JP2000204245A - Plastic additive - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an additive which is added to a plastic to give a composition not suffering from a dye bleeding and discoloration even when molded at a high temperature to give a molding excellent in design properties realizing a shade of color by constituting the additive of a polyimide-based polymer, forming the form of the additive of a fiber and/or a film, and/or particles, and specifying the maximum diameter and the maximum length in its cross section to be specified dimension or smaller. SOLUTION: This additive desirably comprises a composite material of a dye and/or a coloring pigment and a polyimide-based polymer, is in the form of a fiber and/or a film, and/or particles, and has the maximum diameter of 3 mm or below, desirably, 50 μm or below and the maximum length of 5 mm or below, desirably, 500 μm or below in its cross section. It is desirable for the sake of brilliancy that a metal layer, desirably, an aluminum layer is laminated on at least either surface of the additive. It is desirable that the polyimide- type polymer is a polyamide-imide containing 4,4'-diaminodicyclohexylmethane residues and/or isophoronediamine residues.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an additive mainly used for a resin molded article, and provides a molded article which is free of color flow and discoloration even at the time of molding at 250.degree. It is intended to provide a heat-resistant coloring material which can be used.

[0002]

2. Description of the Related Art Heretofore, as a technique for obtaining a molded article having a rich design that expresses color shading, a technique of dispersing colored cellulosic fibers in polypropylene or the like is known. However, ABS resin, polycarbonate resin,
25 for molding such as polyethylene terephthalate resin
A temperature of 0 ° C or higher is required, and the above-mentioned cellulose-based colored fibers cannot be used due to discoloration due to resin deterioration due to heat during molding.
At present, there is no coloring material that does not cause color flow or discoloration at the time of molding at 250 ° C. or higher. In addition, the color flow refers to a structure in which a colored pigment is encapsulated in a capsule made of a heat-resistant resin, and when heated and molded at a temperature equal to or higher than the glass transition temperature of the capsule resin, the capsule is broken and the internal pigment is contained in the molded resin. A phenomenon that flows out.

[0003]

It is an object of the present invention to produce a coloring material free from color drift and discoloration even when molding a resin having high heat resistance.

[0004]

Means for Solving the Problems In order to solve the above-mentioned problems, a fine colored material containing a dye, a pigment and a metal in a colorless and transparent heat-resistant polyimide resin is formed into a molding resin. Knead and mold. As a result, the present inventors have found that a molded material having a rich design can be obtained without coloring or discoloration of dyes and pigments, and the present invention has been achieved. That is, the present invention is characterized in that the shape is fibrous or / and film or / and granular, and the maximum diameter of the cross section is 3 mm or less and the maximum length is 5 mm or less. Plastic additives. In a preferred embodiment, the plastic additive is a composite of a dye or / and a color pigment and a polyimide-based polymer. Preferably, a metal layer is further laminated on at least one surface of the plastic additive, and the metal layer is preferably aluminum. Further, it is preferable that the polyimide polymer of the plastic additive is a polyamideimide containing a 4,4′-diaminodicyclohexylmethane residue or / and an isophoronediamine residue, and the maximum diameter of the cross section of the plastic additive is 50 μm or less. Preferably, the maximum length is 500 μ or less.

[0005]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be described sequentially. The dyes or pigments used in the present invention must not cause thermal decomposition and discolor at resin molding temperatures of 250 ° C. or higher. Organic or inorganic pigments are suitable, and inorganic pigments include yellow iron oxide, titanium yellow, red iron oxide, ultramarine, cobalt blue, cobalt violet,
Organic pigments such as titanium oxide, zinc oxide, and carbon black include azo pigments, phthalocyanine pigments, dye lakes, condensed polycyclic pigments, and the like. Particularly preferred are inorganic pigments and organic pigments such as condensed azo pigments, thioindigo pigments, phthalocyanine pigments, perylene pigments, quinacridone pigments, dioxazine pigments, isoindolinone pigments, and quinophthalone pigments.

The polyimide polymer used in the present invention will be described. The polyimide-based polymer used in the present invention is preferably colorless and transparent and heat-resistant. The term “colorless and transparent” used herein refers to a wavelength of 50 μm for a resin film having a thickness of 50 μm.
It means that the light transmittance at 0 nm is 80% or more,
Preferably, it is 90% or more. The term “heat resistance” as used herein means that the glass transition temperature of the resin is 230 ° C. or higher, and preferably 250 ° C. or higher. In general, polyimide-based polymers have high heat resistance but are colored yellow to brown, and do not dissolve in most organic solvents when they contain imide rings. However, polyimide-based polymers used in the present invention are molded at 250 ° C or higher. It is resistant to temperature, is colorless and transparent, and is soluble in an organic solvent while containing an imide ring.

A polyimide polymer satisfying the above is
It is formed from a diamine or a derivative thereof and a polyfunctional carboxylic acid anhydride or a derivative thereof. When expressed in the form of a diamine, the diamine component belonging to Group A below is included in an amount of 70 to 100 mol% of the total diamine component. If it is less than 70 mol%, the coloring becomes unsatisfactory, which is inconvenient. Group A: bis- [4- (3-aminophenoxy) phenyl]
Propane, bis- [4- (2-aminophenoxy) phenyl] propane, bis- [4- (3-aminophenoxy)
Phenyl] sulfone, bis- [4- (2-aminophenoxy) phenyl] sulfone, 1,3-bis (3-aminophenoxy) benzene, bis- [4- (3-aminophenoxy) phenyl] hexafluoropropane, 3, 3
'-Diaminodiphenylsulfide, 3,3'-diaminodiphenylsulfone, 3,3'-diaminobenzophenone, 3,3'-diaminodiphenylpropane, 3,
3'-diaminodiphenylhexafluoropropane,
4,4 '-[1,3 phenylenebis (1-methylethylidene) bisaniline, 3,3'-[1,3-phenylenebis (1-methylethylidene) bisaniline, isophoronediamine, 4,4'-diaminodicyclohexylmethane , 3,3'-Diaminodicyclohexylmethane, 1,
One or more of 3-bisaminomethylcyclohexane, 1,4-bisaminomethylcyclohexane and the like.

If the polyfunctional carboxylic acid component forming the polyimide-based polymer of the present invention is shown in the form of an acid or an acid anhydride, it contains at least 30 mol% of the following Group B acid component. If it is less than 30 mol%, the heat resistance becomes poor, which is inconvenient. Group B: pyromellitic anhydride, trimellitic anhydride, diphenyl ether-3,3'-4,4'tetracarboxylic anhydride, benzophenone-3,3'-4,4'-tetracarboxylic anhydride, biphenyl- 3,3'-4,4'-
Tetracarboxylic anhydride, diphenylsulfone-3,
Aromatic polyfunctional carboxylic acid components such as 3'-4,4'-tetracarboxylic anhydride or alkylene glycol bis [anhydrotrimellitate] having 1 to 6 carbon atoms;

In addition to the above-mentioned diamine component and carboxylic acid component, other diamine components and carboxylic acid components may be contained as long as heat resistance, solvent solubility, non-coloring property, transparency and the like are allowed. Examples of the diamine component include m-phenylenediamine, p-phenylenediamine, 4,4′-diaminodiphenylmethane, 2,4-tolylenediamine, and 1,4-tolidine. Examples of the acid component include aliphatic or alicyclic dicarboxylic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid, dodecane diacid, and 1,4-cyclohexane dicarboxylic acid, terephthalic acid, isophthalic acid, orthophthalic acid, Aromatic carboxylic acids such as 6-naphthalenedicarboxylic acid can be mentioned.

The polyimide polymer of the present invention is a polymer containing an imide bond in the molecule as the above-mentioned diamine component residue and polyfunctional carboxylic acid component residue, and examples thereof include polyimide, polyamideimide, polyetherimide, and polyesterimide. However, polyamideimide is preferred. By appropriately selecting and copolymerizing the above-mentioned diamine component and polyfunctional carboxylic acid component, a composition satisfying all of heat resistance, solvent solubility, non-colored transparency and the like can be obtained.

The polyimide polymer used in the present invention can be produced by a usual method such as a diamine method or an isocyanate method, but the isocyanate method is preferred from the viewpoint of reactivity, cost and the like. When polymerizing by the isocyanate method, it is obtained by heating a diisocyanate as a diamine component and a polyfunctional acid component in an organic solvent. Examples of the polymerization solvent include ether solvents such as diethylene glycol dimethyl ether and tetrahydrofuran, ketone solvents such as cyclohexanone, nitrile solvents such as acetonitrile, nitro solvents such as nitromethane, ester solvents such as γ-butyrolactone and cellosolve acetate, dimethylacetamide, Amide solvents such as N-methyl-2-pyrrolidone, sulfur-containing solvents such as dimethylsulfoxide and sulfolane, and solvents having a relatively high relative dielectric constant such as tetramethylurea are preferred.

The polymerization temperature is preferably 50 to 200 ° C., and a tertiary amine compound, an alkali metal compound, an alkaline earth metal compound, a tin compound, a titanium compound, a zinc compound, or the like may be used as a catalyst.

As a measure of the molecular weight of the polyimide-based polymer of the present invention, 30% in N-methyl-2-pyrrolidone is used.
0.2 to 2.0 dl /
g, and preferably 0.5 to 1.6. 0.2d
If it is less than 1 / g, the shape retention of the composite colorant is poor, which is not preferable. If it exceeds 2.0 dl / g, the solution viscosity will increase,
This is inconvenient when complexing with dyes and pigments.

Next, a method for producing the plastic additive of the present invention will be described. The dye and / or pigment may be coated with a heat-resistant, non-colored and transparent polyimide-based polymer. One specific method is to dissolve the polyimide-based polymer of the present invention in a solvent and further dissolve or / and finely disperse a dye or / and a color pigment. This is a method in which the obtained colored solution or / and dispersion liquid is coated on a release film, dried, peeled off, and finely cut (pulverized) to form a film-like fine piece. The second is a method of forming fibers by dry spinning or wet spinning (or dry-wet spinning) from the above colored solution or / dispersion, and then finely cutting (crushing) to obtain fibrous fine fragments. . As a variant, fine colored fibrous fragments can be produced by spinning the above colored solution or / and dispersion into a poor solvent at a high speed and applying a shearing force in the solution.

As another method, a granular composite can be prepared by spraying and drying the above colored solution or / and dispersion liquid in heated air (or an inert gas). Alternatively, a dye or pigment microcapsule can be prepared by mixing and stirring an aqueous dispersion of a dye or color pigment and an organic solvent solution of a polyimide polymer.

As a preferred embodiment of the plastic additive of the present invention, a case where a metal layer is further compounded will be described.
The above-mentioned colored solution or / and dispersion liquid is coated on both sides of a metal foil and dried to form a three-layer film of a colored polyimide layer / metal foil / colored polyimide layer, and then finely cut (crushed) into a three-layer film. Form the plastic additive of the strip. By mixing this with a molding resin, a glittering colored molded product can be obtained, and a design with a different taste is expected. In the above, if a plastic additive obtained by coating and drying a colorless and transparent polyimide-based resin solution containing no dye or pigment on the metal foil and then cutting (crushing) the resin is mixed with the molding resin, the molding becomes a glittering silver color. Things are obtained.

As the solution of the polyimide-based polymer, the solution at the time of polymerization can be used as it is.
In some cases, the solvent may be diluted with another solvent including a poor solvent, or the solvent may be removed by a reprecipitation method or the like at the time of polymerization and then redissolved in another solvent.

As the solvent for the polyimide polymer of the present invention, ether solvents such as diethylene glycol dimethyl ether and tetrahydrofuran, methyl ethyl ketone,
Ketone solvents such as cyclohexanone, nitrile solvents such as acetonitrile, nitro solvents such as nitromethane, ester solvents such as cellosolve acetate and γ-butyrolactone, amide solvents such as dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone solvent,
In addition to good solvents such as alcoholic solvents such as ethyl alcohol and ethyl cellosolve, toluene, xylene, solvesso and the like can be used as diluting solvents for these.

The shape of the plastic additive of the present invention may be fibrous, film-like or granular, but the maximum diameter of the cross section is 3 mm or less, preferably 1 mm or less, particularly preferably 100 μm or less. Its maximum length is 5 mm or less, preferably 1 mm or less. In any case, if it exceeds 3 mm or 5 mm, it is not preferable from the viewpoint of the design of the colored molded product, and in addition, a flow abnormality or the like occurs during melt molding, which is inconvenient.

[0020]

When the plastic additive of the present invention is mixed with an ABS resin, a polycarbonate resin or the like and melt-molded, 2
Even at the time of molding at 50 ° C. or more, there is no color flow or discoloration, and a colored molded product having a good design can be obtained. This is due to the action of sealing a heat-resistant dye or color pigment with a heat-resistant transparent non-colored polyimide-based polymer.

[0021]

EXAMPLES The present invention will be described below with reference to examples, but of course is not intended to limit the present invention. The measurement was performed by the following method. 1. Logarithmic viscosity: A solution prepared by dissolving 0.5 g of a polymer in 100 ml of N-methyl-2-pyrrolidone was measured at 25 ° C. with an Ubbelohde viscometer. 2. Glass transition temperature: measured by the TMA method. 3. Light transmittance: measured with a UV-visible spectrophotometer. 4. Moldability: Color flow and uniformity of the molded product were visually observed.

Example 1 Synthesis of Polyamideimide Resin A In a reaction vessel equipped with a stirrer, a cooling tube, a thermometer, and a nitrogen introducing tube, 96 g of trimellitic anhydride, 86 g of cyclohexanedicarboxylic acid, and 222 g of isophorone diisocyanate were charged with γ-butyrolactone. Charge with 316g, 150 ℃
For 2 hours, and then the temperature was raised to 180 ° C., and the reaction was further performed for 3 hours. While cooling, 158 g of N-methyl-2-pyrrolidone was added for dilution. This polymer has a logarithmic viscosity of 0.45 dl / g, a glass transition temperature of 260 ° C., and a wavelength of 550 nm of a 30 μm thick film formed by a casting method.
Was 91%.

Example 2 Synthesis of polyamideimide resin B Trimellitic anhydride 192 was placed in the same reaction vessel as in Example 1.
g and isophorone diisocyanate (222 g) were charged together with γ-butyrolactone (326 g), reacted at 150 ° C. for 2 hours, heated to 180 ° C., and further reacted for 3 hours.
While cooling, 163 g of methyl 2-pyrrolidone was added for dilution. The logarithmic viscosity of this polymer is 0.38 dl
/ G, the glass transition temperature was 293 ° C., and the light transmittance of the cast film having a thickness of 30 μ at a wavelength of 550 nm was 90%.

(Example 3) Synthesis of polyamideimide C Trimellitic anhydride 192 was placed in the same reaction vessel as in Example 1.
g, dicyclohexylmethane diisocyanate 157
g and isophorone diisocyanate (89 g) were charged together with 350 g of γ-butyrolactone, reacted at 150 ° C. for 2 hours, and then heated to 180 ° C. for further 3 hours. While cooling, 175 g of N-methyl-2-pyrrolidone was added for dilution. The logarithmic viscosity of this polymer is 0.47 dl / g,
The cast film having a glass transition temperature of 238 ° C. and a thickness of 30 μm had a light transmittance of 90% at a wavelength of 550 nm.

Example 4 Production of Plastic Additives and Design Moldings-1 Preparation of Coating Solution A pigment and an additive were blended with a polyamideimide A solution according to the following formulation, stirred for about 30 minutes with a dissolver, and kneaded with a three-roll mill. <Blending Formula> Polyamideimide A 100 (parts) NOVOPERM YELLOW P-HG ^*) 6 Toyobo Byron RV220 1.2 N-methyl-2-pyrrolidone 11 ^*) manufactured by Clariant Japan Co. Then, an equal amount mixed solvent of ethanol and toluene was added to this dispersion so that the solid content concentration became 25%. 2. Coating process The above pigment dispersion is applied to one side of a soft rolled aluminum foil with a film thickness of 1
After roll coating to 5 μm and drying at 80 ° C. for 1 minute, the same coating and drying were performed on the back surface, and the
Heat treatment was performed at a temperature of 3 ° C. for 3 minutes. 3. Grinding process About 100 sheets of the above-mentioned coating sheets were stacked and cut with a guillotine cutter so that both the width and the length became about 0.5 mm to obtain a coloring additive. Add this powder to acrylonitrile butadiene-styrene resin (ABS resin)
% And injection-molded at 250 ° C. to obtain a design molded product without peeling or color flow.

Example 5 Production of Plastic Additives and Designed Molded Article 2 In the same manner as in Example 4, except that the polyamideimide A was changed to the polyamideimide B and the pigment was changed to bengara during the formulation of the coating liquid. A coloring additive was produced. This powder was mixed with a polyethylene terephthalate resin at 3% to obtain 280
As a result of injection molding at a temperature of ° C., a red dot-shaped design product without peeling or color flow was obtained.

Example 6 Production of Plastic Additives and Designed Molding-3 The same method as in Example 4 except that polyamideimide A was changed to polyamideimide C and the pigment was changed to phthalocyanine blue in the formulation of the coating liquid. To produce a coloring additive. This powder is mixed with 3% of polycarbonate resin to obtain 2
Injection molding was performed at 80 ° C. The molded product was a uniform design molded product without color flow.

(Example 7) Manufacture of plastic additive material and design molded product-4 The dispersion liquid kneaded with a three-roll mill in Example 4 was transferred to a tank, transported by a gear pump, and put into water through a nozzle having a diameter of 0.1 mm. I pushed it out. After removing solvent sufficiently, length is 1mm
And dried to obtain a thread-like coloring additive. This colored composite was mixed with an ABS resin under the same conditions as in Example 4 and injection-molded. A uniform design molded article without color flow was obtained.

(Example 8) Production of plastic additive material and design molded product-5 A silver color additive and ABS were produced in the same manner as in Example 4 except that a clear solution obtained by removing the coloring pigment from the coating solution of Example 4 was used. A resin molded body was manufactured. A silver-colored molded product without color drift was obtained.

(Comparative Example 1) When the coating sheet of Example 4 was pulverized with a guillotine cutter, a colored composite was obtained in the same manner as in Example 4 except that the width was 5 mm and the length was 7 mm. The mixture was injection-molded by mixing 3%, but the colored composite was cracked, and a uniform molded article having a rough surface such as a rough surface could not be obtained.

Comparative Example 2 A colored composite was produced in the same manner as in Example 4 except that the polyamideimide A of Example 4 was changed to the following polymer solution, and N-methyl-2-pyrrolidone was changed to methyl ethyl ketone. <Resin solution> TOYOBO Polyester Byron 200 40 parts (glass transition temperature 76 ° C) Toluene 30 Methyl ethyl ketone 30 3% of this colored composite was mixed with ABS resin and injection-molded in the same manner as in Example 4. A uniform design molded product could not be obtained.

[0032]

According to the present invention, a resin mixed with a colorant which is a composite of a colorless and transparent polyimide polymer having a high glass transition temperature is mixed with 25
By injection molding at 0 ° C. or higher, it was possible to obtain a molded product in which the colored portion had a clear contrast with the non-colored portion.

 ────────────────────────────────────────────────── ─── Continuing from the front page (72) Inventor Hiroki Yamaguchi 2-1-1 Katata, Otsu-shi, Shiga F-term in Toyobo Co., Ltd. Research Laboratory (reference) 4J002 AA011 BN151 CF061 CG001 CM042 FA002 FA042 FA082 FD096

Claims (6)

[Claims] The present invention is characterized in that it is made of a polyimide-based polymer and has a fibrous shape and / or a film shape and / or a granular shape, and has a maximum cross-sectional diameter of 3 mm or less and a maximum length of 5 mm or less. Plastic additives. 2. The plastic additive according to claim 1, which is a composite of a dye and / or a coloring pigment and a polyimide-based polymer. 3. The plastic additive according to claim 1, wherein a metal layer is further laminated on at least one surface of the plastic additive. 4. The polyimide-based polymer as a plastic additive is a polyamideimide containing 4,4′-diaminodicyclohexylmethane residue and / or isophoronediamine residue.
Plastic additives. 5. The plastic additive according to claim 3, wherein the metal layer is aluminum in the plastic additive on which the metal layer is laminated. 6. The maximum diameter of the cross section of the plastic additive is 50.
The plastic additive according to any one of claims 1 to 5, wherein the plastic additive has a maximum length of 500 µ or less.