JPH05255608A - Pigment composition and method for coloring thermoplastic polymer molding using the same - Google Patents

Abstract

PURPOSE:To provide a pigment composition excellent in fluidity and moldability, capable of uniformly coloring the subject polymer molded products with their physical properties retained, thus useful for molding, etc., comprising a pigment, specific graft copolymer, and thermoplastic polymer at specified proportion. CONSTITUTION:The objective pigment composition comprising (A) a pigment such as azo pigment, (B) a graft copolymer produced by grafting vinyl polymer block, via divalent organic linking group, onto polysiloxane block at a weight ratio A/B of (1:10) to (10:1), and (C) the rest of a thermoplastic polymer.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a pigment composition and a method for coloring a thermoplastic polymer molding using the same. Various kinds of inorganic pigments and organic pigments are added to thermoplastic polymers for the purpose of coloring and shading. And injection molding, compression molding, film formation, using a thermoplastic polymer containing such a pigment,
Molded products of various shapes, films, sheet-shaped molded products, and fibrous molded products are processed by melt molding such as spinning. When a thermoplastic polymer containing a pigment is melt-molded, it is required that the pigment is uniformly distributed in the resulting molded product, and therefore the molded product is uniformly colored. The present invention relates to a pigment composition that meets such a demand and a method for coloring a thermoplastic polymer molded product using the same.

[0002]

2. Description of the Related Art Conventionally, as a method for coloring a thermoplastic polymer molding, 1) the surface of the pigment is treated with a surface-active substance or a dispersant is used for the purpose of stably dispersing the pigment in the thermoplastic polymer. Examples of use 2) Examples of using lubricants such as fatty acid metal soaps and waxes for the purpose of improving the lubricity between the pigment and the thermoplastic polymer (JP-A-63-9271)
7, JP-A-63-120767), 3) An example of using a fluidity improver such as an aliphatic polyester for the same purpose as 2) (JP-A-63-6051, JP-A-2-16315).
7), 4) For the purpose of reducing the viscosity of the melt of the thermoplastic polymer containing the pigment, fatty acid esters (JP-A-1-
271456, JP-A-2-163157, JP-A-3-6
6753) and imide compounds (JP-A-3-223383)
There is an example of using.

However, the conventional method 1) has a drawback that it is not versatile because its effect is limited to a specific thermoplastic polymer. Further, the above-mentioned conventional method 2) cannot be applied to a thermoplastic polymer having poor thermal stability, causing discoloration or contamination of the obtained molded product, and having a melting temperature of 250 ° C. or higher during molding. There is a drawback. Further, the conventional method of the above 3) has a drawback in that although the fluidity can be improved, the coloring homogeneity of the obtained molding is insufficient, and there is almost no effect particularly when the pigment is blended at a high ratio. There is. And the conventional method of the above 4) has a drawback that the physical properties of the obtained molded product are deteriorated.

[0004]

The problem to be solved by the present invention is that, in the conventional method, it is impossible to homogenize a wide range of general molded products obtained by melt molding without deteriorating the physical properties thereof. It is a point.

[0005]

However, the present inventors have
As a result of diligent research to solve the above problems, the pigment and the graft copolymer having a specific structure in which a vinyl polymer block is graft-bonded to a polysiloxane block are contained in predetermined proportions, respectively, and as a total amount thereof, a predetermined amount or more is contained. It has been found that the use of pigment compositions is correct and suitable.

That is, in the present invention, a pigment and a graft copolymer in which a vinyl polymer block is graft-bonded to a polysiloxane block through a divalent organic linking group are prepared by: pigment / the graft copolymer = 1/10 -10/1 (weight ratio)
And a total amount of these components of 30% by weight or more, the balance being composed of a thermoplastic polymer, and a composition in which the pigment composition is blended with a thermoplastic polymer. And a method for coloring a thermoplastic polymer molded article, which comprises melt-molding the thermoplastic polymer at a temperature equal to or higher than the melting point of the thermoplastic polymer.

The pigment used in the pigment composition of the present invention includes 1) inorganic pigments such as titanium oxide and carbon black,
2) Organic pigments such as azo pigments, phthalocyanine pigments, quinacdrine pigments, isoindolinone pigments, and quinophthalone pigments. The type, particle shape, particle size and the like of such pigment are not particularly limited.

The graft copolymer used in the pigment composition of the present invention is a polysiloxane block grafted with a vinyl polymer block via a divalent organic linking group. The polysiloxane block includes a linear polysiloxane block and a crosslinked polysiloxane block.

The linear polysiloxane block is a line selected from a dialkylsiloxane unit, a disubstituted alkylsiloxane unit having a non-radical-polymerizable substituent in the alkyl group, and a siloxane unit having both an alkyl group and a substituted alkyl group. The siloxane unit is composed of one or more kinds. Examples of the siloxane unit having both an alkyl group and a substituted alkyl group include a glycidoxypropyl.methylsiloxane unit and a ureidopropyl.methylsiloxane unit. In the present invention, the dialkyl siloxane unit is preferably a dimethyl siloxane unit,
The linear polysiloxane block preferably contains 70 mol% or more of dimethylsiloxane units.

The crosslinked polysiloxane block is a polysiloxane block in which the linear polysiloxane block is crosslinked by a siloxane bond. The siloxane unit forming such a crosslinked siloxane bond (hereinafter referred to as a crosslinked siloxane unit) includes RSi
A crosslinked siloxane unit represented by O _3/2 and a crosslinked siloxane unit represented by SiO ₂ are included. Here, R is an organic group having a carbon atom directly bonded to a silicon atom, and R-
As the crosslinked siloxane unit represented by SiO _3/2 , a methylsiloxane unit (CH ₃ —SiO _3/2 ) is preferable. In the present invention, as the polysiloxane block, the crosslinked siloxane units are all siloxane units (the linear siloxane units + the crosslinked siloxane units + the linked siloxane units described later).
Those containing 20 mol% or less are preferable, and those containing 10 mol% or less are more preferable.

Examples of the divalent organic connecting group include ethylene group, propylene group, 3-oxo-4-oxa-1,7-
Examples include a heptanediyl group, a 2-methyl-3-oxo-4-oxa-1,7-heptanediyl group, a trimethylenethiooxy group, and the like.

The vinyl polymer block is obtained by vinyl polymerizing a vinyl monomer. Such a vinyl polymer block includes a homopolymer block obtained by polymerizing a single vinyl monomer and a copolymer block obtained by copolymerizing two or more kinds of vinyl monomers. As the vinyl monomer forming the vinyl polymer block, 1) alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate and cyclohexyl methacrylate, 2)
Alkyl acrylates such as methyl acrylate, ethyl acrylate and butyl acrylate, 3) styrene,
aromatic vinyl monomers such as α-methylstyrene, 4) vinyl esters such as vinyl benzoate and vinyl acetate,
5) Vinyl monomers having a sulfonic acid group such as styrene sulfonate, vinyl sulfonate, and (meth) allyl sulfonate, 6) (meth) acrylamide, N, N-dimethylacrylamide, vinylcaprolactam, N- Vinyl monomers having an amide group such as vinylcaprolactam,
7) 2-hydroxyethyl (meth) acrylate, 2-
Hydroxyalkyl (meth) acrylates such as hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8) 2,2,3,3-tetrafluoropropyl acrylate, 2 , 2,2-trifluoroethyl acrylate, hexafluoroisopropyl methacrylate, 2,2,2-trifluoroethyl methacrylate and other fluoroalkyl (meth) acrylates,
9) 2,2,3,3-tetrafluoropropyl-2-
(Trifluoromethyl) propenoate, 2,2,2-
Fluoroalkyl (fluoromethyl) propenoates such as trifluoroethyl-2- (trifluoromethyl) propenoate, 10) 1- (trifluoromethyl) vinyl acetate, fluorine-substituted vinyl esters such as vinyl (trifluoro) acetate , 11) Fluorine-substituted vinyl aromatic hydrocarbons such as 3-fluorostyrene and α-trifluoromethylstyrene.

In the graft copolymer used in the pigment composition of the present invention, the vinyl polymer block is graft-bonded to the silicon atom in the siloxane unit contained in the polysiloxane block via the divalent organic linking group. .. In the present invention, it is preferable that the polysiloxane block contains 0.1 to 5 mol% of siloxane units grafted with such vinyl polymer blocks (hereinafter referred to as linked siloxane units) in all siloxane units.
Those containing 5 to 3 mol% are more preferable.

Next, a method for producing the graft copolymer used in the pigment composition of the present invention will be described. First, a compound capable of forming a silanol group by hydrolysis (hereinafter referred to as a silanol group-forming compound) is hydrolyzed in an aqueous medium in the presence of a hydrolysis catalyst such as an acid or an alkali to produce a silanol compound. Next, the silanol compound is polycondensed in the presence of a polycondensation catalyst such as an inorganic acid or an organic acid to form an aqueous emulsion of polysiloxane. In order to reduce the average particle size of the aqueous emulsion and form a stable aqueous emulsion of polysiloxane, it is necessary to appropriately use a surfactant in the hydrolysis reaction system of the silanol group-forming compound or the condensation polymerization reaction system of the silanol compound. it can. Finally, a vinyl monomer and a radical polymerization catalyst are added to an aqueous emulsion of polysiloxane to carry out graft polymerization to introduce a vinyl polymer block into the polysiloxane.

Examples of the silanol group-forming compound include
There are various alkoxysilanes, chlorosilanes, hydrogensilanes, acyloxysilanes, cyclosiloxane compounds and the like. Polysiloxane is produced from such a silanol group-forming compound as a raw material. In order to form a linear siloxane block in the polysiloxane, two silanol groups are formed by hydrolysis, which is a raw material of a linear siloxane unit. A non-radical-polymerizable silanol group-forming compound as described above and a radical-polymerizable silanol group-forming compound that is a raw material of a linked siloxane unit and that forms two silanol groups by hydrolysis are used. Further, in order to form a crosslinked polysiloxane block in polysiloxane, in addition to the above-mentioned raw material, three or four silanol groups are formed by hydrolysis, which is a raw material of a crosslinked siloxane unit. A silanol group-forming compound is used.

Examples of the silanol group-forming compound that forms the linear siloxane unit include 1) silane compounds such as dimethyldimethoxysilane, dimethyldichlorosilane, dimethyldihydrogensilane and dimethylchlorosilanol, and 2) hexa. Siloxane compounds such as methyldisiloxane and octamethylcyclotetrasiloxane, 3) γ-glycidoxypropyl methyl dimethoxysilane, γ-ureidopropyl methyl dimethoxysilane, N, N-dimethylaminopropyl methyl dimethoxysilane And a silane compound having a hydrocarbon group substituted with a polar group such as.

Examples of the silanol group-forming compound that forms the linked siloxane unit include methacryloyloxypropyl methyl dimethoxysilane, vinyl methyl dimethoxysilane, aryl methyl dimethoxysilane, and mercaptopropyl methyl dimethoxy. There are silane compounds such as silane having a functional group such as a radically polymerizable group or a thiol group in the molecule.

Examples of the silanol group-forming compound that forms the crosslinked siloxane unit include 1) 3 such as methyltrimethoxysilane, methyltrichlorosilane, methyldichlorosilanol, and methylchlorodisilanol.
There are silane compounds that form four silanol groups, such as silane compounds that form four silanol groups, 2) tetramethoxysilane, tetrachlorosilane, and trichlorosilanol.

In the present invention, the silanol group-forming compound as described above is used as a main raw material for producing the graft copolymer, but the molecular weight of the polysiloxane obtained by polycondensation of the silanol compound and the polysiloxane can be controlled. For the purpose of controlling the structure of the terminal group of, a silanol group-forming compound capable of forming one silanol group by hydrolysis can be appropriately used. The ratio of the silanol group-forming compound used is usually 2 mol% or less, preferably 1 mol% or less, as a siloxane unit in all silanol group-forming compounds.

The silanol group-forming compound capable of forming one silanol group by hydrolysis is 1).
Trimethylmethoxysilane, trimethylchlorosilane,
A silane compound such as trimethylhydrogensilane,
2) siloxane compounds such as hexamethyldisiloxane,
3) Silane compounds such as γ-glycidoxypropyl dimethyl methoxysilane, γ-ureidopropyl dimethyl methoxysilane and N, N-dimethylaminopropyl dimethyl methoxysilane 4) Methacryloyloxypropyl dimethyl methoxy There are silane compounds such as silane, vinyl dimethyl methoxy silane, aryl dimethyl methoxy silane, and mercaptopropyl dimethyl methoxy silane.

In order to produce the graft copolymer used in the pigment composition of the present invention, the silanol group-forming compound is hydrolyzed in an aqueous medium as described above, and the resulting silanol compound is polycondensed to give a poly An aqueous emulsion of siloxane is obtained. The water-based medium used here contains 30% by weight of water.
The homogeneous solvent contains at least 90% by weight, preferably at least 90% by weight. Solvents that can be used in combination with water include water-soluble solvents such as methanol, ethanol, isopropanol, acetone and tetrahydrofuran.

Graft polymerization is carried out by adding a radical polymerization catalyst and a vinyl monomer to an aqueous polysiloxane emulsion and stirring the mixture in an inert gas atmosphere. The reaction at this time can be carried out in the temperature range from room temperature to the boiling point of the vinyl monomer used.

Thus, an aqueous emulsion of a graft copolymer in which a vinyl polymer block is graft-bonded to the polysiloxane block via a divalent organic connecting group is obtained. The present invention is not particularly limited as to the method for separating the graft copolymer from the aqueous emulsion, but 1) sodium chloride, potassium chloride,
Alkali metal salts such as potassium bromide and sodium sulfate,
2) A method in which a water-soluble alkaline earth metal salt such as calcium chloride or magnesium chloride is added and the graft copolymer is salted out and separated is advantageous. One or more of these salts may be added as they are, or may be added as a concentrated aqueous solution. If necessary, the salt-separated product is further centrifuged, separated by filtration, washed with water or the like to remove salts, and dried.

In the graft copolymer used in the pigment composition of the present invention, the polysiloxane block preferably has a molecular weight of 7,000 to 500,000.
Those of 0 to 100,000 are more preferable. The proportion of the vinyl polymer block in the graft copolymer varies depending on the type of the vinyl polymer block or the thermoplastic polymer to be applied, but is 10 to 90% by weight from the viewpoint of the physical properties of the obtained molded product. It is preferable that the amount is 30% to 70% by weight, and it is more preferable that the amount is 30 to 70% by weight.

The pigment composition of the present invention comprises a pigment and a graft copolymer, the pigment / the graft copolymer = 1/10 to 10
It is contained at a ratio of 10/1 (weight ratio), and is contained in a total amount of 30% by weight or more, and the balance is composed of a thermoplastic polymer. Therefore, in the pigment composition, if necessary, a thermoplastic polymer is blended at a ratio of 70% by weight or less, and the thermoplastic polymer is blended with the pigment composition of the present invention and subjected to melt molding. The same thing as a thermoplastic polymer is preferable.

The pigment composition of the present invention is prepared as a masterbatch by kneading the pigment, the graft copolymer and, if necessary, the thermoplastic polymer by a known kneading method. Such a kneading method includes a mill, a calendar, a kneader, and an extruder. The kneading temperature is
It is higher than the softening point of the graft copolymer to be used, or higher than the melting point of the thermoplastic polymer when a thermoplastic polymer is used in combination, and is generally 160 to 300 ° C.

The thermoplastic polymer to be blended with the pigment composition of the present invention and subjected to melt molding includes 1) aromatic polyesters such as polyethylene terephthalate and polybutylene terephthalate, 2) poly ε-caprolactam and polyhexamethylene azide. Polyamides such as pamide, 3) vinyl hydrocarbons such as polypropylene and polystyrene, 4) polyacetal, 5) polyphenylene ether, 6) polyvinyl chloride, and vinyl chloride resins such as vinyl chloride / vinyl acetate.

According to the present invention, a homogeneously colored thermoplastic polymer molded product can be obtained by melt-molding a composition obtained by mixing the pigment composition with the thermoplastic polymer as described above. The blending amount of the pigment composition with respect to the thermoplastic polymer is not particularly limited, but usually the thermoplastic polymer 1
The pigment is added in an amount of 0.1 to 10 parts by weight per 00 parts by weight. As a method of blending the pigment composition with the thermoplastic polymer, a pigment composition and a thermoplastic polymer chip are dry blended, and a method of melt-kneading the same, a molten pigment composition and a molten thermoplastic polymer are used. There is a method of kneading.

Moldings of various shapes are obtained by melt molding using a mixture of a pigment composition and a thermoplastic polymer, and the temperature of the melt molding is not lower than the melting point of the thermoplastic polymer used. As the melt molding method, there are 1) an injection molding method, a compression molding method, 2) a film or sheet molding method using a calender method, an inflation method, and a stretch film forming method, and 3) a melt spinning method for obtaining a fibrous molded product. is there.

In the present invention, in order to uniformly color the thermoplastic polymer molded product, the graft copolymer can be appropriately selected according to the type of the thermoplastic polymer or pigment used. Usually, a graft copolymer having a melting temperature lower than the melting point of the thermoplastic polymer is used, and the melting temperature is from room temperature to 2
Although it is 80 ° C, it is preferable to use a graft copolymer having a melting temperature of 80 to 250 ° C.

[0031]

[Examples] In order to make the constitution and effects of the present invention more concrete, a synthesis example of a graft copolymer will be described as Test Category 1.
Further, an example of preparation of a pigment composition is shown as a test category 2, and an example of evaluation of a melt-molded article and a molded article using a mixture of the pigment composition and a thermoplastic polymer is given as a test category 3. In each of the following examples, "part" means "part by weight" and "%" means "% by weight". The characteristic values of the graft copolymer are measured as follows.

Molecular Weight of Polysiloxane Block in Graft Copolymer A part of an aqueous emulsion of polysiloxane before graft polymerization of vinyl monomer is taken out, tetrahydrofuran is added thereto, and the mixture is shaken and agitated to remove polysiloxane. Extracted. In this case, in order to enhance the extraction effect of polysiloxane from the aqueous emulsion, an appropriate amount of calcium chloride was added as needed. Tetrahydrofuran was distilled off from the obtained polysiloxane extract under reduced pressure to obtain a polysiloxane for measuring a molecular weight.
The molecular weight (in terms of polystyrene) was measured using GPC.

Melting temperature The sample was placed in a melting point measuring device, and the temperature rising rate was adjusted to 1 ° C. per minute from the point where the sample began to be heated and melted, and the temperature when the entire sample was melted was measured. And set this as the melting temperature.

Test Category 1 (Synthesis Example of Graft Copolymer) -Synthesis Example 1 Octamethylcyclotetrasiloxane 100.6 g
(0.34 mol), hexamethyldisiloxane 1.6 g
(10 mmol), γ-methacryloxypropylmethyldimethoxysilane 2.0 g (8.8 mmol), dodecylbenzenesulfonic acid 1.1 g, and ion-exchanged water 315 g.
It was dissolved in and homogenized with a homomixer. Next, this was homogenized by passing through a homogenizer to obtain 421 g of silanol compound aqueous emulsion. This was placed in a flask and polycondensed at 80 ° C. for 5 hours. Then, the mixture was gradually cooled for 16 hours, neutralized with a saturated aqueous solution of sodium carbonate, and filtered to obtain an aqueous polysiloxane emulsion. The aqueous emulsion of polysiloxane obtained here was charged into another flask, and 1.6 g of potassium persulfate and 400 g of ion-exchanged water.
Was added and heated to 70 ° C. After replacing the reaction system with nitrogen,
45 g (0.43 mol) of styrene was added dropwise over 2 hours. After the completion of dropping, heat to 80 ° C. and age for 4 hours.
The mixture was gradually cooled to ℃ and filtered. Calcium chloride in the filtrate 11.
After salting out by adding 6 g, it was filtered, washed with 1000 g of warm water, and dried. A white powder was obtained. The white powder graft copolymer thus obtained had a polysiloxane block molecular weight of about 11,000.

Synthetic example 2 156.9 g of octamethylcyclotetrasiloxane
(0.53 mol), hexamethyldisiloxane 1.4 g
(8.4 mmol), γ-methacryloxypropylmethyldimethoxysilane 3.1 g (13.5 mmol), dodecylbenzenesulfonic acid 1.7 g, and ion-exchanged water 49.
It was dissolved in 0 g and an aqueous polysiloxane emulsion was obtained in the same manner as in Synthesis Example 1. The aqueous polysiloxane emulsion obtained here, 0.53 g of potassium persulfate, 245 g of ion-exchanged water, and 18.2 g of methyl methacrylate (0.
18 mol) and calcium chloride, and further Synthesis Example 1
A white powder was obtained in the same manner as. The white powder graft copolymer thus obtained had a polysiloxane block molecular weight of about 20,000.

Synthesis Example 3 Octamethylcyclotetrasiloxane 97.7 g (0.
33 mol), γ-glycidoxypropylmethyldimethoxysilane 4.3 g (19.6 mmol), γ-methacryloxypropylmethyldimethoxysilane 7.6 g (3
2.4 mmol) were mixed to obtain a mixed siloxane monomer. This was added to 300 g of ion-exchanged water in which 1.0 g of dodecylbenzenesulfonic acid was dissolved, dispersed with a homomixer, and then uniformly emulsified with a homogenizer to obtain an aqueous emulsion of silanol compound. Then, 31 g of dodecylbenzene sulfonic acid and 217 g of ion-exchanged water were charged into a flask and well dissolved, and then the temperature was adjusted to 80 to 8
The temperature was raised to 5 ° C., and the silanol compound aqueous emulsion was added dropwise over 2 hours. After the dropping is completed, 1 at 85 ℃
Aged for hours. After aging, the mixture was cooled to room temperature and neutralized with sodium carbonate to obtain an aqueous emulsion of polysiloxane. Ion-exchanged water (483 g) and potassium persulfate (1.5 g) were dissolved in the obtained polysiloxane aqueous emulsion, transferred to another flask, and heated to 70 ° C. while flowing nitrogen. And styrene 100g (0.96mol)
Was slowly added dropwise. After completion of the dropping, the mixture was aged for 3 hours and calcium chloride was used to obtain a white powder in the same manner as in Synthesis Example 1. The thus obtained white powder graft copolymer had a polysiloxane block molecular weight of about 67,000.

Synthesis Example 4 The polysiloxane aqueous emulsion obtained in Synthesis Example 3 was placed in a flask, and 483 g of ion-exchanged water, 1.5 g of potassium persulfate, and trifluoroethyl methacrylate 100 were added.
A white powder was obtained in the same manner as in Synthesis Example 1 using g (0.59 mol) and calcium chloride.

Synthesis Example 5 An aqueous emulsion of the polysiloxane obtained in Synthesis Example 1 was placed in a flask, 400 g of ion-exchanged water and 1.6 g of potassium persulfate were added, and the mixture was heated to 70 ° C. After substituting the reaction system with nitrogen, 45 g (0.43 mol) of styrene was added dropwise. After completion of the dropping, the mixture was heated to 80 ° C. and kept for 1 hour. Further, 50 g of an aqueous solution containing 5.8 g (0.04 mol) of sodium allylsulfonate was added dropwise. 80 after dropping
The mixture was heated to ° C and aged for 2 hours, and white powder was obtained in the same manner as in Synthesis Example 1. The white powder graft copolymer thus obtained contains sulfonic acid groups in the vinyl polymer block, and the polysiloxane block has a molecular weight of about 1100.
It was 0.

Synthesis Example 6 153.7 g of octamethylcyclotetrasiloxane
(0.52 mol), methyltrimethoxysilane 15.0
g (0.11 mol), γ-methacryloxypropylmethyldimethoxysilane 6.2 g (27.0 mmol), dodecylbenzenesulfonic acid 2.8 g and ion-exchanged water 23
It was dissolved in 4 g, and an aqueous polysiloxane emulsion was obtained in the same manner as in Synthesis Example 1. Aqueous emulsion of polysiloxane obtained here, potassium persulfate 2.5 g, deionized water 967.5 g, methyl methacrylate 82.5 g
(0.83 mol), cyclohexyl methacrylate 8
A white powder was obtained in the same manner as in Synthesis Example 1 using 2.5 g (0.49 mol) and calcium chloride. The white powder graft copolymer thus obtained had a polysiloxane block molecular weight of about 80,000.

Synthesis Example 7 Octamethylcyclotetrasiloxane 97.7 g (0.
33 mol), 1.8 g of hexamethyldisiloxane (1
1.1 gm), γ-methacryloxypropylmethyldimethoxysilane 3.2 g (13.8 mmol), methyltrimethoxysilane 19.0 g (0.14 mol), dodecylbenzenesulfonic acid 2.8 g and ion-exchanged water 23
It was dissolved in 4 g, and an aqueous polysiloxane emulsion was obtained in the same manner as in Synthesis Example 1. Then, an aqueous emulsion of the polysiloxane obtained above, potassium persulfate 2.
5 g, deionized water 967.5 g, methyl methacrylate 50.0 g (0.50 mol), 4-fluorostyrene 25.0 g (0.20 mol) and calcium chloride were used in the same manner as in Synthesis Example 1. , White powder was obtained. The thus-obtained white powder graft copolymer had a polysiloxane block molecular weight of about 85,000.

Synthesis Example 8 The polysiloxane aqueous emulsion obtained in Synthesis Example 6 was charged into a flask, and 967.5 g of ion-exchanged water, 2.5 g of potassium persulfate, 148.5 g of methyl methacrylate.
(1.49 mol), 2-ethylhexyl methacrylate 16.5 g (0.13 mol), and calcium chloride were used in the same manner as in Synthesis Example 6 to obtain a white powder. The white powder graft copolymer thus obtained had a polysiloxane block molecular weight of about 80,000.

The contents of the graft copolymers obtained in Synthesis Examples 1 to 8 were calculated from the charging ratio of the synthetic raw materials, and the results are summarized in Table 1.

[0043]

[Table 1]

In Table 1, B-1: polystyrene block B-2: polymethylmethacrylate block B-3: polytrifluoroethylmethacrylate block B-4: styrene / sodium allylsulfonate = 10
/ 1 (molar ratio) copolymer block B-5: methyl methacrylate / cyclohexyl methacrylate = 63/37 (molar ratio) copolymer block B-6: methyl methacrylate / 4-fluorostyrene = 71/29 (molar ratio) Copolymer block B-7: Methyl methacrylate / 2-ethylhexyl methacrylate = 92/8 (molar ratio) Copolymer block

Test Category 2 (Preparation Example of Pigment Composition) Examples 1 to 5 The graft copolymers and pigments shown in Table 2 were melt-kneaded with a Labo Plastomill and melt-extruded, and then the pigment was passed through a tip cutter. A composition was prepared. Melt kneading temperature is
In the cases of Examples 1 to 3, the temperature was 230 ° C, and in Examples 4 and 5, the temperature was 180 ° C.

[0046]

[Table 2]

In Table 2, * 1: a mixture of Synthesis Example 2 / Synthesis Example 5 = 4/1 (weight ratio) P-1: a mixture of phthalocyanine blue pigment / carbon black = 28/2 (weight ratio) P-2 : Mixture of isoindolinone pigment / berylene red pigment / carbon black = 12/5/3 (weight ratio)

Examples 6 to 10 Using the graft copolymer, carbon black, milled carbon fiber and polycarbonate resin shown in Table 3, melt-kneading with a Labo Plastomill and melt-extruding, and then chip-shaped pigment through a chip cutter. A composition was prepared. The melt-kneading temperature was 230 ° C. in the case of Examples 6 to 8, and Examples 9 and 1
When it was 0, the temperature was 290 ° C.

[0049]

[Table 3]

Test Category 3 (Melting molding and evaluation example of molded article) Examples 11 to 13 Pigment compositions (M-1 to M-3) obtained in Test Category 2 were melted at 180 ° C and melted. It was a thing. Polyethylene terephthalate 100 obtained by melting this melt at 300 ° C.
The mixture was metered into 5 parts per part, mixed with a static mixer, discharged from a spinneret, and spun and drawn according to a usual method to obtain 75 denier 24 filament polyester yarn. In each of the examples, there is no stain or clogging of the spinneret, and the spinning and drawing state is good,
No stain was generated on the stretching roller or the guide.

Comparative Example 1 15 parts of the pigment composition (R-1) and 86.5 parts of polyethylene terephthalate chips were dry blended, and 3 parts thereof were added.
Melted at 00 ° C. Melt-spin using this melt,
A polyester yarn of 5 denier 24 filaments was obtained.
During spinning, the spinneret was significantly soiled. The pigment composition (R-1) used here was phthalocyanine blue pigment 2
7 parts, carbon black 3 parts and polyester chip 2
It was obtained by melt-kneading 70 parts at 300 ° C.

Comparative Example 2 Polyethylene terephthalate 100 melted at 300 ° C.
The pigment dispersion liquid (R-2) was metered into 5 parts to 5 parts, and the same procedure as in Examples 11 to 13 was performed to obtain 7 parts.
A polyester yarn of 5 denier 24 filaments was obtained.
A large amount of gas was generated from the melt during the spinning process, and many yarn breakages occurred during the drawing process. The pigment dispersion liquid (R-2) used here was 70 parts of 2,2-di (hydroxyphenyl) propanedilaurate as a dispersion medium and phthalocyanine blue pigment / carbon black = 9 as a pigment.
It is obtained by kneading 30 parts of the mixture of 1/1 (weight ratio) with a roll kneader.

Examples 14 and 15 Each of the pigment compositions (M-4 and M-5) obtained in Test Category 2 was melted at 180 ° C., and the melt was melted at 280 ° C. to obtain nylon 6 of 100. The mixture was press-fitted and mixed from the spinning head so as to be 4 parts per part. This was discharged from the spinneret to obtain an undrawn yarn of 224 denier 24 filaments. This unstretched yarn was stretched 3.2 times according to the usual method,
A nylon drawn yarn of 70 denier 24 filament was obtained. In the spinning process, the extrusion pressure of the melt was stable in the range of 1.1 to 1.2 times that in the case of Nylon 6 alone containing no pigment composition. Further, in the drawing step, there was no yarn breakage and almost no stain on the guides or rollers was observed.

Comparative Examples 3 and 4 The pigment-dispersed pastes (R-3 and R-4) at room temperature were mixed so that nylon 6 in a molten state at 280 ° C. was 4 parts per 100 parts, and Nylon stretched yarn of 70 denier 24 filament was obtained in the same manner as in Examples 14 and 15. In the spinning process, the extrusion pressure of the melt varied in the range of 1.5 to 2.5 times that in the case of Nylon 6 alone without the pigment dispersion paste. Further, many yarn breakages occurred in the spinning process and the drawing process. The pigment pastes (R-3, R-4) used here were prepared as follows. R-3: adipic acid / sodium sulfoisophthalic acid =
80 parts of polyester having an average molecular weight of 3000 containing 95/5 (molar ratio) and 1,6-hexanediol / ethylene glycol = 1/1 (molar ratio) as a monomer component, and isoindolinone pigment / berylene red Pigment / carbon black = 12/5/3 (weight ratio) and 20 parts of a pigment. R-4: 80 parts of poly ε-caprolactone having an average molecular weight of 1500, which is obtained by adding ε-caprolactone to glycerin,
A pigment obtained by using 20 parts of the pigment of R-3 above.

The color spots of the synthetic fiber yarns obtained in Examples 11 to 15 and Comparative Examples 1 to 4 were evaluated according to the following criteria.
The results are shown in Table 4. -Evaluation of color spot A plain weave fabric was prepared using each synthetic fiber yarn. A light source was placed on the woven fabric so that the incident angle was 45 degrees, and the color spots of the woven fabric were visually observed under transmitted light, and evaluated according to the following criteria. ◯: No color spots are observed Δ: Slight color spots are observed ×: Color spots are significantly observed

[0056]

[Table 4]

Examples 16 to 21 and Comparative Examples 5 to 11 The materials shown in Table 5 were taken in a predetermined ratio with respect to 100 parts by weight of the polycarbonate resin chip, sufficiently dry blended with a tumbler, and then extruded at 280 ° C. It was melt-kneaded by a ruder. Using this melt-kneaded product, a cup-shaped molded product having a wall thickness of 4 mm, a height of 20 mm and a bottom diameter of 6.3 mm was continuously shot for 30 shots at a cylinder temperature of 280 ° C. and a mold temperature of 100 ° C. With respect to the 30 molded products, the colored state of the surface was visually observed and evaluated according to the following criteria, and the number of each grade is shown in Table 5. Grade A: Homogeneously colored and has a smooth surface Grade B: There is a colored surface, but there is a smooth surface Grade C: There is a markedly colored spot, and the surface is rough

[0058]

[Table 5]

In Table 5, M-6 to M-10: Pigment composition obtained in Test Category 2 A-1: Acetylated product of ε-caprolactone adduct of trimethylolpropane (average molecular weight 50000) A-2: Terephthalic acid (Average molecular weight 30,000) F-1: carbon black / milled carbon fiber = 1/1
(Weight ratio) mixture F-2: carbon black R-5: F-1 / A-1 = 2/1 (weight ratio) mixture R-6: F-1 / A-2 = 2/1 (weight ratio) Ratio) mixture R-7: F-2 / A-1 = 10/3 (weight ratio) mixture R-8: F-2 / A-2 = 10/3 (weight ratio) mixture

[0060]

As is apparent from the above, the present invention described above can be applied to a wide variety of general molded products obtained by melt molding without hindering the molding process and reducing the physical properties thereof. There is an effect that the molded product can be uniformly colored.

Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display area C09C 3/12 PCH 6904-4J // B29B 15/08 7722-4F

Claims (2)

[Claims] 1. A pigment and a graft copolymer in which a vinyl polymer block is graft-bonded to a polysiloxane block through a divalent organic linking group, the pigment / the graft copolymer = 1/10 to 10 / A pigment composition, characterized in that it is contained in a ratio of 1 (weight ratio), and the total amount of these is 30% by weight or more, and the balance comprises a thermoplastic polymer. 2. A thermoplastic polymer, which comprises melt-molding a mixture obtained by blending the pigment composition according to claim 1 with a thermoplastic polymer at a temperature equal to or higher than the melting point of the thermoplastic polymer. Method for coloring molded article.