA41H BA41Q BA41R BA45H BA45Q BA45R BA59H BA59Q BA59R BB01H BB01Q BB01R BB11H BC43H BC43Q BC43R BC48H BC48Q BC48R BC65H BC65Q BC65R BC73HBCBCHBCBCH BC73Q79 HC46 HC54 HC63 HG09

Claims (10)

[Claims] 1. A polymer dye having a structure represented by the following formula (1). Embedded image (Wherein, D is an organic dye residue, X is -O-, -NH- or -NR'-, R 'represents an alkyl group having 1 to 12 carbon atoms, p and q are integers each including 0, r represents an integer, provided that the sum of p and q is 1 or more.) 2. A polymer dye having a structure represented by the following formula (2). Embedded image (Wherein, R is a hydrogen atom or a methyl group, and Z is (Where D is an organic dye residue, X is -O-, -NH- or -NR'-, R 'represents an alkyl group having 1 to 12 carbon atoms, p and q are each an integer of 0 or more, r represents an integer, provided that the sum of p and q is 1 or more.), and m and n each represent an integer. ) 3. A polymer dye obtained by reacting an organic dye with a maleic anhydride graft polymer of a polyolefin. 4. The polymer dye according to claim 3, wherein the polyolefin is polyethylene or polypropylene. 5. An organic dye having a primary amino group, a secondary amino group or a hydroxyl group.
The polymer dye according to any one of claims 1 to 7. 6. The polymer dye according to claim 1, wherein the weight average molecular weight is 1,000 to 100,000. 7. The polymer dye according to claim 1, comprising 2 to 80% by weight of an organic dye. 8. A resin colorant comprising the polymer dye according to any one of claims 1 to 7. 9. A method for producing a polymer dye, wherein a maleic anhydride graft polymer of a polyolefin is reacted with an organic dye by heating. 10. A resin composition comprising the resin colorant according to claim 9.