WO2014027593A1

WO2014027593A1 - Coloring agent composition, aromatic polycarbonate resin composition, molded article, and plasticizer for aromatic polycarbonate resin

Info

Publication number: WO2014027593A1
Application number: PCT/JP2013/071392
Authority: WO
Inventors: 博文山口; 芳明安井
Original assignee: Dic株式会社
Priority date: 2012-08-16
Filing date: 2013-08-07
Publication date: 2014-02-20
Also published as: KR102071326B1; JPWO2014027593A1; CN104583318B; TW201412870A; CN104583318A; KR20150044873A; JP5578387B2; TWI575019B

Abstract

The purpose of the present invention is to provide: a plasticizer for an aromatic polycarbonate resin, which has excellent heat resistance to such an extent that the plasticizer can withstand the melt kneading with an aromatic polycarbonate resin, can improve the loosening property of a pigment in a composition that contains the pigment at a high concentration, and can prevent the formation of coarse particles; a coloring agent composition prepared using the plasticizer; an aromatic polycarbonate resin composition produced by diluting the composition with an aromatic polycarbonate resin; and a molded article produced from the aromatic polycarbonate resin composition. For the purpose of achieving the purpose, a plasticizer for an aromatic polycarbonate resin is provided, which comprises an alkyl ester of an aromatic polycarboxylic acid, wherein an alkyl chain in the alkyl ester is a linear alkyl ester chain having 16 to 26 carbon atoms.

Description

Colorant composition, aromatic polycarbonate resin composition, molded article, and plasticizer for aromatic polycarbonate resin

The present invention relates to a colorant composition containing an aromatic polycarbonate resin, a pigment and an ester-based additive, an aromatic polycarbonate resin composition obtained using the colorant composition, and a molded article thereof.

Conventionally, aromatic polycarbonate resin is excellent in impact resistance, heat resistance, etc., and the molded product obtained is also excellent in dimensional stability, etc., so housings for electric and electronic equipment, automotive parts, or It is widely used as a raw material resin for manufacturing precision molded products such as optical disc-related parts. In particular, home appliances, electronic devices, and housings of image display devices are used because they can take advantage of their beautiful appearance to obtain molded products with high commercial value.

The molded product is colored in order to improve the decorativeness of the molded product of the polycarbonate resin.

Generally, the plastics containing the polycarbonate resin are colored at the stage of injection molding or extrusion molding, and various forms of colorants are used at this stage. The colorant is a color component obtained by adding a dispersion aid to a pigment or dye, or is obtained by simply adding a resin and mixing or melt-kneading. Various changes.

Conventionally, as the colorant, a colorant composition such as a commonly known dry color that is a powdery colorant, a commonly known liquid color that is a liquid colorant, or a commonly known masterbatch color that is a granular colorant has been used. Each of the colorant compositions is obtained by concentrating pigments and dyes required for a resin molded product to a concentration higher than that in the molded product, and kneaded with a carrier resin similar to the resin to be colored. Therefore, it is diluted in accordance with the pigment concentration ratio in the molding stage.

Generally, organic pigments, inorganic pigments and the like are used as pigments used for preparing the colorant composition. All of these pigments have a very high content in the colorant composition of, for example, 5 to 70% by mass, so that the aggregated pigment particles do not loosen well even when melt-kneaded with the carrier resin, so-called unsolved. Coarse particles called glue (unfrayed) are formed. The coarse particles are mixed in the colored resin composition for molding obtained by mixing the colorant composition containing such coarse particles and the polycarbonate resin. This coarse particle causes poor appearance of the resulting molded product. As described above, since the colorant composition containing coarse particles impairs the commercial value of a molded product and causes a decrease in yield, it is usually attempted to remove coarse particles using a filter provided in a melt kneader. When the particle size of the coarse particles is large or the number is large, the filter is likely to be clogged, resulting in deterioration of the productivity of the molded product.

In order to improve the looseness of the pigment, a method of mixing a mineral wax such as montanic ester wax together with the pigment is generally used. However, natural resources such as montanic acid ester wax have been depleted in recent years due to over-exploitation, and development of alternative materials such as petroleum wax and synthetic wax has been demanded. Therefore, a method of mixing a surfactant such as a fatty acid, a fatty acid metal salt, a fatty acid ester, and a fatty acid amide together with a pigment is known (for example, Patent Document 1).

However, such aliphatic surfactants do not have sufficient affinity with the aromatic polycarbonate resin. Therefore, in order to obtain the colorant composition having a large amount of pigment, the aromatic polycarbonate resin and the pigment When the surfactant is mixed and kneaded, the pigment is pushed out of the system and cannot be kneaded effectively, resulting in a colorant composition containing the coarse particles. And when it tries to shape | mold the molded article of the aromatic polycarbonate colored using the coloring agent composition containing such a coarse particle, the above deterioration of productivity is caused.

Japanese Patent Laid-Open No. 11-148020

Therefore, the problem to be solved by the present invention is that the composition has excellent heat resistance that can withstand melt kneading with an aromatic polycarbonate resin, and in the composition containing a high concentration of pigment, the looseness of the pigment (peptization) And a plasticizer for an aromatic polycarbonate resin capable of preventing the formation of coarse particles such as unpeptized material, and a colorant composition using the plasticizer, An object of the present invention is to provide an aromatic polycarbonate resin composition obtained by diluting a colorant composition with an aromatic polycarbonate resin and a molded article thereof.

As a result of intensive studies to solve the above problems, the present inventors have found that the alkyl ester of an aromatic polycarboxylic acid is a linear alkyl chain having 16 to 26 carbon atoms. It is found that the ester compound is excellent in heat resistance, improves the looseness (peptization) of the pigment even in polycarbonate, and prevents the formation of coarse particles such as unpeptized material, thereby completing the present invention. It came to.

That is, the present invention is a colorant composition containing an aromatic polycarbonate resin, a pigment and an ester additive, wherein the ester additive is an alkyl ester of an aromatic polycarboxylic acid, and the alkyl chain of the alkyl ester is The present invention provides a colorant composition characterized by being a linear alkyl chain having 16 to 26 carbon atoms.

The present invention also provides an aromatic polycarbonate resin composition obtained by melt-kneading the colorant composition and an aromatic polycarbonate resin for dilution.

Also, the present invention provides a molded product characterized by molding an aromatic polycarbonate resin composition.

Furthermore, the present invention relates to a plastic for an aromatic polycarbonate resin, characterized in that it is an alkyl ester of an aromatic polyvalent carboxylic acid, and the alkyl chain of the alkyl ester is a linear alkyl chain having 16 to 26 carbon atoms. An agent is provided.

According to the present invention, the composition has excellent heat resistance that can withstand melt kneading with an aromatic polycarbonate resin, and improves the looseness (peptization) of the pigment in a composition containing a high concentration of pigment. It is possible to provide a plasticizer for an aromatic polycarbonate resin capable of preventing the formation of coarse particles such as a product, a colorant composition using the plasticizer, and an aromatic polycarbonate for the colorant composition. An aromatic polycarbonate resin composition obtained by diluting with a resin and a molded product thereof can be provided.

The colorant composition of the present invention is a colorant composition containing an aromatic polycarbonate resin, a pigment, and an ester-based additive. The ester additive is an alkyl ester of an aromatic polycarboxylic acid, and the alkyl chain of the alkyl ester is a linear alkyl chain having 16 to 26 carbon atoms.

The aromatic polycarbonate resin used in the colorant composition of the present invention is easily produced, for example, by reacting an aromatic dihydroxy compound with a carbonate precursor such as phosgene or carbonic acid diester. For the reaction, a known method, for example, an interfacial method when phosgene is used, or a transesterification method in which the reaction is performed in a molten state when diester carbonate is used is adopted.

As the aromatic dihydroxy compound, for example, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) is representative. Other examples include bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, and 2,2-bis (4-hydroxyphenyl). Octane, bis (4-hydroxyphenyl) phenylmethane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (4-hydroxy-3-t-butylphenyl) propane, 2, 2-bis (4-hydroxy-3-bromophenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) Bis (hydroxyaryl) alkanes such as propane;

Bis (hydroxyaryl) cycloalkanes such as 1,1-bis (4-hydroxyphenyl) cyclopentane and 1,1-bis (4-hydroxyphenyl) cyclohexane;

Dihydroxy diaryl ethers such as 4,4′-dihydroxydiphenyl ether and 4,4′-dihydroxy-3,3′-dimethyldiphenyl ether;

Dihydroxydiaryl sulfides such as 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide;

Dihydroxydiaryl sulfoxides such as 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide;

Examples include dihydroxydiaryl sulfones such as 4,4′-dihydroxydiphenyl sulfone and 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfone. These are used individually or in mixture of 2 or more types. In addition to these, piperazine, dipiperidyl hydroquinone, resorcin, and 4,4′-dihydroxydiphenyls may be mixed and used. Furthermore, a branched aromatic polycarbonate resin using a polyfunctional compound such as phloroglucin can also be used.

Examples of the carbonate precursor to be reacted with the aromatic dihydroxy compound include phosgene; diaryl carbonates such as diphenyl carbonate and ditolyl carbonate; and dialkyl carbonates such as dimethyl carbonate and diethyl carbonate.

Also, the weight average molecular weight (Mw) of the aromatic polycarbonate resin used in the present invention can be easily measured by gel permeation chromatografy (GPC). The weight average molecular weight (Mw) is preferably 10,000 to 100,000, more preferably 10,000 to 60,000.

In the present invention, the weight average molecular weight (Mw) and the number average molecular weight (Mw) were measured according to the following conditions [GPC measurement conditions]
Measuring device: “HLC-8220 GPC” manufactured by Tosoh Corporation
Column: Guard column “HHR-H” (6.0 mm ID × 4 cm) manufactured by Tosoh Corporation + “TSK-GEL GMHHR-N” (7.8 mm ID × 30 cm) manufactured by Tosoh Corporation + Tosoh Corporation “TSK-GEL GMHHR-N” (7.8 mm ID × 30 cm) + Tosoh Corporation “TSK-GEL GMHHR-N” (7.8 mm ID × 30 cm) + Tosoh Corporation “TSK- GEL GMHHR-N "(7.8 mm ID x 30 cm)
Detector: ELSD ("ELSD2000" manufactured by Oltec)
Data processing: “GPC-8020 Model II data analysis version 4.30” manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Developing solvent Tetrahydrofuran (THF)
Flow rate: 1.0 ml / min Sample: A 1.0% by mass tetrahydrofuran solution in terms of resin solid content filtered through a microfilter (5 μl).
Standard sample: The following monodisperse polystyrene having a known molecular weight was used in accordance with the measurement manual of “GPC-8020 Model II Data Analysis Version 4.30”.

(Monodispersed polystyrene)
“A-500” manufactured by Tosoh Corporation
“A-1000” manufactured by Tosoh Corporation
“A-2500” manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
“F-1” manufactured by Tosoh Corporation
“F-2” manufactured by Tosoh Corporation
“F-4” manufactured by Tosoh Corporation
“F-10” manufactured by Tosoh Corporation
“F-20” manufactured by Tosoh Corporation
“F-40” manufactured by Tosoh Corporation
“F-80” manufactured by Tosoh Corporation
“F-128” manufactured by Tosoh Corporation
“F-288” manufactured by Tosoh Corporation
“F-550” manufactured by Tosoh Corporation

In order to obtain an aromatic polycarbonate resin having a desired molecular weight as the aromatic polycarbonate resin used in the present invention, for example, a known method such as a method using a terminal terminator or a molecular weight regulator or a selection of polymerization reaction conditions is employed.

The aromatic polycarbonate resin used in the present invention may contain an aromatic polycarbonate oligomer. The aromatic polycarbonate oligomer can be obtained, for example, by reacting an aromatic dihydroxy compound with phosgene or a carbonic acid diester using a terminal terminator or a molecular weight regulator. As the aromatic dihydroxy compound, bisphenol A or a mixture of bisphenol A and another divalent phenol is preferable.

Examples of the terminal terminator or molecular weight regulator include phenol, pt-alkylphenol, 2,4,6-tribromophenol, long-chain alkylphenol, aliphatic carboxylic acid, hydroxybenzoic acid, and aliphatic carboxylic acid chloride. Can be mentioned. Specific examples of aromatic polycarbonate oligomers are preferably bisphenol A polycarbonate oligomers terminated with pt-butylphenol, copolycarbonate oligomers of tetrabromobisphenol A and bisphenol A terminated with pt-butylphenol However, it is not always necessary that the oligomer is produced by the same raw materials and reaction methods as the aromatic polycarbonate resin.

Furthermore, the aromatic polycarbonate resin used in the present invention may be used alone, but in order to improve fluidity, a resin obtained by mixing with another resin and alloying may be used. Examples of the resin used for alloying include acrylic-styrene (AS) resin and acrylic-butadiene-styrene (ABS) resin. The mixing ratio of the aromatic polycarbonate resin and other resin such as AS resin and ABS resin when alloying is, for example, 5 to 900 parts by mass of the other resin with respect to 100 parts by mass of the aromatic polycarbonate resin, The amount is preferably 10 to 500 parts by mass of the resin.

The pigment used in the present invention is not particularly limited as long as it is used as a pigment. For example, organics such as azo, phthalocyanine, quinacridone, dioxazine, perylene, and isoindolinone Pigment; carbon black; inorganic pigments such as titanium oxide, iron oxide, chromium oxide, and chrome. Of these, carbon black is preferred. A pigment can be used 1 type or in combination of 2 or more types.

The content of the pigment in the colorant composition is excellent in heat resistance and has good affinity for a carrier resin (diluted resin) described later, and as a result, a better kneading effect can be expressed. The range is preferably from 0.1 to 235 parts by weight, more preferably from 0.1 to 150 parts by weight, still more preferably from 5 to 150 parts by weight, particularly preferably from 10 to 150 parts by weight, based on 100 parts by weight of the aromatic polycarbonate resin.

The ester-based additive used in the present invention is an alkyl ester of an aromatic polycarboxylic acid, and the alkyl chain of the alkyl ester is a linear alkyl chain having 16 to 26 carbon atoms. Here, an ester-based additive in which an alkyl chain having 18 to 24 carbon atoms is excellent in heat resistance and exhibits a better kneading effect with respect to affinity for a carrier resin (aromatic polycarbonate resin). Therefore, an alkyl chain having 20 to 24 carbon atoms is more preferable, and an alkyl chain having 20 to 23 carbon atoms is more preferable.

The ester-based additive (ester compound) used in the present invention includes, for example, an aromatic polyvalent carboxylic acid or acid anhydride (A) thereof and a monoalcohol having a linear alkyl chain having 16 to 26 carbon atoms (A). B) can be suitably obtained by an esterification reaction. In the present invention, the valence of the aromatic polyvalent carboxylic acid refers to the number of carboxyl groups in one molecule, and the acid anhydride refers to the number of carboxyl groups before dehydration condensation.

The aromatic polycarboxylic acid (A) is not particularly limited as long as it is an aromatic compound having two or more carboxyl groups. For example, phthalic acid, isophthalic acid, terephthalic acid, hemimellitic acid, trimellitic acid, trimesin Examples include acids, merophanic acid, planitic acid, pyromellitic acid, and meritic acid, and examples of the anhydride of aromatic polyvalent carboxylic acid include these acid anhydrides. Of these, aromatic compounds having three or more carboxyl groups are preferred because they can exhibit a better kneading effect with respect to affinity for the carrier resin (aromatic polycarbonate resin). A merit acid and these acid anhydrides are mentioned as a preferable thing. These aromatic polyvalent carboxylic acids or acid anhydrides thereof can be used alone or in combination of two or more.

The monoalcohol (B) used in the present invention is a monoalcohol having a linear alkyl chain having 16 to 26 carbon atoms. Examples of the alcohol include hexadecanol (C16), octadecanol (C18), eicosanol (C20), heneicosanol (C21), docosanol (C22), tricosanol (C23), tetracosanol ( C24), pentacosanol (C25), hexacosanol (C26), and the like. Among them, it has excellent heat resistance and can exhibit a better kneading effect with respect to affinity for the carrier resin. Therefore, a monoalcohol having a linear alkyl chain having 18 to 24 carbon atoms is preferable, a monoalcohol having an alkyl chain having 20 to 24 carbon atoms is more preferable, and an alkyl chain having 20 to 23 carbon atoms is preferable. A monoalcohol is more preferable. Specifically, octadecanol (C18), eicosanol (C20), heneicosanol (C21), docosanol (C22), tricosanol (C23), and tetracosanol (C24) are preferable, and eicosanol (C20), Eicosanol (C21), docosanol (C22), tricosanol (C23), and tetracosanol (C24) are more preferable, and eicosanol (C20), heneicosanol (C21), docosanol (C22), and tricosanol (C23) are preferable. Further preferred.

In the present invention, a monoalcohol other than the monoalcohol (B) may be used in combination with the monoalcohol (B) as long as the effects of the present invention are not impaired. Examples of monoalcohols other than monoalcohol (B) include octanol (C8), decanol (C10), dodecanol (C12), tetradecanol (C14), heptacosanol (C27), octacosanol (C28), and nonacosanol (C29). Triancontanol (C30), Hentriancontanol (C31), Dotriacontanol (C32), Cellomerisyl alcohol (C33), Tetratriacontanol (C34), Heptatriacontanol (C35), Hexatria Examples thereof include contanol (C36).

The substitution position of the hydroxyl group in the monoalcohol (B) or monoalcohol other than the monoalcohol (B) used in the present invention may be either the 1-position or the 2-position, but the 1-position is preferably used.

As a method for producing an ester-based additive (ester compound) used in the present invention, a method in which the aromatic polycarboxylic acid (A) and the monoalcohol (B) are charged into a reactor and subjected to a normal esterification reaction. Etc. Moreover, it is preferable to use an esterification catalyst for the purpose of promoting this esterification reaction.

A metal or an organometallic compound can be used as the esterification catalyst. Specific examples include at least one metal or organometallic compound selected from the group consisting of Group 2, Group 4, Group 12, Group 13, Group 14 of the Periodic Table. More specifically, for example, metals such as titanium, tin, zinc, aluminum, zirconium, magnesium, hafnium, germanium; titanium tetraisopropoxide, titanium tetrabutoxide, titanium oxyacetylacetonate, tin octoate, 2-ethyl Examples thereof include metal compounds such as hexanetin, zinc acetylacetonate, zirconium tetrachloride, zirconium tetrachloride, tetrahydrofuran complex, hafnium tetrachloride, hafnium tetrachloride tetrahydrofuran complex, germanium oxide, and tetraethoxygermanium. Of these, titanium alcohols such as titanium tetraisopropoxide, titanium tetrabutoxide, and titanium oxyacetylacetonate have good reactivity, ease of handling, and storage stability of the ester compound obtained by the esterification reaction. Coxide is preferred.

The amount of the esterification catalyst used may be an amount that can control the esterification reaction and can suppress the coloring of the resulting ester compound, and the aromatic polycarboxylic acid (A) and the monoalcohol. The range of 10 to 2,000 ppm is preferable with respect to the total amount with (B), and the range of 20 to 1,000 ppm is more preferable.

When the ester compound is produced, the esterification catalyst may be added at the same time as the aromatic polyvalent carboxylic acid (A) and the monoalcohol (B) are charged into a reactor. You may add in the middle of temperature rising, and you may divide | segment and add an esterification catalyst.

In the esterification reaction, the charge ratio between the polyvalent carboxylic acid (A) and the monoalcohol (B) is particularly limited for the polyvalent carboxylic acid (A) with respect to the alcoholic hydroxyl group of the monoalcohol (B). For example, the carboxyl group of the polyvalent carboxylic acid (A) is in the range of 0.80 to 1.20 equivalent, more preferably 1.00 equivalent of the alcoholic hydroxyl group of the monoalcohol (B). It is preferable to adjust to a range of 0.90 to 1.10 equivalents.

The reaction temperature at the time of producing the ester compound is 60 to 300 ° C. because the reaction can be accelerated while suppressing the evaporation and sublimation of each raw material, and the thermal decomposition and coloring of the ester compound produced by the reaction can be suppressed. The range is preferable, and the range of 100 to 250 ° C. is more preferable.

The ester compound obtained by the above production method is stable and resistant to hydrolysis even under high temperature and high humidity, and is less likely to cause bleeding because of its good compatibility with the aromatic polycarbonate resin. Further, by adjusting the acid value and the hydroxyl value and adjusting the affinity according to the surface treatment state of the pigment, it is possible to improve the looseness of the target colorant, so that it is 30 or less. Those having a hydroxyl value and having an acid value of 15 or less are preferred, those having a hydroxyl value of 20 or less and having an acid value of 10 or less are more preferred, particularly preferred are those having a hydroxyl value of 15 or less. And an acid value of 5 or less.

The form of the ester compound (ester-based additive) thus obtained is not particularly limited, and examples thereof include powder, granule, pellet, plate, and flake. The production method is not particularly limited, but the molten ester compound is taken out into a stainless steel vat or a belt conveyor with a cooling device, and then ground, ground, flakes, etc. by a pulverizer, etc .; And the like; a method of directly taking out particles and pellets from a molten state; a method of kneading with an aromatic polycarbonate resin as a carrier resin at a certain ratio and taking out as a master batch; and the like.

The content of the ester-based additive thus obtained in the colorant composition is preferably 0.1 to 235 parts by mass, more preferably 0.5 to 120 parts by mass with respect to 100 parts of the aromatic polycarbonate resin. 0.8 to 100 parts by mass is more preferable.

The mechanism of action by which the above-mentioned ester-based additives exhibit excellent looseness (peptization) of pigments is not clear at the present time, but by having an aromatic skeleton, it has more heat resistance than that of conventional aliphatic skeletons Excellent in resistance to decomposition even at high temperatures during melt-kneading, and can continue to exhibit the original plasticizing effect and surface-active effect, resulting in a reduction in melt viscosity even in colorant compositions containing pigments at high concentrations It is thought that it was possible. In addition, it is considered that the structure has a high affinity with the aromatic polycarbonate resin, which is a carrier resin, and the ester additive effectively acts on the carrier resin and the pigment to enhance the kneading effect. As a result, the looseness of the pigment in the colorant composition is improved and the formation of coarse particles such as unpeptized material is reduced, leading to a reduction in the filtration pressure of the filter installed in the melt kneader. It is thought that. Thus, the ester additive can be suitably used as a plasticizer for an aromatic polycarbonate resin and as a pigment dispersant.

The colorant composition of the present invention is obtained by mixing the above aromatic polycarbonate resin, pigment and ester-based additive, but the order of mixing is not particularly limited. For example, an aromatic polycarbonate resin, a pigment and an ester-based additive may be kneaded simultaneously (Method 1), or a kneaded product of a pigment and an ester-based additive may be obtained in advance and then kneaded with an aromatic polycarbonate resin. Good (Method 2). More specifically, for example, in the case of Method 1, the aromatic polycarbonate resin, the pigment and the ester-based additive are mixed in advance so that the materials are well mixed, and then at a temperature in the range of 220 to 300 ° C., You may melt-knead using a single screw or a twin screw extruder. In the case of method 2, the pigment and the ester-based additive are melt-kneaded using a single-screw or twin-screw extruder at a temperature in the range of 80 to 150 ° C., and then the obtained kneaded product is You may melt-knead with an extruder etc. with an aromatic polycarbonate resin.

The colorant composition thus obtained is used as a masterbatch color, and the form thereof is not particularly limited, and examples thereof include pellets, plates, and flakes.

The colorant composition of the present invention may contain other optional components in addition to the above components, for example, additives such as a lubricant, an antistatic agent, an ultraviolet absorber, and an antioxidant as necessary. Good.

The colorant composition of the present invention thus obtained is an aromatic polycarbonate resin composition colored by kneading with an aromatic polycarbonate resin for dilution (referred to as an aromatic polycarbonate resin for dilution in the present invention). be able to. More specifically, the range of 100 to 1,000,000 parts by weight, preferably 200 to 100,000 parts by weight of the aromatic polycarbonate resin for dilution is diluted with respect to 100 parts by weight of the colorant composition of the present invention. An aromatic polycarbonate resin composition can be obtained by melt-kneading at a temperature equal to or higher than the melting point of the aromatic polycarbonate resin for heating, for example, in the range of 250 to 300 ° C.

As content of the ester-type additive in the aromatic polycarbonate resin composition obtained at this time, for example, with respect to a total of 100 parts by mass of the aromatic polycarbonate resin and the aromatic polycarbonate resin for dilution in the colorant composition The amount is preferably 0.00001 parts by weight to 0.14 parts by weight, and more preferably 0.00008 parts by weight to 0.10 parts by weight.

Then, a molded product of the aromatic polycarbonate resin can be formed by molding the aromatic polycarbonate resin composition of the present invention. Specifically, molded products of various shapes can be obtained by performing injection molding, T-die film molding, and the like on the aromatic polycarbonate resin composition of the present invention using various extruders, injection molding machines, and the like. . Examples of the aromatic polycarbonate resin for dilution include those similar to the aromatic polycarbonate resin used in the colorant composition, and the same type of aromatic polycarbonate resin used in the colorant composition may be used in combination. preferable. In addition to the molding method as described above, the colorant composition and the aromatic polyester resin for dilution are mixed in advance by a mixer, blender, etc., and then injected into an injection molding machine and melt-kneaded and directly molded. can give.

The molded product of the present invention is formed by molding the aromatic polycarbonate resin composition. Examples of such molded products include home appliance parts such as TV parts, VTR parts, hair dryer housings, iron parts, microwave oven parts, various optical discs; electronic communication parts such as relay cases, LED lamps, and computer structural parts; Lighting fixture parts such as covers and flashlight housings; headlamp lenses, door handles, meter covers, motorcycle windshields and motorcycle parts such as louvers; optical machine parts such as camera bodies and parts; structure of copying machines and printers OA equipment parts such as parts, FDD parts, personal computer parts; molded products for electrical and electronic equipment applications represented by mechanical parts such as pump parts and electric tool housings;

Daily necessities such as toys, stroller parts, water supply parts, water bottles, combs; stationery such as fountain pens and pencil sharpeners; miscellaneous goods such as ski goggles, kendo armor, windsurfing fins, pachinko parts, and helmets Molded products for related applications;

Molded products for medical and security applications such as artificial kidney cases, eye drops containers, construction helmets, protective glasses, and fire extinguisher parts;

Examples thereof include molded products for sheet and film applications such as packaging films, capacitor films, and optical films for FPD (flat panel display).

Hereinafter, examples of the present invention will be given, and the present invention will be described in detail while comparing with comparative examples. In the examples, “parts” and “%” are based on mass unless otherwise specified.

Example 1 (Preparation of plasticizer for aromatic polycarbonate resin)
176.8 g of phthalic anhydride (hereinafter abbreviated as “PA”) and docosanol (98) were added to a 3 L four-necked flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a trough tube for fractional distillation. %)), 84 g of toluene, 51 g of toluene, and 0.31 g of titanium tetraisopropoxide (hereinafter abbreviated as “TiPT”), and then nitrogen gas is reduced to a tower top temperature of 100 ° C. or less. The temperature was raised to 230 ° C. while blowing in the range of 100 to 500 ml / min so as to maintain. Next, a dehydration esterification reaction was performed while removing water generated at 230 ° C. When the acid value of the reaction product became 2 or less, 0.25 g of 85% phosphoric acid aqueous solution was charged, pressure reduction was started, the pressure was reduced to 0.67 kPa or less at 230 ° C., and toluene and unreacted alcohol were removed. Removed. After the outflow of toluene and unreacted alcohol ceased, the reduced pressure was released and the temperature was lowered, and the reaction product was filtered out through diatomaceous earth to obtain a plasticizer (1) for aromatic polycarbonate resin. The number average molecular weight (Mn) of the plasticizer (1) was 1,090, the weight average molecular weight (Mw) was 1,160, the acid value was 2.2, and the hydroxyl value was 3.3. The appearance of the plasticizer (1) was a white solid.

Example 2 (same as above)
220.8 g of trimellitic anhydride (hereinafter abbreviated as “TMA”) in a 3 L four-necked flask equipped with a thermometer, a stirrer, a nitrogen introducing tube and a trough tube for fractional distillation, and docosanol ( 984.2% product), 534.2g octadecanol (product containing 98% octadecanol), 442.5g toluene, 60g toluene, 0.36g TiPT, and nitrogen gas was added to the top of the tower. The temperature was raised to 230 ° C. while blowing in the range of 100 to 500 ml / min so as to maintain the temperature at 100 ° C. or lower. Next, a dehydration esterification reaction was performed while removing water generated at 230 ° C. When the acid value of the reaction product became 2 or less, 0.29 g of 85% phosphoric acid aqueous solution was charged, pressure reduction was started, and the pressure was reduced to 0.67 kPa or less at 230 ° C. to remove toluene. After toluene did not flow out, the reduced pressure was released, the temperature was lowered, and the liquid temperature was maintained at 100 ° C., and the solution was taken out into a metal SUS vat to obtain an aromatic polycarbonate resin plasticizer (2). The number average molecular weight (Mn) of the plasticizer (2) was 1,850, the weight average molecular weight (Mw) was 1,930, the acid value was 3.3, and the hydroxyl value was 4.5. The appearance of the plasticizer (2) was a white solid.

Example 3 (same as above)
In a 3 L four-necked flask equipped with a thermometer, stirrer, nitrogen inlet tube, and fractional distillation tube, 192.0 g of TMA, 929.1 g of docosanol (98% content), and 56 g of toluene Then, after charging 0.33 g of TiPT, the temperature was raised to 230 ° C. while blowing nitrogen gas in the range of 100 to 500 ml / min so as to maintain the tower top temperature at 100 ° C. or lower. Next, a dehydration esterification reaction was performed while removing water generated at 230 ° C. When the acid value of the reaction product became 2 or less, 0.27 g of 85% phosphoric acid aqueous solution was charged, pressure reduction was started, and the pressure was reduced to 0.67 kPa or less at 230 ° C. to remove toluene. After the toluene flow out, the reduced pressure was released, the temperature was lowered, and the solution was taken out into a metal SUS vat while maintaining the liquid temperature at 100 ° C. to obtain a plasticizer (3) for aromatic polycarbonate resin. The number average molecular weight (Mn) of the plasticizer (3) was 1,670, the weight average molecular weight (Mw) was 1,750, the acid value was 2.0, and the hydroxyl value was 7.3. The appearance of the plasticizer (3) was a white solid.

Example 4 (same as above)
218.4 g of pyromellitic acid (hereinafter abbreviated as “PMA”) and octadecanol in a 3 L four-necked flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a trough tube for fractional distillation After charging 882.4 g (containing 98%), 55 g of toluene, and 0.33 g of TiPT, in a range of 100 to 500 ml / min so as to keep the nitrogen gas at a top temperature of 100 ° C. or lower. The temperature was raised to 230 ° C. while blowing. Subsequently, dehydration esterification reaction was performed while removing water generated at 230 ° C. When the acid value of the reaction product became 2 or less, 0.26 g of 85% phosphoric acid aqueous solution was charged, pressure reduction was started, and the pressure was reduced to 0.67 kPa or less at 230 ° C. to remove toluene. After toluene did not flow out, the reduced pressure was released, the temperature was lowered, and the solution was taken out into a metal SUS vat while maintaining the liquid temperature at 100 ° C. to obtain a plasticizer (4) for aromatic polycarbonate resin. The number average molecular weight (Mn) of the plasticizer (4) was 1,900, the weight average molecular weight (Mw) was 1,970, the acid value was 5.5, and the hydroxyl value was 4.1. Moreover, the external appearance of the plasticizer (4) was a white solid.

Example 5 (same as above)
In a 3 L four-necked flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a fractional distillation tube, 190.5 g of pyromellitic acid (hereinafter abbreviated as “PMA”) and docosanol (98 %), 929.1 g of toluene, 56 g of toluene, and 0.34 g of TiPT, and then nitrogen gas was blown in a range of 100 to 500 ml / min so as to maintain the top temperature at 100 ° C. or lower. The temperature was raised to 230 ° C. Next, a dehydration esterification reaction was performed while removing water generated at 230 ° C. When the acid value of the reaction product became 2 or less, 0.27 g of 85% phosphoric acid aqueous solution was charged, pressure reduction was started, and the pressure was reduced to 0.67 kPa or less at 230 ° C. to remove toluene. After the toluene flow out, the reduced pressure was released, the temperature was lowered, and the solution was taken out into a metal SUS vat while maintaining the liquid temperature at 100 ° C. to obtain a plasticizer (5) for aromatic polycarbonate resin. The number average molecular weight (Mn) of the plasticizer (5) was 2,260, the weight average molecular weight (Mw) was 2,390, the acid value was 4.1, and the hydroxyl value was 8.1. Moreover, the external appearance of the plasticizer (5) was a white solid.

Comparative Example 1 (Preparation of plasticizer for aromatic polycarbonate resin for comparison)
In a 3 L four-necked flask equipped with a thermometer, stirrer, nitrogen inlet tube and fractional distillation tube, 108.8 g pentaerythritol, 908.8 g stearic acid, 51 g toluene, and TiPT After charging 0.31 g, the temperature was raised to 230 ° C. while blowing nitrogen gas in the range of 100 to 500 ml / min so as to maintain the tower top temperature at 100 ° C. or lower. Next, a dehydration esterification reaction was performed while removing water generated at 230 ° C. When the acid value of the reaction product became 2 or less, 0.24 g of 85% phosphoric acid aqueous solution was charged, pressure reduction was started, and the pressure was reduced to 0.67 kPa or less at 230 ° C. to remove toluene. After the toluene flow out, the reduced pressure was released, the temperature was lowered, and the solution was taken out into a metal SUS vat while maintaining the liquid temperature at 100 ° C., to obtain a plasticizer (1 ′) for comparison aromatic polycarbonate resin. The number average molecular weight (Mn) of this plasticizer (1 ′) was 1,620, the weight average molecular weight (Mw) was 1,680, the acid value was 1.9, and the hydroxyl value was 15.0. Further, the appearance of the plasticizer (1 ′) was a white solid.

Tables 1 and 2 show the raw materials and characteristic values used for preparing the plasticizers for aromatic polycarbonate resin (1) to (5) and the plasticizer for aromatic polycarbonate resin for comparison (1 ′).

Footnotes in Table 1 PA: phthalic anhydride TMA: trimellitic anhydride PMA: pyromellitic acid

Example 6 (Preparation of colorant composition)
700 parts of carbon black, 1265 g of aromatic polycarbonate resin (bisphenol A, powdered aromatic polycarbonate resin having a viscosity average molecular weight of 21,500 obtained by a conventional method from p-tert-butylphenol (molecular weight regulator) and phosgene) Plasticizer for aromatic polycarbonate resin (1) 35 g In a polyethylene bag, the bag was closed. Thereafter, the bag was shaken well so that the materials were mixed together to obtain a mixture.

Next, the above mixture was kneaded using a twin screw extruder to obtain the colorant composition (1) of the present invention. A twin screw extruder having a screw diameter of 32 mm and an L / D value of 52 was used, and the jacket temperature was set to 270 to 280 ° C. In the preparation of the resin colorant composition (1), the current value when kneaded under the condition that the rotation speed of the screw was 200 rpm was measured, and the value when the current was stabilized was evaluated according to the following criteria. The lower this value, the lower the melt viscosity of the melt-kneaded product, which means that the kneadability is excellent and the productivity is also excellent. The evaluation results are shown in Table 3.

<Evaluation criteria for current during kneading>
◎: Less than 30A (ampere) ○: 30-32A
X: 32A or more

Further, the colorant composition (1) and the aromatic polycarbonate resin for dilution were melt-kneaded with a single screw extruder to prepare a colored aromatic polycarbonate resin composition (1). When preparing this composition, the looseness (peptidity) of the colorant composition (1) was evaluated according to the following method. In addition, as polycarbonate for dilution, the aromatic polycarbonate resin used for preparation of the said colorant composition was used.

<Method of confirming the unravelability (= looseness)>
Mass ratio of colorant composition (1) and aromatic polycarbonate resin for dilution to a tester equipped with a filtration pressure tester on the outlet side of a single screw extruder having a screw diameter of 30 mm and an L / D value of 30 Was mixed at a mixing ratio of 9.52 / 90.48, and finally extruded from the filtration tester to obtain an aromatic polycarbonate resin composition (1). Here, the temperature of the jacket of the single screw extruder was set to 280 ° C. The configuration of the filter attached to the filtration pressure tester was # 80 × baked 40 μm × # 80.

When extruding the aromatic polycarbonate resin composition (1) from the filtration pressure tester, the pressure (resin pressure) when the aromatic polycarbonate resin composition (1) is allowed to flow into the filter inlet side and the filter outlet side are discharged. The pressure at that time was measured, the difference (filtration pressure, Mpa) was determined, and this was used as the filtration pressure test value, and evaluated according to the following criteria. The lower the filtration test value, the smaller the formation of coarse particles such as unpeptized material, which means that the “flocculation (peptization)” is excellent.

A: Filtration pressure is less than 6 MPa B: Filtration pressure is 6-9 MPa
Δ: Filtration pressure exceeds 9 MPa ×: Test suspended due to clogging

Examples 2-5
Colorant compositions (2) to (5) of the present invention were obtained in the same manner as in Example 1 except that the plasticizer for aromatic polycarbonate resin shown in Table 3 was used. Colored aromatic polycarbonate resin compositions (2) to (5) were obtained. The same evaluation as in Example 1 was performed, and the results are shown in Table 3.

Comparative Examples 2-4
Comparative colorant compositions (1 ′) to (3 ′) were obtained in the same manner as in Example 1 except that the plasticizer for comparative aromatic polycarbonate resin shown in Table 4 was used. Colored aromatic polycarbonate resin compositions (1 ′) to (3 ′) were obtained. The same evaluation as in Example 1 was performed, and the results are shown in Table 3.

Footnotes in Table 4 Plasticizer for polycarbonate for comparison (2 '): Montanate ester wax [manufactured by Clariant Co., Ltd., Licolub WE4. ]
Comparative plasticizer for polycarbonate (3 '): modified polyethylene wax [Evonik INDUSTRIES, TEGOMER E 525. ]
Unable to measure: Could not measure due to filter clogging.

Claims

A colorant composition comprising an aromatic polycarbonate resin, a pigment and an ester-based additive, wherein the ester-based additive is an alkyl ester of an aromatic polyvalent carboxylic acid, and the alkyl chain of the alkyl ester has 16 to 16 carbon atoms. A colorant composition comprising 26 linear alkyl chains.
The ester additive is obtained by esterifying an aromatic polyvalent carboxylic acid or acid anhydride (A) thereof and a monoalcohol (B) having a linear alkyl chain having 16 to 26 carbon atoms. The colorant composition according to claim 1, which has been obtained.
The colorant composition according to claim 1, wherein the monoalcohol (B) is at least one monoalcohol selected from the group consisting of eicosanol, heneicosanol, docosanol, tricosanol and tetracosanol.
The colorant composition according to any one of claims 1 to 3, wherein the aromatic polyvalent carboxylic acid or acid anhydride (A) thereof is trivalent or higher.
4. The aromatic polycarboxylic acid or acid anhydride (A) thereof is one or more selected from the group consisting of trimellitic acid, pyromellitic acid and acid anhydrides thereof. A colorant composition according to claim 1.
The colorant composition according to any one of claims 1 to 5, wherein the pigment is carbon black.
The colorant composition according to any one of claims 1 to 6, comprising 10 to 150 parts by mass of a pigment and 0.8 to 100 parts by mass of an ester-based additive with respect to 100 parts by mass of the aromatic polycarbonate resin. object.
An aromatic polycarbonate resin composition obtained by melt-kneading the colorant composition according to any one of claims 1 to 7 and an aromatic polycarbonate resin for dilution.
A molded product obtained by molding the aromatic polycarbonate resin composition according to claim 8.
A plasticizer for an aromatic polycarbonate resin, which is an alkyl ester of an aromatic polyvalent carboxylic acid, wherein the alkyl chain of the alkyl ester is a linear alkyl chain having 16 to 26 carbon atoms.