JP3269337B2 - Colored resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel colored resin composition, and more particularly, to a copolymer of a monomer having an .alpha.,. Beta. Unsaturated double bond and a dibasic acid having an unsaturated group or an anhydride thereof. The present invention relates to a colored resin composition useful as a coloring material such as a printing ink, a paint, and a thermoplastic resin coloring material, which contains a polymer resin and a derivative thereof as a dispersant or a flushing agent for a pigment.

[0002]

2. Description of the Related Art Conventionally, in the production of paints and printing inks, a dispersant or flushing agent is used for dispersing a pigment in a paint vehicle or printing ink varnish or for flushing an aqueous wet cake into an oily vehicle or oily varnish. As the agent, for example, rosin soap, rosin-modified resin, plasticizer, surfactant and lecithin which is a phospholipid have been used. However, for example, when these dispersing agents and flushing agents are used in paints and printing inks, the water resistance of the coating film, heat resistance and weather resistance and the like are reduced, and bleeding and the like, the problem that physical properties are reduced, In addition, when natural phospholipids such as lecithin are used, sufficient effects such as problems such as deterioration and decay due to oxidation or rancidity have not been obtained at present.

[0003] The coloring material of the thermoplastic resin coloring material includes a powdery dry color in which a pigment and a dispersant are mixed, a liquid color or a paste color in which the pigment is dispersed in a liquid dispersant at ordinary temperature, and a Pellet in which the pigment is dispersed in a solid resin, a flake or bead-shaped masterbatch, and the like, for example, as a dispersant, stearic acid, zinc stearate, magnesium stearate,
Aluminum stearate, calcium stearate,
One or more kinds of ethylene bisamide, polyethylene wax, polypropylene wax, and derivatives thereof, for example, waxes and resins composed of an acid-modified product or a hydroxyl-modified product have been generally used. However, for example, when these dispersants are used as a coloring material of a thermoplastic resin coloring material, a high-speed spinning of a colored thermoplastic resin with a diameter of several tens of microns or a high degree of pigment dispersion such as when forming a film is performed. When required, the above dispersants may not be satisfactory. That is, yarn breakage during spinning due to poor pigment dispersion, clogging of a filter of a melt spinning machine, poor molding in a film, and the like. In order to solve these problems, efforts have been made to improve the processing method of the coloring material of the thermoplastic resin coloring material and to improve the pigment dispersibility by using a powerful kneader, but all exhibit sufficient pigment dispersing ability. Was not something to do.

In order to improve these disadvantages, JP-A-58-10820, JP-A-58-198534, and JP-A-5-202234 disclose a monobasic acid, a dibasic acid and / or a dibasic acid. Although various polyolefins such as graft-modified resins and copolymer resins modified with an anhydride or the like are described, when modified with a monobasic acid, the number of polar groups is small (low acid value; 100 mg KOH). / G or less),
Further, the coating performance of the pigment particles (dispersibility of the pigment) was not sufficient due to the random arrangement. Further, a modified resin obtained by grafting a dibasic acid or an anhydride thereof to a polyolefin has a lower acid value than a copolymer resin described later,
The pigment coating performance (dispersibility of the pigment) was not satisfactory. In the case of a copolymer resin of a dibasic acid having an unsaturated double bond or an anhydride thereof and another compound having an unsaturated double bond, the pigment coating performance (dispersibility of the pigment) is high at a high acid value. Is improved, and it is excellent in terms of hue and coloring power, and there is almost no problem in ordinary use. However, remaining in the copolymer resin, considered to be derived from unreacted monomers, odors and yellowing may occur, applications requiring weather resistance and heat resistance, for example, the color of a thermoplastic resin coloring material In some cases, materials are not suitable for engineering plastics, paints are retorted, and printing inks are not suitable for soft packaging. Alternatively, phenomena such as thread breakage may occur in the field of fiber processing which requires extremely high pigment dispersion.

[0005]

DISCLOSURE OF THE INVENTION The present invention is directed to a colored resin composition which improves the above-mentioned various disadvantages, is excellent in hue, coloring power, dispersibility, water resistance, heat resistance, weather resistance, etc., and does not cause deterioration in various physical properties. The purpose is to get things.

[0006]

The present invention provides a pigment (a) comprising 0.01 to 90% by weight of a monomer having an α, β unsaturated double bond and a dibasic acid or a dibasic acid having an unsaturated double bond. Copolymer resins with their anhydrides and / or their derivatives, wherein the content of unreacted substances is 2% or less and / or their derivatives (b) 1 to 9
0% by weight, and 0.1 to 98% by weight of the thermoplastic resin (c)
A colored resin composition comprising:

As the pigment (a) in the present invention, there are organic pigments and inorganic pigments, and known pigments conventionally used for coloring printing inks, paints or thermoplastic resins can be used. Such pigments include azo-based pigments,
Anthraquinone, phthalocyanine, quinacridone, isoindolinone, dioxane, berylen,
Organic pigments such as quinophthalone and verinone, cadmium sulfide, cadmium selenide, ultramarine, titanium dioxide,
There are inorganic pigments such as iron oxide, chromate and carbon black. The pigment (a) in the present invention is contained in the colored resin composition in an amount of 0.01 to 90% by weight. If the content is less than 0.01% by weight, the desired hue and tinting strength cannot be obtained.
If it exceeds 0% by weight, problems occur in dispersibility, workability and the like.

Next, a copolymer resin of a monomer having an α, β unsaturated double bond and a dibasic acid or an anhydride thereof having an unsaturated double bond, wherein the content of unreacted substances is 2%
% Or less and / or their derivatives (b) will be described. In the present invention, the copolymer resin having an unreacted substance content of 2% or less and / or a derivative (b) thereof is contained in the colored resin composition in an amount of 1 to 90% by weight. If the content is less than 1% by weight, problems occur in the dispersibility and processability of the pigment, and if it exceeds 90% by weight, water resistance,
Problems arise in heat resistance, weather resistance, and the like.

The monomer having an α, β unsaturated double bond is not particularly limited as long as the copolymer resin has good compatibility with a paint vehicle, a printing ink varnish, or a thermoplastic resin for coloring. . Examples thereof include α-olefin, styrene, vinyl ether, vinyl ester, (meth) acrylic acid ester monomer and other copolymerizable vinyl monomer or vinylidene monomer. Among them, a monomer having 8 to 30 carbon atoms is particularly preferable. One or more of these are used.

More specifically, for example, in the case of α-olefin, ethylene, propylene, butylene, isobutylene,
Pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-
Eicosene, 1-docosene, 1-tetracosene, 1-hexacocene, 1-octacocene, 1-triaconten,
1-dotriaconten, 1-tetratoaconten, 1-
Hexatria content, 1-octatria content, 1
-Tetracontent and the like and mixtures thereof.
Commercially available products include dialen 10 (carbon number 10), dialen 124 (carbon number 12-14), dialen 208
(C 20-28), Dialen 30 (C 30)
<Mitsubishi Chemical Corporation>, Viper 260 (molecular weight 260
0), Viper 2800 (molecular weight 2800) <manufactured by Petrolite Co., Ltd.>, etc., and an α-olefin having 8 to 30 carbon atoms is most preferable.

Examples of the vinyl ether include methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, isobutyl vinyl ether, hexyl vinyl ether, octyl vinyl ether, nonyl vinyl ether,
Decyl vinyl ether, octadecyl vinyl ether,
Examples thereof include linear or branched aliphatic or alicyclic alkyl vinyl ethers such as 2-ethylhexyl vinyl ether, cyclohexane dimethanol monovinyl ether, tetraethylene glycol monovinyl ether, and trimethylolpropane trivinyl ether, and p-dioxene, and mixtures thereof. And a vinyl ether having 8 to 30 carbon atoms is most preferred.

The (meth) acrylate monomers include methyl acrylate, ethyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate,
Acrylic esters and / or methacrylic esters of linear or branched aliphatic alcohols such as 2-ethylhexyl acrylate, decyl acrylate, dodecyl acrylate, lauryl acrylate, stearyl acrylate, and the like, and mixtures thereof, Most preferred are 8 to 30 acrylates and / or methacrylates. In the present invention, the (meth) acrylate monomer means an acrylate monomer and / or a methacrylate monomer.

Other copolymerizable vinyl monomers include vinyl esters, vinyl pyridine, vinyl acetate, vinyl propionate, vinyl laurate, vinyl stearate, vinyl palmitate, vinyl n-decanoate, styrene, α Examples thereof include -methylstyrene, β-methylstyrene, p-octylstyrene, p-nonylstyrene, acrylonitrile, methacrylonitrile, and vinylidene chloride, and derivatives thereof, with vinyl monomers having 8 to 30 carbon atoms being most preferred.

In the present invention, the dibasic acid having an unsaturated double bond or its anhydride includes maleic acid, fumaric acid, itaconic acid, crotonic acid, citraconic acid, maleic anhydride, itaconic anhydride and citraconic anhydride. And one or more kinds are used, but maleic anhydride is industrially advantageous.

The copolymer resin of the present invention is obtained by copolymerizing the above monomer having an α, β unsaturated double bond with a dibasic acid having an unsaturated double bond or an anhydride thereof by using a polymerization initiator. The polymerization (hereinafter, abbreviated as the copolymerization) is performed, but it is necessary to reduce unreacted substances to 2% or less. That is, when 2% or more of the unreacted material remains, the unreacted material bleeds on the surface of the coating film or the colored molded product, and not only causes foaming or silver stalk, but also causes a problem in paints and printing inks. It adversely affects the weather resistance and heat resistance of the resin to be colored. Examples of a method for keeping the remaining unreacted substance at 2% or less include a method of washing and reprecipitating the copolymer resin with water or a solvent, and a method of degassing and removing under reduced pressure. The removal treatment is preferable from the viewpoint of productivity. The method for measuring unreacted substances may be a known method, and generally, gas chromatography (hereinafter, referred to as GC)
This is done using The composition ratio between the monomer having an α, β unsaturated double bond and the dibasic acid having an unsaturated double bond or its anhydride is such that the acid value of the copolymer resin is 100 to 700 mgKOH / g (hereinafter, referred to as mgKOH /
g is omitted) from the viewpoint of the dispersibility of the pigment.

The colored resin composition of the present invention is rich in pigment dispersibility and coloring power, because the carboxyl group and its anhydride in the copolymer resin (b) have high affinity for the pigment. Conceivable. That is, a large number of polar bonds are formed between the carboxyl group and its anhydride in the copolymer resin (b) and the basic group in the pigment,
By forming a protective colloidal core / shell structure around which a thermoplastic resin (c) described later wraps,
It is considered that secondary aggregation of the pigment particles was prevented.

The polymerization initiator used in the copolymerization of the present invention includes benzoyl peroxide, lauryl peroxide, cumene peroxide, diisopropyl peroxycarbonate, di-t-butyl peroxide,
Peroxides such as t-butylperoxybenzoate, azobisisobutyronitrile, azobis-2,4-
An azo compound such as dimethylvaleronitrile is exemplified.

The copolymer resin (b) of the present invention having an unreacted substance content of 2% or less has a weight average molecular weight of 10,000.
５００500,000 and the melt viscosity at 150 ° C. is in the range of 1,000 to 20,000 poise, or the weight average molecular weight is in the range of 10,000 to 500,000, and the acid value is in the range of 100 to 700. Is preferred. If the weight average molecular weight is 500,000 or more, the melt viscosity is 20,000 poise or more, or the acid value exceeds 700, even if it is applied to a liquid material such as paint or printing ink, the viscosity becomes too high, Coating unevenness and printing unevenness may occur. In addition, when applied to a coloring material of a thermoplastic resin coloring material, workability becomes a problem, and color unevenness and poor dispersion are likely to occur in the molding resin.
A weight average molecular weight of 10,000 or less, a melt viscosity of 1,000 poise or less, or an acid value of 100
When the amount is less than the above, bleeding of the coating film becomes a problem in the case of paints and printing inks, and in the case of a coloring material of a thermoplastic resin coloring material, a problem arises in granulation suitability, and the pigment dispersibility is not very good.

Examples of the copolymerization method of the present invention include solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization, high-pressure polymerization and the like, but are not particularly limited in these polymerization methods and reaction operations. However, bulk polymerization and high pressure polymerization are preferred. That is, in solution polymerization, it is difficult to increase the molecular weight by a chain transfer reaction of a solvent (about 1000 in weight average molecular weight).
0 or less and a melt viscosity at 150 ° C. of 1000 poise or less), which has the disadvantage of complicating the desolvation process. In addition, in emulsion polymerization and suspension polymerization, although a high molecular weight is possible, physical properties such as water resistance and weather resistance are significantly reduced due to the presence of an excessive amount of surfactants and metal salts, and there is a problem in terms of wastewater treatment. Many. On the other hand, in the case of bulk polymerization, since no solvent is used at all, it is possible to increase the molecular weight, and it is possible to avoid the incorporation of excessive additives that greatly affect the physical properties. In the case of high-pressure polymerization, a pressurized kettle is required, but a remarkable increase in the molecular weight and a high conversion can be achieved. In the case of high-pressure polymerization, a solvent may or may not be used. In addition, the molecular weight and viscosity can be controlled by the reaction temperature or the amount of the polymerization initiator in the bulk polymerization method, and the reaction temperature, the degree of pressure, or the chain transfer of the solvent in the high-pressure polymerization method, and the weight average molecular weight is 10,000 to 50.
000 and a melt viscosity at 150 ° C. of 1
Both polymerization methods are preferred because a resin in the range of 000 to 20,000 poise can be synthesized. The method of measuring the weight average molecular weight or the melt viscosity at 150 ° C. may be a known method. Generally, gel permeation chromatography (hereinafter referred to as GPC) is used for the molecular weight, and constant weight extrusion is used for the melt viscosity. This is performed using a capillary-type rheometer.

In the present invention, a derivative obtained by further modifying the copolymer resin obtained as described above in which the amount of residual unreacted substances is reduced to 2% or less can be used as the component (b). . The derivative is a carboxylic acid in a copolymer resin or a carboxyl group based on an anhydride thereof, and reacted with a compound having at least one or more hydroxyl group in the molecule to esterify or react with the carboxyl group,
Compounds having at least one amino group in the molecule are reacted with amidation or imidization, or the carboxyl group is reacted with a metal compound to be chelated. By performing the modification as described above, the acid value, molecular weight, viscosity,
Various physical properties such as softening point, strength, various resistances, flexibility, compatibility, and pigment dispersibility can be appropriately controlled. However, it is essential that the residual unreacted substance is also reduced to 2% or less in the derivative modified as described above. In the present invention, the unreacted product refers to an unreacted monomer in the copolymerization or an unreacted modifier (a compound having a hydroxyl group or a compound having an amino group) in the modification.

The compound having a hydroxyl group used in the esterification is not particularly limited as long as it has one or more hydroxyl groups in the molecule. For example, methanol, ethanol, propanol, isopropanol,
Butanol, sec-butanol, tert-butanol, pentanol, amyl alcohol, hexanol,
Heptanol, octanol, 2-ethylhexyl alcohol, nonanol, decanol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, polyethylene glycol monomethyl ether, polypropylene glycol monomethyl ether, α-oxybutyric acid, 12-hydroxystearic acid and the like and The mixture is used,
It is not particularly limited to these.

The amino compound used for amidation and imidation is not particularly limited as long as it has one or more amino groups in the molecule. Examples thereof include methylamine, ethylamine and propylamine. , Isopropylamine, butylamine, amylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, laurylamine, myristylamine, cetylamine, stearylamine, oleylamine, aniline, o-toluidine, 2-ethylaniline, 2-fluoroaniline , O-anisidine, m-toluidine, m-anisidine, m-phenetidine, p-toluidine, 2,3-dimethylaniline, 5-aminoindan, aspartic acid, glutamic acid, γ-aminobutyric acid and the like, and mixtures thereof. But it is lower, but the invention is not particularly limited thereto.

Further, as the metal compound used for chelation, for example, sodium, potassium, calcium,
Acetates such as magnesium, aluminum, zinc, nickel, iron, cobalt, manganese and copper, acetylacetone salts, organometallic compounds represented by metal alkoxides and inorganic metal compounds represented by oxides, and the like. However, the present invention is not limited to this. In addition, these modification reactions may be aqueous, solvent-based, solvent-free, or water-solvent combined systems, but it is preferable to wash unreacted substances with a solvent or water, or to perform a degassing removal treatment under reduced pressure. . Also,
The acid value of the derivative thus obtained is preferably from 5 to 800, and more preferably from 20 to 500. Acid value is 5
If it is less than 30, good pigment dispersibility and coloring property are hardly obtained, and in the case of a colored molded article, color unevenness and flow marks are liable to occur. When the acid value exceeds 800, it easily absorbs moisture and not only causes a fire and a silver stalk on the surface of a coating film or a colored molded product, but also adversely affects the weather resistance, heat resistance, etc. of a paint, a printing ink, and a resin to be colored. There is. In addition, the measuring method of an acid value may be a known method, and is generally JIS K007.
0 (1996).

As the thermoplastic resin (c), a resin having a melt flow rate (hereinafter, referred to as MFR) of 0.1 to 400 is preferable. When the MFR is 0.1 or less, the melt viscosity of the colored resin composition is too high. Therefore, poor coloring may occur in printing inks and paints, and color unevenness and flow marks may occur in coloring materials such as thermoplastic resin coloring materials.
On the other hand, when the MFR is 400 or more, bleeding, weather resistance, heat resistance, and the like of a coloring material such as a printing ink, paint, or thermoplastic resin coloring material may be adversely affected.

The content of the thermoplastic resin (c) of the present invention is 0.1 to 98% by weight in the colored resin composition. If the content is less than 0.1% by weight, there is a problem in compatibility with the resin to be colored.
With the above, the desired hue or coloring property cannot be obtained.

Among the thermoplastic resins (c) of the present invention, the polyolefin resins include crystalline or amorphous polypropylene, low-density or high-density polyethylene, random, block or graft copolymers of ethylene / propylene, -Butene ethylene and propylene copolymers, α-olefin and ethylene or propylene copolymers, ethylene / vinyl acetate copolymers, ethylene / methyl acrylate copolymers, ethylene / ethyl acrylate copolymers, etc. And one or more of these are used.

The thermoplastic resins other than polyolefins include polyesters such as polymethylpentene, polystyrene, polyethylene terephthalate and polydiene-based polybutylene terephthalate, acrylonitrile-butadiene-styrene (ABS) resin, and acrylonitrile-EPDM-. Thermoplastic resins such as styrene (AES) resin, other acrylic resins, polybutadiene, polyamide, polycarbonate, polyacetal, polyarylate, polyvinyl acetate, polyvinyl chloride, polyvinylidene chloride, polyurethane, and the like. Two or more are used. The shape of the thermoplastic resin (c) is not particularly limited, and may be a powder or a pellet.

In producing the colored resin composition of the present invention, a dry powder pigment may be used, or an aqueous wet cake of the pigment (also referred to as a wet cake or a filter cake) may be used. For example, when a dry powder pigment is used, the powder pigment (a) and two components of a copolymer resin and / or its derivative (b) in which unreacted monomers are reduced to 2% or less are required in advance. Surfactants and other additives are added accordingly, and mixed with a Henschel mixer or the like, and then melt-kneaded and dispersed with a kneader, roll mill, or extruder. Alternatively, the powder pigment (a), water, and unreacted monomer are added in an amount of 2%. The three components of the copolymer resin and / or its derivative (b) reduced to the following are added with a surfactant and other additives as necessary, and mixed with a Henschel mixer or a disper, and then flasher, kneader, and extruded. Mill, roll mill, ball mill, steel mill, sand mill, attritor, high-speed mixer, homomixer, etc., heat kneading, and then Removal of moisture, and evaporated to dryness at atmospheric pressure or under reduced pressure, the colored resin composition of interest is obtained. The latter method can be applied to the case where not only a dry powder pigment but also an aqueous wet cake is used. The thermoplastic resin (c) may be further added, mixed and dispersed after mixing and dispersing (a) and (b), or (a)
It may be mixed and dispersed simultaneously with (b). Then, depending on the purpose of use, the composition comprising the above-mentioned (a) (b) or (a) (b) (c) is added to a varnish for printing ink, a binder for paint or a hot-melt resin for coloring thermoplastic resin. The colored resin composition of the present invention can be produced by adding the substance and diluting and kneading the mixture.

The colored resin composition of the present invention can be used for almost all paints, printing inks, and coloring materials of thermoplastic resin coloring materials, such as polyolefin resin, acrylic resin, alkyd resin, vinyl resin, and polyester resin. , Polyamide resin, polyimide resin, ABS resin, polystyrene resin, polyurethane resin, phenol resin,
Amino resin, polyether resin, polycarbonate resin, polyacetal resin, polyarylate resin, epoxy resin, polysulfone resin and other polybutadiene,
It can also be blended with an elastomer such as polyisoprene. The colored resin composition of the present invention is a lubricant, a hot melt resin, in addition to a paint, a printing ink and a thermoplastic resin coloring material.
It can also be used for coloring applications such as thermal inks and adhesives.

The colored resin composition of the present invention may contain a thermoplastic resin or a derivative thereof by functional group modification, cross-linking modification, grafting and blocking modification, or a low polymer by thermal decomposition, as long as the effects of the present invention are not impaired. Various thermoplastic resins such as coalescing resin and wax, and a small amount of various additives such as an antioxidant, a stabilizer such as an ultraviolet absorber, and a surfactant can also be added.

[0031]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to examples. In the examples, “parts” means “parts by weight” and “%” means “% by weight”.

[Production Example 1] Dialen 124 (α having 12 to 14 carbon atoms)
-Olefin) (649 g) (manufactured by Mitsubishi Chemical Corporation) and 0.6 g of di-t-butyl peroxide were charged to a flask, and after purging with nitrogen, 369 g of maleic anhydride was added every 2 minutes while heating and stirring at 150 ° C. 3 g and 1.2 g of di-t-butyl peroxide were added in 0.6 g every 20 minutes. After the addition was completed, 0.6 g of di-t-butyl peroxide was further added, and the temperature of the system was maintained at 180 ° C. to further proceed the reaction. Further, after 1 hour and 3 hours, 1.2 g of t-butyl peroxide was added and reacted for 3 hours. Thereafter, the temperature of the system was maintained at 200 ° C., and unreacted monomers were removed under reduced pressure for 4 hours to terminate the reaction. The contents were taken out while hot and cooled and solidified.
The unreacted product amount, weight average molecular weight, melt viscosity at 150 ° C., and acid value of the obtained copolymer resin (b) were determined. Table 1 shows the results.

[0032]

Production Example 2 757.4 g of 1-octadecene, 2.7 g of di-t-butyl peroxide, 294.
After charging 2 g, 2.1 g of di-t-butyl peroxide and 120 g of xylene into an autoclave and purging with nitrogen, the system was pressurized to 3 kg / m 2, and the system was kept at 160 ° C. with stirring and further reacted for 6 hours. . Thereafter, the temperature of the system was maintained at 200 ° C., and unreacted monomers were removed under reduced pressure to terminate the reaction. The content was taken out during heating, cooled and solidified to obtain a copolymer resin (b).

[0033]

Production Example 3 788 g of the resin obtained by the method of Production Example 1,
Ethylene glycol monomethyl ether (molecular weight: 75
0) 212 g, 0.7% sodium paratoluenesulfonate
9 g was charged into a flask, melted in a nitrogen stream while stirring, and subjected to a dehydration reaction at a reaction temperature of 180 ° C. for 6 hours. After the completion of the reaction, the contents were taken out with heating, cooled and solidified.
Further, it was thoroughly washed with 3 kg of isopropyl alcohol and 3 kg of water, and dried to obtain a derivative (b) of a copolymer resin.

[0034]

[Production Example 4] Resin 787 obtained by the method of Production Example 2
g and stearylamine (213 g) were charged into a flask and melted in a nitrogen stream while stirring.
A time reaction was performed. After the completion of the reaction, the contents were taken out with heating, cooled and solidified. Further isopropyl alcohol 3
After washing thoroughly with 3 kg of water and 3 kg of water and drying, a derivative (b) of a copolymer resin was obtained.

[0035]

Production Example 5 300 g of the resin obtained in Production Example 1 and 22.1 g of potassium acetate were charged into a flask, melted in a nitrogen stream with stirring, and subjected to a deacetic acid reaction at a reaction temperature of 180 ° C. for 6 hours. Thereafter, the temperature of the system was maintained at 200 ° C., and unreacted monomers were removed under reduced pressure for 4 hours to terminate the reaction. The content was taken out during heating, cooled and solidified to obtain a copolymer resin derivative (b).

[0036]

Production Example 6 A flask was charged with 208 g of styrene, 144 g of dialene 10 (carbon number 10) (manufactured by Mitsubishi Chemical Corporation), and 2.7 g of di-t-butyl peroxide, and the mixture was purged with nitrogen, and then heated and stirred at 150 ° C. , Maleic anhydride 2
94.2 g was added every 2 minutes and 9.8 g di-tert-butyl peroxide was added every 20 minutes and 0.7 g each. After completion of the addition, the temperature of the system was maintained at 160 ° C., and the reaction was performed for 3 hours. Thereafter, the temperature of the system was maintained at 200 ° C., and unreacted monomers were removed under reduced pressure for 4 hours to terminate the reaction. The contents were taken out while hot and cooled and solidified. The content was taken out during heating, cooled and solidified to obtain a copolymer resin (b).

[0037]

[Production Example 7] Dialen 208 (20 to 28 carbon atoms)
638 g (manufactured by Mitsubishi Chemical Corporation), 650 g of stearyl methacrylate, 120 g of maleic anhydride, 3.6 g of di-tert-butyl peroxide, and 400 g of ethyl acetate were charged into an autoclave, and after purging with nitrogen, pressurized to 3 kg / m 2 and stirred. The temperature of the system was maintained at 160 ° C., and the reaction was further performed for 6 hours. After that, keep the temperature of the system at 200 ° C,
The unreacted monomers were removed under reduced pressure to terminate the reaction. The content was taken out during heating, cooled and solidified to obtain a copolymer resin (b).

[0038]

Production Example 8 2-ethylhexyl vinyl ether 624
g, 0.6 g of di-t-butyl peroxide was charged into a flask, and after purging with nitrogen, while heating and stirring at 150 ° C., 412 g of maleic anhydride was added at 13.7 g every 2 minutes, and di-t-butyl peroxide was added. 1.2 g of oxide was added 0.6 g every 20 minutes. After the addition, di-t-
0.6 g of butyl peroxide was added, and the temperature of the system was adjusted to 18
The temperature was kept at 0 ° C. to further proceed the reaction. After another hour and 3
After a lapse of time, 1.2 g of t-butyl peroxide was added and reacted for 3 hours. Thereafter, the temperature of the system is set to 200
The reaction was terminated by removing unreacted monomers for 4 hours under reduced pressure while maintaining the temperature. The content was taken out during heating, cooled and solidified to obtain a copolymer resin (b).

[0039]

Preparation Example 9 620 g of vinyl stearate and 2.7 g of di-t-butyl peroxide were charged into a flask, and after purging with nitrogen, 206 g of maleic anhydride was heated and stirred at 150.degree. And 2.1 g of di-tert-butyl peroxide were added in 0.7 g increments every 20 minutes. After the addition was completed, the temperature of the system was maintained at 160 ° C., and the reaction was further performed for 3 hours. Thereafter, the temperature of the system was maintained at 200 ° C., and unreacted monomers were removed under reduced pressure for 4 hours.
The reaction was terminated. The content was taken out during heating, cooled and solidified to obtain a copolymer resin (b).

[0040]

[Production Example 10] Dialen 124 (C12-14)
(Manufactured by Mitsubishi Chemical Corporation) 362 g, cyclohexane dimethanol monovinyl ether 328 g, vinyl laurate 45
After charging 2 g and 0.6 g of di-t-butyl peroxide into a flask and purging with nitrogen, 206 g of maleic anhydride was added at 6.9 g every 2 minutes while heating and stirring at 150 ° C. 1.2 g of oxide was added 0.6 g every 20 minutes. After the addition, di-t-
0.6 g of butyl peroxide was added, and the temperature of the system was adjusted to 18
The temperature was kept at 0 ° C. to further proceed the reaction. After another hour and 3
After a lapse of time, 1.2 g of t-butyl peroxide was added and reacted for 3 hours. Thereafter, the temperature of the system is set to 200
The reaction was terminated by removing unreacted monomers for 4 hours under reduced pressure while maintaining the temperature. The content was taken out during heating, cooled and solidified to obtain a copolymer resin (b).

[0041]

[Production Example 11] Dialen 124 (C12-14)
Production Example 1 using 649 g (manufactured by Mitsubishi Chemical Corporation), 0.6 g of di-t-butyl peroxide, and 369 g of maleic anhydride.
The reaction was carried out in the same manner as described above. At this time, the reaction was terminated in the same manner as in Production Example 1 except that the unreacted monomer was not treated under reduced pressure. Take out the contents when hot, cool and solidify,
A copolymer resin was obtained. Production Example 2 as in Production Example 1
The unreacted amount, the weight average molecular weight, the melt viscosity at 150 ° C., and the acid value of the copolymer resin obtained in Nos. To 11 and the derivative (b) thereof were determined. Table 1 shows the results.

[0042]

Example 1 50 parts of the resin obtained in Production Example 1 phthalocyanine blue "Lionoble-FG7330" (manufactured by Toyo Ink Mfg. Co., Ltd.) 50 parts The above two components were mixed and heated and kneaded at 160 ° C. with a three-roll mill. Thus, a mill base (pigment composition) was obtained. 100 parts of the obtained mill base was mixed with 100 parts of polypropylene "Mitsui Hypol J900P" (manufactured by Mitsui Petrochemical Industries, Ltd.) using a Henschel mixer and pelletized with a single screw extruder having a screw diameter of 65 mm to obtain a master batch. At this time, a master batch could be obtained smoothly without breaking strands or pulsating flow. Polypropylene “Mitsui High Pole J800” (Mitsui Petrochemical Co., Ltd., MFR:
22) 100 parts of the obtained master batch was mixed with 3 parts of the obtained master batch, and spun at 230 ° C. under a hopper, a kneading section and a die section at 230 ° C. with a vertical test spinning machine (a spinning tester manufactured by Fuji Filter Co., Ltd.). The film was drawn three times to obtain a 5-denier polypropylene fiber. Good dispersibility was exhibited without any problem in spinnability, clogging and stretching.

[0043]

Comparative Example 1 A mill base was obtained and a masterbatch was prepared in the same manner as in Example 1 except that polypropylene wax "VISCOL 660P" (manufactured by Sanyo Chemical Industries, Ltd.) was used instead of the resin obtained in Production Example 1. . At this time, a master batch could be obtained smoothly without breaking strands or pulsating flow. Using the obtained masterbatch,
When the yarn was spun in the same manner as in Example 1, yarn breakage due to clogging occurred.

[0044]

Comparative Example 2 A mill base was obtained and a master batch was prepared in the same manner as in Example 1 except that the resin obtained in Production Example 11 was used instead of the resin obtained in Production Example 1. Although pulsation occurred, the strand did not break and a master batch was obtained. When spinning was performed using the obtained master batch in the same manner as in Example 1, yarn breakage due to foaming and pulsation occurred.

[0045]

Comparative Example 3 Maleic anhydride-grafted polypropylene wax "UMEX 1010" (manufactured by Sanyo Chemical Industries, Ltd., resin acid value: 60) instead of the resin obtained in Production Example 1
mgKOH / g), and a mill base was obtained in the same manner as in Example 1 to prepare a master batch. At this time, the strand was broken, but a master batch could be obtained. Example 1 using the obtained masterbatch
When the yarn was spun in the same manner as described above, yarn breakage due to clogging occurred.

[0046]

Comparative Example 4 A maleic anhydride graft-modified polyethylene wax "HIWAX 1105A" (manufactured by Mitsui Petrochemical Co., Ltd., resin acid value: 6) instead of the resin obtained in Production Example 1
Except that 0 mgKOH / g) was used, a mill base was obtained in the same manner as in Example 1 to prepare a master batch. At this time, a master batch could be obtained smoothly without breaking strands or pulsating flow. When spinning was performed using the obtained master batch in the same manner as in Example 1, yarn breakage due to foaming and pulsation occurred.

In order to compare the clogging property of the undispersed pigment with Example 1, the master batches obtained in Example 1 and Comparative Examples 1 to 4 were prepared using polypropylene “Mitsui Noblen JH-G” (Mitsui Toatsu Chemicals, Inc.). MFR: 4) 10 parts were mixed with 100 parts, and 3 kg of each mixture was extruded with a single screw extruder with a screw diameter of 30 mm equipped with a wire mesh of 500 mesh at the tip, and the pressure rise value at the tip was measured. The results were compared and the results are shown in Table 2. Further, in order to compare the dispersive color developing properties of the pigment, one part of the master batch obtained in Example 1 and 100 parts of the polypropylene “Mitsui Hipole J800” and 5 parts of titanium oxide were blended. Was kneaded with a two-roll mill and formed into a 2 mm-thick plate by a cooling press. This is the color difference meter KURABO C
640 n using color-7E (manufactured by KURABO)
measured at a wavelength of m and the Kubelka in its reflectance
-Determine the Munk function (k / s) and calculate the k /
The value obtained by taking the ratio of s is called color intensity, and is shown in Table 2.

[0048]

Example 2 Resin obtained in Production Example 3 40 parts Titanium oxide “Taipe CR-50” (manufactured by Ishihara Sangyo) 30 parts Carbon black “Mitsubishi Carbon # 44” (manufactured by Mitsubishi Chemical Corporation) 10 parts Quinacridone red “ Fastogen Super Magenta RE03 ”(manufactured by Dainippon Ink and Chemicals, Inc.) 5 parts Phthalocyanine Blue“ Lionoble-POBS ”(manufactured by Toyo Ink Mfg.) 10 parts Phthalocyanine Green“ Riono Green 2Y301 ”(manufactured by Toyo Ink Mfg.) 5 Parts 30 parts of water were added to the above six components, and premixed with a Henschel mixer. As a twin-screw co-rotating screw extruder, screw diameter 30 mm, L / D value 42, rotation number 30
Using a 0 rpm extruder, dehydration, kneading and extruding at a set temperature of 160 ° C., a pigment mill base was obtained. 100 parts of the obtained mill base was replaced with polypropylene "Mitsui Hypole J
900P "(MFR: 40, manufactured by Mitsui Petrochemical Industries, Ltd.)
00 parts with a Henschel mixer and screw diameter 4
Pelletization was performed with a 5 mm single screw extruder to obtain a master batch. At this time, a master batch could be obtained smoothly without breaking strands or pulsating flow. A 3-denier polypropylene fiber was obtained in the same manner as in Example 1 of the obtained masterbatch. Good dispersibility was exhibited without any problem in spinnability, clogging and stretching.

[0049]

Comparative Example 5 A masterbatch was obtained in the same manner as in Example 2 except that polyethylene wax "HI-WAX NL500" (manufactured by Mitsui Petrochemical Industries, Ltd.) was used instead of the resin obtained in Production Example 2. At this time, a master batch could be obtained smoothly without breaking strands or pulsating flow. The obtained master batch was spun in the same manner as in Example 1, but the yarn was broken due to clogging. The clogging property of the undispersed pigment and the disperse coloring property of the pigment of the master batch obtained in Example 2 and Comparative Example 5 were evaluated in the same manner as in Example 1, and detailed results are shown in Table 2.

[0050]

Example 3 Resin obtained in Production Example 4 20 parts Condensed azo yellow "Chromophthal Yellow GR" 43 parts (manufactured by Ciba Geigy) Titanium oxide "Typure R-101" 5 parts (manufactured by EI DuPont) Kinacridone Red “Fast Gen Super Magenta RE03” 1 part (Dainippon Ink & Chemicals, Inc.) Phthalocyanine Blue “Rionoble-7110V” 1 part (Toyo Ink Mfg.) Polyethylene “NUC G5291” 30 parts (Nippon Unicar, MFR: 50) The above five components were premixed with a Henschel mixer and used as a twin-screw co-rotating screw extruder with a screw diameter of 3
Using an extruder having an L / D value of 0 mm, an L / D value of 42 and a rotation speed of 400 rpm, the mixture was extruded and extruded at a set temperature of 160 ° C., and then cut with a pelletizer to directly obtain a master batch. At this time, a master batch could be obtained smoothly without breaking strands or pulsating flow. Polyethylene “HIZEX 2100J” (Mitsui Petrochemical Co., Ltd., MFR:
6) To 100 parts, 3 parts of the obtained master batch was mixed and molded into a plate with an injection molding machine at a back pressure of 0 kg / cm2.

[0051]

Comparative Example 6 A master batch was obtained in the same manner as in Example 3 except that the resin obtained in Production Example 4 was replaced with an acid-modified polyethylene wax “Acrylin 540A” (manufactured by Allied Signal). At this time, a master batch could be obtained smoothly without breaking strands or pulsating flow. The obtained masterbatch was formed into a plate in the same manner as in Example 3. Retention of mechanical properties of molded articles obtained in Example 3 and Comparative Example 6 (retention of mechanical properties of resin colored with master batch with respect to mechanical properties of uncolored resin <100%>), Tables 3 and 4 show the results of evaluating the color unevenness on the molded product surface. Further, based on the size and number of the coarse particles of the pigment, the degree of dispersion of the pigment is determined by Luzex45.
Table 4 shows the evaluation results obtained by measuring with an image processor (manufactured by Toyo Ink Mfg. Co., Ltd.).

[0052]

Example 4 70 parts of resin obtained in Production Example 5 Phthalocyanine Green “Liono Green Y102” (manufactured by Toyo Ink Mfg. Co., Ltd.) 30 parts The above two components were mixed and kneaded at 160 ° C. in a kneader, followed by mill base. I got The obtained mill base (80 parts) was mixed with 120 parts of polyethylene “Mirason 11P” (manufactured by Mitsui Petrochemical Industry Co., Ltd., MFR: 7.2) using a Henschel mixer, pelletized with a single screw extruder having a screw diameter of 65 mm, and a master batch was prepared. Obtained. At this time, a master batch could be obtained smoothly without breaking strands or pulsating flow. The obtained masterbatch was formed into a plate in the same manner as in Example 3.

[0053]

Comparative Example 7 A mill base was obtained and a masterbatch was prepared in the same manner as in Example 4 except that polyethylene wax "Sunwax 151P" (manufactured by Sanyo Chemical Industries, Ltd.) was used instead of the resin obtained in Production Example 5. did. At this time, a master batch could be obtained smoothly without breaking strands or pulsating flow. The obtained masterbatch was used in Example 3
A plate was formed in the same manner as described above. As in Example 3, Tables 3 and 4 show the results of evaluating the retention of mechanical properties, the color unevenness of the surface of the molded product, and the degree of dispersion of the pigment of the molded products obtained in Example 4 and Comparative Example 7. Was.

[0054]

Example 5 Resin obtained in Production Example 2 150 parts Benzidine yellow aqueous wet cake (pigment content: 37%) 300 parts "Lionol Yellow GGT" (manufactured by Toyo Ink Mfg. Co., Ltd.) Polyethylene "Sumikasen G808" 20 parts (Sumitomo Chemical Co., Ltd., MFR: 200) The above three components were put in a kneader, heated to 150 ° C. and kneaded. After 20 minutes, the resin softened and the water evaporated, and the resin was adsorbed and transferred to the pigment in the aqueous pigment wet cake and gradually increased in viscosity. Furthermore, 300 parts of the above-mentioned aqueous wet cake of the pigment was added, and subsequently heated and kneaded,
As the residual moisture evaporated, the viscosity became extremely high after one hour, and flushing and dispersion were completed. Subsequently, the cooling was suddenly started to room temperature, followed by kneading and grinding.
When the particle diameter reached several mm, the colored resin composition was taken out and the operation was completed. Next, 50 parts of the colored resin composition, 2.5 parts of diethylethanolamine, and 47 parts of water
And 0.5 part of an antifoaming agent (silicone emulsion) were charged into a disper, dissolved and dispersed. Furthermore, 75% by weight of this composition was added to polyethylene wax "Topco PW
2.5 parts of "-M-10" (manufactured by Toyo Petrolite Co., Ltd.) and 22.5 parts of the resin obtained in Production Example 2 were added, followed by continuous dispersion to complete the formation of the ink. This printing ink had a viscosity of 18 seconds (Zahn Cup # 4: manufactured by Rigo Co., Ltd.) and had good storage stability. Flexographic or gravure printing of this printing ink on ace paper (manufactured by Jujo Paper Co., Ltd.) with water or a diluent of water / isopropyl alcohol (1/1) was performed. Could be obtained.

[0055]

Comparative Example 8 A printing ink was obtained in the same manner as in Example 5, except that the resin obtained in Production Example 2 was replaced with rosin glycerin ester "Ester Gum H" (manufactured by Arakawa Chemical Industries, Ltd.). At this time, the printing ink had a viscosity of 20 seconds (Zahn cup # 4) although it had a slight odor. Example 5
When printing was performed in the same manner as in Example 5, there was no practical problem, but the printability and printing effect were inferior to those in Example 5, and the gloss was particularly inferior. Table 5 shows the detailed results of Example 5 and Comparative Example 8.

[0056]

Example 6 Resin obtained in Production Example 120 120 parts Aqueous wet cake of phthalocyanine blue (pigment content: 46%) "Lionol Blue FG7334P" (manufactured by Toyo Ink Mfg. Co., Ltd.) 650 parts Ethylene / vinyl acetate copolymer Resin “SUMITATE HE10” (manufactured by Sumitomo Chemical Co., Ltd., MFR: 300) 20 parts 25% ammonia water 280 parts Isopropyl alcohol 50 parts The above four components are put into a ball mill, and kneaded for 20 hours to be kneaded to disperse the colored resin composition in water. Created body. The obtained colored resin composition aqueous dispersion was in a good dispersed state without aggregation or sedimentation of the pigment. Next, 100 parts of the aqueous dispersion of the colored resin composition, 2.5 parts of diethylethanolamine and 0.5 part of an antifoaming agent (silicone emulsion) were charged into a disper, mixed and dispersed. Further, 75 parts of this composition was mixed with polyethylene wax “Topco PW-M-1”.
0 "and 22.5 parts of the resin obtained in Production Example 6 were added, followed by dispersion to complete ink formation. This printing ink had a viscosity of 16 seconds (Zerncup # 4) and had good storage stability.

[0057]

Comparative Example 9 A printing ink was obtained in the same manner as in Example 6, except that hydrogenated rosin "Stevelite" (manufactured by Rika Hercules) was used instead of the resin obtained in Production Example 6. At this time, the printing ink had a viscosity of 25 seconds (Zahn cup # 4) although it had a slight odor. When printing was performed in the same manner as in Example 5, there was no practical problem. Table 5 shows the detailed results of Example 5 and Comparative Example 9.

[0058]

Example 7 Resin obtained in Production Example 40 40 parts Titanium oxide "Taipek CR-50" (manufactured by Ishihara Sangyo Co., Ltd.) 100 parts Gun blue "Gunjo # 2000" (manufactured by Daiichi Kasei Kogyo Co., Ltd.) 1 part Kinacridone Red " Shinkasha Red YRT759D "(manufactured by Ciba-Geigy) 1 part Acrylic resin (MFR: 350) 33 parts Butyl cellosolve 80 parts The above-mentioned 6 components are stirred for 1 hour with a disper, then kneaded and dispersed with a sand mill for 1 hour, and pigment content 40. % Pigment paste (colored resin composition) was prepared. The composition of the acrylic resin was methyl methacrylate / ethyl acrylate /
Styrene / methacrylic acid = 20/40/32/8% by weight
It is. To 100 parts of this pigment paste, 7 parts of the above acrylic resin, 3 parts of amino resin "Cymel 303" (manufactured by Mitsui Cyanamid) and 133 parts of butyl cellosolve were added and mixed well to obtain an acrylic baking paint having a pigment content of 0.16%. Was. Furthermore, apply it to a tin plate with a spray coater,
Baking was performed in an oven at 200 ° C. for 10 minutes. The paintability was good.

[0059]

Comparative Example 10 A pigment paste was obtained in the same manner as in Example 7, except that the acrylic resin used in Example 7 was used instead of the resin obtained in Production Example 7. An acrylic resin, an amino resin and butyl cellosolve were added to the obtained pigment paste in the same manner as in Example 7 to obtain a baked paint, which was applied. At this time, the surface smoothness was slightly inferior to Example 7. For Example 7 and Comparative Example 10, the gloss of the coating film,
The sharpness, colorability and dispersibility of the hue were evaluated, and detailed results are shown in Table 6.

[0060]

Example 8 Resin obtained in Production Example 40 40 parts Carbon black "MB-45" (manufactured by Mitsubishi Chemical Corporation) 60 parts Polybutylene terephthalate "Novadur 5010R3" (manufactured by Mitsubishi Engineering Plastics Corporation, MFR: 350) 6 parts Dimethylformamide 14 parts 2,6-ditert-butyl-p-cresol 1 part The above four components are charged into a kneader, and heated and kneaded. When the contents become viscous and fluid, start cooling and knead for 1 hour. Next, 25 parts of water is added to precipitate a kneaded material, which is pulverized in a kneader under pressure. Take this out, 7
The pigment paste (colored resin composition) was obtained by drying in a hot air dryer at 0 ° C. for 12 hours. 80 parts of xylene was added to 20 parts of the obtained colored resin composition and mixed well to obtain a pigment paste. It readily dissolved and dispersed. To 20 parts of the pigment paste, 6 parts of xylene and 92 parts of the amino resin used in Example 7 were added and mixed well to obtain a black baking paint having excellent dispersibility. Example 7
When baked at 280 ° C. in the same manner as in the above, the coating property was good.

[0061]

Comparative Example 11 Rosin pentaerythritol ester "Hariester P" was used instead of the resin obtained in Production Example 8.
A colored resin composition was obtained in the same manner as in Example 8, except that (Harima Chemical Industry Co., Ltd.) was used. The baked paint was obtained from the obtained colored resin composition in the same manner as in Example 8 and applied. At this time, aggregates were generated on the coating film surface. For Example 8 and Comparative Example 11, the gloss, clearness of hue, coloring and dispersibility of the coating film were evaluated, and detailed results are shown in Table 6.

[0062]

Example 9 35 parts of resin obtained in Production Example 6 Aqueous wet cake of phthalocyanine blue (pigment content: 35%) "Lionol Blue SM" (manufactured by Toyo Ink Mfg. Co., Ltd.) 1030 parts Ethylene vinyl alcohol copolymer Resin “Soareite K” (Nihon Gosei Kagaku Kogyo, MFR: 45) 5 parts Sodium dodecylbenzenesulfonate 5 parts Xylene 90 parts Water 600 parts The above five components were put into a disper, mixed and dispersed to prepare an aqueous pigment paste. Next, this pigment aqueous paste was put into a flasher and stirred while the temperature was raised to 150 ° C. The water was evaporated and the content was taken out when the content became high in viscosity, and was taken out and dried with a spray drier to obtain a colored resin composition. 79 parts of carnauba wax (mp: 83 ° C.) and paraffin wax (m) were added to 17 parts of the obtained colored resin composition.
p: 55 ° C.) 17 parts and 15 of the resin obtained in Production Example 6
113 parts of a% MEK solution was added, and dispersed with an attritor containing glass beads for 2 hours to prepare a thermal ink. This thermal ink is coated on a 6 mm thick polyethylene terephthalate film by a solvent coating method.
Coating was performed at 100 ° C. for 2 minutes so that the coating thickness after drying was 4 μm, to obtain a thermal transfer recording medium. The coatability was good.

[0063]

Comparative Example 12 A colored resin composition was obtained in the same manner as in Example 9 except that polymerized rosin “Pentalin CJ” (manufactured by Rika Hercules) was used instead of the resin obtained in Production Example 6. The obtained colored resin composition was replaced with a polystyrene resin "Esbrite 500S" in place of the resin obtained in Production Example 6.
A thermal ink was prepared in the same manner as in Example 9 except that a 15% xylene solution of "B" (manufactured by Sumitomo Chemical Co., Ltd.) was used to obtain a thermal transfer recording medium. The coatability was good, but there was a slight odor. For Example 9 and Comparative Example 12, the transfer energy sensitivity and the transfer image quality were measured at temperatures of 60 to 14.
Thermal gradient tester "HG-100" (manufactured by Toyo Seiki Seisaku-sho) under the conditions of 0 ° C., pressure: 2 kg / cm, thermocompression bonding time: 3 seconds, printing speed: 60 characters / sec, 8-dot thermal head Was evaluated with a high-density thermal printer.
The rub resistance of the transfer ink surface was determined by using a paperboard abrasion tester (manufactured by Kumagai Riki Kogyo Co., Ltd.) to measure the rub resistance against rough paper having a smoothness of 5 to 10 seconds at a temperature of 23 ° C. and a load of: 500
gw / cm, number of friction: evaluated under the condition of 100 reciprocations. Thermal transfer paper, mirror coated paper and OH
A P-sheet was used. Detailed results are shown in Table 7.

[0064]

Example 10 70 parts of resin obtained in Production Example 9 20 parts of carbon black "Mitsubishi Carbon MA-100" (manufactured by Mitsubishi Chemical Corporation) 10 parts of ethylene / vinyl acetate copolymer resin "DQDJ-7197" (Nippon Unicar MFR: 350) The above two components were mixed and heated and kneaded at 160 ° C. in a three-roll mill to obtain a mill base (colored resin composition). A thermal ink was prepared from the obtained mill base in the same manner as in Example 9 to obtain a thermal transfer recording medium. The coatability was good.

[0065]

Comparative Example 13 A colored resin composition was obtained in the same manner as in Example 10 except that microcrystalline wax (mp: 75 ° C.) was used instead of the resin obtained in Production Example 9. The obtained pigment composition was replaced with the acrylonitrile-styrene copolymer resin “TTR-0” in place of the resin obtained in Production Example 9.
A thermal ink was prepared in the same manner as in Example 9 except that a 15% xylene solution of "2" (manufactured by Fujikura Kasei) was used to obtain a thermal transfer recording medium. The coatability was good. Example 10
Evaluation was performed for Comparative Example 13 in the same manner as in Example 9, and detailed results are shown in Table 7.

[0066]

Examples 11 to 12 100 parts of resin obtained in Production Examples 9 to 10 Carbon black "Mitsubishi Carbon # 10" (manufactured by Mitsubishi Chemical Corporation) 10 parts Negative charge control agent "Pontron E81" (manufactured by Orient Chemical Company) 3 Part Polypropylene wax "Viscol 550P" 2 parts (Sanyo Kasei Kogyo Co., Ltd.) Polystyrene "Esprite 2V" 5 parts (Showa Denko KK, MFR: 32) The above five components are mixed and heated and kneaded at 130 ° C with a two-roll mill. To obtain a mill base, which was roughly pulverized by a hammer mill, finely pulverized by a jet mill, and then classified to obtain a toner (colored resin composition) having an average particle diameter of 13 μm.
The obtained toner was mixed with iron oxide powder “EFV200” (manufactured by Nippon Iron Powder Co., Ltd.) as a carrier to prepare a developer having a toner concentration of 5%.

[0067]

Comparative Example 14 A toner was obtained in the same manner as in Example 11 except that m-xylene bisstearic acid amide "Slipax ZXS" (manufactured by Nippon Kasei) was used instead of the resins obtained in Production Examples 9 to 10. Was. The obtained toner was used in Example 11
A developer was prepared in the same manner as described above.

The developers obtained in Examples 11 to 12 and Comparative Example 14 were placed in a modified copier "NC3000" (manufactured by Copier) and unfixed to A4 paper with 1/3 black solid. Created an image. Subsequently, this was passed through a heating roll type fixing tester having a Teflon upper part and a silicon rubber lower part in a stepwise manner at a roll temperature of 100 to 240 ° C., and passed at a linear velocity of 800 cm / min to perform fixing evaluation. The fixability was evaluated by attaching a cellophane tape to the fixed image and peeling it off.
J was determined by measuring D (image density). The hot setting temperature was determined by measuring the ID of the portion where the roll portion in contact with the solid black portion was in contact with the blank portion again, and measuring the ID of the other blank portion.
The lowest temperature increased 5% or more from D. Further, using a copying machine “NC3000” (manufactured by Copier), the temperature was reduced to 30 ° C.
A continuous copying test was performed under the condition of a humidity of 80%. The storage stability of the obtained developer was 2 at a temperature of 50 ° C. and a humidity of 80%.
Evaluation was performed under the condition of 4 hours. Detailed results are shown in Table 8.

[0069]

Example 13 Resin obtained in Production Example 10 10 parts Phthalocyanine blue "Lionol-7110V" 50 parts (manufactured by Toyo Ink Mfg. Copolymerized polyester "Byron GM900" 10 parts (manufactured by Toyobo Co., Ltd., MFR: 2) Polyethylene terephthalate “UNIPET RT543” 27 parts (Nihon Unipet, MFR: 0.5) Partially saponified product of montanic acid “LuwaxOP” 3 parts (BASF, saponification value: 150 mg KOH / g) A mill base was obtained in the same manner as in Example 1, and a master batch was obtained. At this time, a master batch could be obtained smoothly without breaking strands or pulsating flow. Polyethylene terephthalate "Unipet RT
543 "(Nihon Unipet, MFR: 0.5) 10
0 parts were mixed with 3 parts of the obtained master batch, and the vertical test spinning machine used in Example 1 was used to mix the lower part of the hopper with 230 parts.
After spinning at 230 ° C., a kneading section and a die section, the fiber was drawn four times, and then heat-treated at 140 ° C. to obtain a 3-denier polyester fiber. Good dispersibility was exhibited without any problem in spinnability, clogging and stretching. Intrinsic viscosity of polyethylene terephthalate without master batch 0.735
The intrinsic viscosity of the fiber obtained relative to dl / g is 0.725
dl / g, and the intrinsic viscosity retention was 98.6%.

[0070]

Comparative Example 15 A masterbatch was obtained in the same manner as in Example 13, except that the copolymer polyester "Vylon GM900" was used instead of the resin obtained in Production Example 1. At this time, a master batch could be obtained smoothly without breaking strands or pulsating flow. Intrinsic viscosity of polyethylene terephthalate without addition of master batch 0.795dl
/ G of the fiber obtained is 0.498 dl
/ G, and the intrinsic viscosity retention was 62.7%. When spinning was performed in the same manner as in Example 13 using the obtained master batch, yarn breakage due to clogging occurred.

[0071]

Example 14 Resin obtained in Production Example 8 20 parts Phthalocyanine blue “Lionol Blue-7110V” 50 parts (manufactured by Toyo Ink Mfg. Co., Ltd.) Nylon 6 “Unitika Nylon A1020” 10 parts (manufactured by Unitika Ltd., MFR: 20) Nylon 6 “Unitika Nylon A1030BRL” 20 parts (Unitika Ltd., MFR: 1) A mill base was obtained from the above four components in the same manner as in Example 1, and further a master batch was obtained. At this time, a master batch could be obtained smoothly without breaking strands or pulsating flow. Nylon 6 "Unitika Nylon A1030BR
L "(100 parts) was mixed with the obtained master batch (3 parts), and a 5-denier nylon fiber was obtained in the same manner as in Example 1. Good dispersibility was exhibited without any problem in spinnability, clogging and stretching.

[0072]

Comparative Example 16 A master batch was obtained in the same manner as in Example 14 except that nylon 6 "Unitika Nylon A1020" was used instead of the resin obtained in Production Example 8. At this time, a master batch could be obtained smoothly without breaking strands or pulsating flow. The obtained master batch was treated in the same manner as in Example 14 to obtain a 5-denier nylon fiber. There was no problem in spinnability.

[0073]

Example 15 Resin obtained in Production Example 1 15 parts Phthalocyanine blue “Lionol Blue-7110V” 55 parts (manufactured by Toyo Ink Mfg. Co., Ltd.) Polyamide “Versamide DPX640” 10 parts (manufactured by Henkel Hakusui, MFR: 120) Special nylon 20 parts of resin "Macromelt 6900" (manufactured by Henkel Hakusui Co., Ltd., MFR: 10) A mill base was obtained from the above five components in the same manner as in Example 1, and a master batch was further obtained. At this time, a master batch could be obtained smoothly without breaking strands or pulsating flow. Special nylon resin "Macromelt 6902"
3 parts of the obtained masterbatch was mixed with 100 parts (manufactured by Henkel Hakusui Co., Ltd., MFR: 3) to obtain 3 denier nylon fiber in the same manner as in Example 1. Good dispersibility was exhibited without any problem in spinnability, clogging and stretching.

[0074]

Comparative Example 17 A masterbatch was obtained in the same manner as in Example 15 except that a special nylon resin "Macromelt 6903" (manufactured by Henkel Hakusui Co., MFR: 100) was used instead of the resin obtained in Production Example 1. Was. At this time, a master batch could be obtained smoothly without breaking strands or pulsating flow. When spinning was performed using the obtained master batch in the same manner as in Example 14, yarn breakage due to clogging occurred.

In order to evaluate the clogging property of the undispersed pigment, 10 parts of each of the master batches obtained in Example 13 and Comparative Example 15 were added to 100 parts of polyethylene terephthalate “Unipet RT543”, and Examples 14 and 15 were used. 10 parts each of the master batches obtained in Comparative Examples 16 and 17 were treated with nylon 6 “Unitika Nylon A1030BRL” 1
Then, 3 kg of each mixture was extruded with a single-screw extruder having a screw diameter of 30 mm equipped with a wire mesh of 500 mesh at the tip, and the pressure rise value at the tip was measured. The results are shown in Table 2. Further, in order to evaluate the dispersive color developing property of the pigment, 1 part of each of the master batches obtained in Example 13 and Comparative Example 15 was added to 100 parts of polyethylene terephthalate “Unipet RT543”, and Example 1 was used.
4 and 15 and 1 part of the master batch obtained in Comparative Examples 16 and 17 was treated with nylon 6 “Unitika Nylon A1030BR”.
L "and 100 parts of titanium oxide.
A mixture of 5 parts of "R-80" was kneaded with a two-roll mill and formed into a 2 mm-thick plate by a cooling press. In the same manner as in Example 1, the color difference meter KURABO Color-
It was measured at a wavelength of 640 nm using 7E (manufactured by KURABO), and the results of the color intensity according to the k / s ratio are shown in Table 2. In addition, the absorption intensity of Examples 13 and 14 was 10
Expressed as 0%.

[0076]

Example 16 15 parts of resin obtained in Production Example 7 50 parts of phthalocyanine blue “Lionol Blue-POBS” (manufactured by Toyo Ink Mfg. Co., Ltd.) 5 parts of titanium oxide “Kronos KR-460” (manufactured by Titanium Industry Co., Ltd.) 5 parts of ABS resin “ 30 parts of JSR ABS35 (manufactured by Nippon Synthetic Rubber Co., Ltd., MFR: 60) A mill base was obtained in the same manner as in Example 3 except that the above four components were used.
Further, a master batch was obtained. At this time, a master batch could be obtained smoothly without breaking strands or pulsating flow. 100 parts of ABS resin “JSR ABS10” (manufactured by Nippon Synthetic Rubber Co., Ltd., MFR: 0.5) was mixed with 3 parts of the obtained master batch, and molded into a plate in the same manner as in Example 5.

[0077]

Comparative Example 18 A masterbatch was obtained in the same manner as in Example 16 except that a metal soap (zinc stearate) was used instead of the resin obtained in Production Example 7. At this time, a master batch could be obtained smoothly without breaking strands or pulsating flow. The obtained master batch was prepared in Example 16
A plate was formed in the same manner as described above.

[0078]

Example 17 20 parts of resin obtained in Production Example 7 20 parts of condensed azo yellow “Chromophthal Yellow GR” (manufactured by Ciba Geigy) 25 parts of quinacridone red “Fast Gen Super Magenta RE03” (manufactured by Dainippon Ink and Chemicals, Inc.) ) Titanium oxide "Typek CR-60" (manufactured by Ishihara Sangyo) 5 parts Polystyrene resin "Stylon 683" 15 parts (Made by Asahi Kasei Corporation, MFR: 2.8) 15 parts of polystyrene resin "Stylon 666" (Made by Asahi Kasei Corporation) , MFR: 7.5) The above six components were obtained in the same manner as in Example 3 to obtain a mill base.
Further, a master batch was obtained. At this time, a master batch could be obtained smoothly without breaking strands or pulsating flow. Polystyrene resin "Stylon 683" 10
0 parts were mixed with 3 parts of the obtained master batch, and molded into a plate in the same manner as in Example 3.

[0079]

Comparative Example 19 A masterbatch was obtained in the same manner as in Example 17 except that polystyrene wax “Hymer SB130” (manufactured by Sanyo Chemical Industries, Ltd.) was used instead of the resin obtained in Production Example 7. At this time, a master batch could be obtained smoothly without breaking strands or pulsating flow.
The obtained master batch was formed into a plate in the same manner as in Example 17.

The mechanical properties of the molded articles obtained in Examples 16 and 17 and Comparative Examples 18 and 19 (the mechanical properties of the resin colored with the master batch relative to the mechanical properties <100%> of the uncolored resin) Table 3 shows the physical property retention). Table 2 shows the results of evaluating the color unevenness on the molded product surface. Further, based on the size and the number of the coarse particles of the pigment, the degree of dispersion of the pigment was measured with a Luzex 450 image processor (manufactured by Toyo Ink Mfg. Co., Ltd.), and the evaluation results are shown in Table 4.

[0081]

[Table 1]

[0082]

[Table 2]

[0083]

[Table 3]

[0084]

[Table 4]

[0085]

[Table 5]

[0086]

[Table 6]

[0087]

[Table 7]

[0088]

[Table 8]

[0089]

The coloring resin composition of the present invention has excellent pigment dispersibility regardless of the pigment content, and is suitable for coloring textile products requiring high pigment dispersion, heat-sensitive inks, printing inks and paints. It has a great effect on the gloss, the sharpness of the hue, and the coloring property of the developer such as toner. Also, conventionally, there is no coating defects such as bumps and color unevenness due to many dispersion defects, and a good coating film is obtained.
It is also excellent in coating processability and can obtain good coating film properties. In particular, it is extremely effective for coloring a thermoplastic resin which is a molding material, exhibits high dispersion and high color development, and enables coloring without color unevenness.

Continuation of the front page (72) Inventor Akiyoshi Iguchi 2-3-1 Kyobashi, Chuo-ku, Tokyo Examiner, Toyo Ink Manufacturing Co., Ltd. Satoshi Morikawa (56) References JP-A-6-87980 (JP, A) JP JP-A-6-256531 (JP, A) JP-A-6-256702 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08J 3/22

Claims (9)

(57) [Claims] 1. Pigment (a) 0.01 to 90% by weight, α,
A copolymer resin of a monomer having a β-unsaturated double bond and a dibasic acid having an unsaturated double bond or an anhydride thereof and / or a derivative thereof, wherein the content of an unreacted substance is 2% or less. (B) 1 to 90% by weight of a copolymer resin and / or a derivative thereof (b), and a thermoplastic resin (c)
A colored resin composition comprising 0.1 to 98% by weight. 2. The method according to claim 2, wherein the monomer having an α, β unsaturated double bond contains at least one monomer selected from copolymerizable α-olefin, styrene, vinyl ether, vinyl ester and derivatives thereof. The colored resin composition according to claim 1, characterized in that: 3. The colored resin composition according to claim 1, wherein the monomer having an α, β unsaturated double bond has 8 to 30 carbon atoms. 4. The colored resin composition according to claim 1, wherein the dibasic acid having an unsaturated double bond or its anhydride is maleic anhydride. 5. The copolymer resin (b) having an unreacted substance content of 2% or less has a weight average molecular weight of 10,000 to 500.
000 and a melt viscosity at 150 ° C. of 10
The weight average molecular weight is in the range of 10,000 to 500,000, or
The colored resin composition according to any one of claims 1 to 4, wherein a resin acid value is in a range of 100 to 700 mgKOH / g. 6. The copolymer resin (b) having an unreacted substance content of 2% or less is prepared by a high-pressure polymerization method or a bulk polymerization method. 5. The colored resin composition according to any one of 5. 7. The colored resin composition according to claim 1, wherein the melt flow rate of the thermoplastic resin (c) is in the range of 0.1 to 400. 8. The colored resin composition according to claim 1, wherein the thermoplastic resin (c) is a polyolefin resin. 9. The colored resin composition according to claim 1, which is used for molding a thermoplastic resin.