CN104583318A - Coloring agent composition, aromatic polycarbonate resin composition, molded article, and plasticizer for aromatic polycarbonate resin - Google Patents
Coloring agent composition, aromatic polycarbonate resin composition, molded article, and plasticizer for aromatic polycarbonate resin Download PDFInfo
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- CN104583318A CN104583318A CN201380043448.5A CN201380043448A CN104583318A CN 104583318 A CN104583318 A CN 104583318A CN 201380043448 A CN201380043448 A CN 201380043448A CN 104583318 A CN104583318 A CN 104583318A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0016—Plasticisers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0041—Optical brightening agents, organic pigments
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2469/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
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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
Technical field
The present invention relates to the dye compositions comprising aromatic polycarbonate resin, pigment and ester system additive, the aromatic copolycarbonate resin composition using this dye compositions to obtain and its products formed.
Background technology
All the time, shock-resistance, thermotolerance etc. due to aromatic polycarbonate resin are excellent and the dimensional stability of gained products formed etc. are also excellent, so can be widely used as the production of raw material for use resin of the precise forming categories such as the relevant parts of the shell class of electric/electronic device, automotive part class or CD.Particularly in the housing etc. of home appliance, electronics, image display, in order to realize its beauty outward appearance, obtain the high products formed of commodity value and used.
In order to improve the ornamental of the products formed of above-mentioned polycarbonate resin, carry out the painted of products formed.
In general, comprise the painted of the Plastic of above-mentioned polycarbonate resin and carry out in the stage of injection molding, extrusion moulding, employ the tinting material of various form in this stage.Tinting material in pigment or dyestuff, adds dispersing auxiliary and the coloring components obtained or add the coloring components that resin only carries out mixing or carrying out melting mixing and obtain, according to application target, the kind of Plastic, it is coloured to branch and various change occurs.
All the time, as above-mentioned tinting material, the dye compositions such as the common name dry color of powdered colorant, the common name mill base as liquid coloring agent or the common name Masterbatch as particulate colored dose can be used as.No matter which kind of dye compositions, being all the pigment required for synthetic resin or dyestuff are concentrated into more than the concentration in products formed, is that the resin of colored object is mixing with similar vector resin.Thus carry out diluting using according to the concentration ratio of pigment at formative stage.
Pigment for the preparation of dye compositions generally can use pigment dyestuff, mineral dye etc.The containing ratio of these pigment in dye compositions is all very high, be such as 5 ~ 70 quality %, therefore, even if with vector resin melting mixing, the granules of pigments condensed also successfully cannot separate wadding, and forms the so-called big particle being called as non-dispergation thing (not separating wadding thing).Mixing the dye compositions and polycarbonate resin that comprise such big particle, in the shaping resin combination be colored obtained, this big particle can mix existence.This big particle can cause the forming composition bad order obtained.So, the dye compositions comprising big particle can damage the commodity value of products formed, become the reason making decrease in yield, therefore, under normal circumstances, attempt utilizing the strainer be arranged on melting mixing machine to remove big particle, but easily cause this filter stoppage when the particle diameter of big particle is large or when quantity is many, become the major cause that the productivity of products formed is deteriorated.
In order to improve the Xie Xuxing of pigment, generally use the method mineral system waxes such as montanic acid ester type waxes and pigment are mixed together.But the natural resource such as montanic acid ester type waxes because of its overexploitation, amount exhaustion tails off in recent years, require the equivalent material developing petroleum wax, synthesis is wax etc.So, there will be a known the method (such as patent documentation 1) tensio-active agents such as lipid acid, fatty acid metal salt, fatty acid ester, fatty acid amide etc. and pigment are mixed together.
But, fatty family tensio-active agent like this and the affinity of aromatic polycarbonate resin insufficient, therefore, in order to the above-mentioned dye compositions that the compounding amount obtaining pigment is many, aromatic polycarbonate resin, pigment and above-mentioned tensio-active agent are carried out mixing and mixing time, pigment can be expressed into outside system, cannot effectively carry out mixing, its result, can become the dye compositions comprising above-mentioned big particle.And, when wanting the products formed of the aromatic copolycarbonate having used the dye compositions comprising such big particle painted to carry out shaping, the deterioration of productivity as described above can be caused.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 11-148020 publication
Summary of the invention
the problem that invention will solve
Therefore, the problem that the present invention will solve is, a kind of aromatic polycarbonate resin softening agent is provided, it has the thermotolerance that can tolerate with the excellence of the melting mixing of aromatic polycarbonate resin, and the Xie Xuxing (solution colloidality) of pigment can be improved in the composition of pigment comprising high density, and the formation of the big particles such as non-dispergation thing can be prevented, and then provide the dye compositions of this softening agent of use, the aromatic copolycarbonate resin composition dilution of this dye compositions aromatic polycarbonate resin obtained and its products formed.
for the scheme of dealing with problems
The present inventor etc. conduct in-depth research to solve above-mentioned problem, found that, the alkyl ester of aromatic polycarboxylic acid and the alkyl chain of this alkyl ester are the excellent heat resistance of the ester cpds of the straight-chain alkyl chain of carbonatoms 16 ~ 26, and in polycarbonate, also can improve the Xie Xuxing (solution colloidality) of pigment, prevent the formation of the big particles such as non-dispergation thing, thus complete the present invention.
Namely, the invention provides a kind of dye compositions, it is characterized in that, it is the dye compositions containing aromatic polycarbonate resin, pigment and ester system additive, this ester system additive is the alkyl ester of aromatic polycarboxylic acid, and the alkyl chain of this alkyl ester is the straight-chain alkyl chain of carbonatoms 16 ~ 26.
In addition, the invention provides a kind of aromatic copolycarbonate resin composition, it is characterized in that, foregoing colorants composition and dilution aromatic polycarbonate resin are carried out melting mixing and obtain by it.
In addition, the invention provides a kind of products formed, it is characterized in that, aromatic copolycarbonate resin composition is carried out shaping forming by it.
And then the invention provides a kind of aromatic polycarbonate resin softening agent, it is characterized in that, it is the alkyl ester of aromatic polycarboxylic acid, and the alkyl chain of this alkyl ester is the straight-chain alkyl chain of carbonatoms 16 ~ 26.
the effect of invention
According to the present invention, a kind of aromatic polycarbonate resin softening agent can be provided, it has the thermotolerance that can tolerate with the excellence of the melting mixing of aromatic polycarbonate resin, and the Xie Xuxing (solution colloidality) of pigment can be improved in the composition of pigment comprising high density, and the formation of the big particles such as non-dispergation thing can be prevented, and then provide the dye compositions of this softening agent of use, the aromatic copolycarbonate resin composition dilution of this dye compositions aromatic polycarbonate resin obtained and its products formed.
Embodiment
Dye compositions of the present invention is the dye compositions containing aromatic polycarbonate resin, pigment and ester system additive.And this ester system additive is the alkyl ester of aromatic polycarboxylic acid, and the alkyl chain of this alkyl ester is the straight-chain alkyl chain of carbonatoms 16 ~ 26.
The aromatic polycarbonate resin used in dye compositions of the present invention such as can by making aromatic dihydroxy compound, reacting and easily manufacture with the carbonate precursor such as carbonyl chloride or carbonic diester.Reaction can adopt known method, such as, use during carbonyl chloride and adopt with the ester-interchange method etc. of molten reaction by when interfacial or use carbonic diester.
As aforementioned fragrance race dihydroxy compound, be such as two (4-hydroxy phenyl) propane (dihydroxyphenyl propane) of 2,2-typically.In addition, such as can enumerate: two (4-hydroxy phenyl) methane, 1, two (4-hydroxy phenyl) ethane of 1-, 2, two (4-hydroxy phenyl) butane of 2-, 2, two (4-hydroxy phenyl) octane of 2-, two (4-hydroxy phenyl) phenylmethane, 2, two (the 4-hydroxy-3-methyl phenyl) propane of 2-, 1, two (4-hydroxyl-3-tert-butyl-phenyl) propane of 1-, 2, two (4-hydroxyl-3-bromophenyl) propane of 2-, 2, two (the 4-hydroxyl-3 of 2-, 5-dibromo phenyl) propane, 2, two (the 4-hydroxyl-3 of 2-, 5-dichlorophenyl) two (hydroxyaryl) alkanes such as propane,
Two (hydroxyaryl) naphthenic of two (4-hydroxy phenyl) pentamethylene, 1, the 1-bis(4-hydroxyphenyl) cyclohexane etc. of 1,1-;
4,4 '-dihydroxydiphenyl ether, 4, the dihydroxyl diaryl ethers such as 4 '-dihydroxyl-3,3 '-dimethyl diphenyl ether;
4,4 '-dihydroxydiphenyl thioether, 4, the dihydroxyl diaryl sulfide class that 4 '-dihydroxyl-3,3 '-dimethyl diphenyl sulfide is such;
4,4 '-dihydroxydiphenyl sulfoxide, 4, the dihydroxyl diaryl sulphoxide classes such as 4 '-dihydroxyl-3,3 '-dimethyl diphenyl sulfoxide;
4,4 '-dihydroxy-diphenyl sulfone, 4, the dihydroxyl diaryl sulfone classes etc. such as 4 '-dihydroxyl-3,3 '-dimethyl diphenyl sulfone.They can be used alone or mix two or more and use.In addition, can also by piperazine, dipiperidino quinhydrones, Resorcinol, 4, the mixing of 4 '-dihydroxydiphenyl class uses.And then, also can use the aromatic polycarbonate resin with side chain having combinationally used the multi-functional compounds such as fluorine glycine.
As the carbonate precursor reacted with aforementioned fragrance race dihydroxy compound, such as, carbonyl chloride can be enumerated; The diaryl carbonate classes such as diphenyl carbonate, carboxylol ester; The dialkyl carbonates such as methylcarbonate, diethyl carbonate etc.
In addition, the weight-average molecular weight (Mw) of the aromatic polycarbonate resin used in the present invention can be passed through gel permeation chromatography (GPC) and easily measure.As weight-average molecular weight (Mw), be preferably 10000 ~ 100000, be more preferably 10000 ~ 60000.
In the present invention, weight-average molecular weight (Mw) and number-average molecular weight (Mw) measure according to following condition.
[GPC condition determination]
Determinator: Tosoh Corporation system " HLC-8220 GPC ",
Post: Tosoh Corporation guard column " HHR-H " (6.0mmI.D. × 4cm)+Tosoh Corporation system " TSK-GEL GMHHR-N " (7.8mmI.D. × 30cm)+Tosoh Corporation system " TSK-GEL GMHHR-N " (7.8mmI.D. × 30cm)+Tosoh Corporation system " TSK-GEL GMHHR-N " (7.8mmI.D. × 30cm)+Tosoh Corporation system " TSK-GEL GMHHR-N " (7.8mmI.D. × 30cm)
Detector: ELSD (Ortec system " ELSD2000 ")
Data processing: Tosoh Corporation system " GPC-8020 type II data analysis 4.30 editions "
Condition determination: column temperature 40 DEG C
Developing solvent tetrahydrofuran (THF) (THF)
Flow velocity 1.0ml/ minute
Sample: the sample (5 μ l) after the tetrahydrofuran solution micro-strainer counting 1.0 quality % by converting with resin solid content filters.
Standard test specimen: according to the mensuration handbook of described " GPC-8020 type II data analysis 4.30 editions ", uses the following monodisperse polystyrene that molecular weight is known.
(monodisperse polystyrene)
Tosoh Corporation system " A-500 "
Tosoh Corporation system " A-1000 "
Tosoh Corporation system " A-2500 "
Tosoh Corporation system " A-5000 "
Tosoh Corporation system " F-1 "
Tosoh Corporation system " F-2 "
Tosoh Corporation system " F-4 "
Tosoh Corporation system " F-10 "
Tosoh Corporation system " F-20 "
Tosoh Corporation system " F-40 "
Tosoh Corporation system " F-80 "
Tosoh Corporation system " F-128 "
Tosoh Corporation system " F-288 "
Tosoh Corporation system " F-550 "
In order to obtain the aromatic polycarbonate resin of the molecular weight of the expectation as the aromatic polycarbonate resin used in the present invention, such as, can adopt the known method such as method, selective polymerization reaction conditions using end-capping reagent or molecular weight regulator.
The aromatic polycarbonate resin used in the present invention can contain aromatic copolycarbonate oligopolymer.Aromatic copolycarbonate oligopolymer such as can make aromatic dihydroxy compound and carbonyl chloride or carbonic diester react and obtain by using end-capping reagent or molecular weight regulator.As aromatic dihydroxy compound, the mixture of preferred dihydroxyphenyl propane or dihydroxyphenyl propane and other dihydric phenols.
As end-capping reagent or molecular weight regulator, such as, can enumerate phenol, p-di-t-alkylphenol, 2,4,6-tribromophenols, chain alkyl phenol, aliphatic carboxylic acid, hydroxy-benzoic acid, aliphatics acyl chlorides etc.As the concrete example of aromatic copolycarbonate oligopolymer, can preferably enumerate: with the bisphenol-a polycarbonate oligopolymer of p-tert-butylphenol end-blocking, by the copolycarbonate oligomer etc. formed with tetrabromo-bisphenol and the dihydroxyphenyl propane of p-tert-butylphenol end-blocking, may not be the oligopolymer manufactured with the raw material identical with aforementioned fragrance adoption carbonate resin, reaction method.
And then the aromatic polycarbonate resin used in the present invention can be used alone, in order to improve liquidity, also can use and carrying out alloying with other mixed with resin and the resin obtained.As the resin of use when carrying out alloying, such as, can enumerate acrylicstyrene (AS) resin, acryl-butadiene-vinylbenzene (ABS) resin etc.As the blending ratio of other resins such as aromatic polycarbonate resin and AS resin, ABS resin when carrying out alloying, such as relative to aromatic polycarbonate resin 100 mass parts, for other resin 5 ~ 900 mass parts, be preferably resin 10 ~ 500 mass parts.
As the pigment used in the present invention, as long as the material of pigment can be used as, be just not particularly limited.Such as can enumerate each pigment dyestuffs such as azo system, phthalocyanine system, quinacridone, dioxazine Xi, perylene system, isoindolinone system; Carbon black; The mineral dye etc. such as titanium oxide base, iron oxide, chromic oxide system, chrome yellow system.Wherein, preferred carbon black.These pigment can use a kind or combinationally use two or more.
For the content of the pigment in dye compositions, from excellent heat resistance, and it is good for the affinity of vector resin described later (letdown resin), and set out in the aspect that result can show better melting effect, relative to aromatic polycarbonate resin 100 mass parts, be preferably the scope of 0.1 ~ 235 mass parts, be more preferably 0.1 ~ 150 mass parts, more preferably 5 ~ 150 mass parts, be particularly preferably 10 ~ 150 mass parts.
The feature of the ester system additive used in the present invention is, it is the alkyl ester of aromatic polycarboxylic acid, and the alkyl chain of this alkyl ester is the straight-chain alkyl chain of carbonatoms 16 ~ 26.Here, in alkyl chain, the alkyl chain of carbonatoms 18 ~ 24 forms excellent heat resistance, the affinity of vector resin (aromatic polycarbonate resin) is shown to the ester system additive of better melting effect, therefore preferably, the more preferably alkyl chain of alkyl chain, the further preferred carbonatoms 20 ~ 23 of carbonatoms 20 ~ 24.
For ester system additive (ester cpds) used in the present invention, such as, suitably can obtain by making aromatic polycarboxylic acid or its acid anhydrides (A) carry out esterification with the monohydroxy-alcohol (B) of the straight-chain alkyl chain with carbonatoms 16 ~ 26.It should be noted that, in the present invention, first number of aromatic polycarboxylic acid refers to the carboxyl number in 1 molecule, in acid anhydrides, refers to the carboxyl number before dehydrating condensation.
For described aromatic polycarboxylic acid (A), as long as the aromatics with more than 2 carboxyls is just not particularly limited, such as, phthalic acid, m-phthalic acid, terephthalic acid, benzene-1, trimellitic acid, trimesic acid, mellophanic acid, prehnitic acid, pyromellitic acid, mellitic acid can be enumerated.As aromatic polycarboxylic acid acid anhydride, the acid anhydrides etc. of described aromatic polycarboxylic acid can be enumerated.Wherein, better melting effect is shown from the viewpoint of for the affine performance with vector resin (aromatic polycarbonate resin), preferably there is the aromatics of more than 3 carboxyls, preferably can enumerate trimellitic acid, pyromellitic acid and their acid anhydrides.These aromatic polycarboxylic acids or its acid anhydrides can only be used singly, or in combination of two or more kinds.
The monohydroxy-alcohol (B) used in the present invention is the monohydroxy-alcohol of the straight-chain alkyl chain with carbonatoms 16 ~ 26.As such alcohol, such as can enumerate hexadecanol (C16), stearyl alcohol (C18), eicosanol (C20), heneicosane alcohol (C21), V-1326 (C22), tricosanol (C23), Tetracosyl alcohol (C24), pentacosane alcohol (C25), n-Hexacosanol (C26) etc., wherein, from excellent heat resistance, and set out in the aspect that the affinity with vector resin can show better melting effect, preferably there is the monohydroxy-alcohol that carbonatoms is the straight-chain alkyl chain of 18 ~ 24, more preferably there is the monohydroxy-alcohol of the alkyl chain of carbonatoms 20 ~ 24, preferably there is the monohydroxy-alcohol of the alkyl chain of carbonatoms 20 ~ 23 further.Specifically, preferred stearyl alcohol (C18), eicosanol (C20), heneicosane alcohol (C21), V-1326 (C22), tricosanol (C23), Tetracosyl alcohol (C24), more preferably eicosanol (C20), heneicosane alcohol (C21), V-1326 (C22), tricosanol (C23), Tetracosyl alcohol (C24), further preferred eicosanol (C20), heneicosane alcohol (C21), V-1326 (C22), tricosanol (C23).
In the present invention, in the scope not damaging effect of the present invention, the monohydroxy-alcohol beyond above-mentioned monohydroxy-alcohol (B) and monohydroxy-alcohol (B) can be used.As the monohydroxy-alcohol beyond monohydroxy-alcohol (B), such as, octanol (C8), decyl alcohol (C10), dodecanol (C12), tetradecanol (C14), Heptacosanol (C27), policosanol (C28), nonacosanol (C29), triacontanol price quote (C30), hentriacontanol (C31), n-Dotriacontanol (C32), psyllostearyl alcohol (C33), inearnatyl alcohol (C34), pentatriacontane alcohol (C35), hexatriacontane alcohol (C36) etc. can be enumerated.
For the position of substitution of the hydroxyl in the monohydroxy-alcohol beyond the monohydroxy-alcohol used in the present invention (B), monohydroxy-alcohol (B), can be any one in 1 or 2, preferably the position of substitution of use hydroxyl be the monohydroxy-alcohol of 1.
As the manufacture method of ester system additive (ester cpds) used in the present invention, can enumerate and aforementioned fragrance race polycarboxylic acid (A) and aforementioned monohydroxy-alcohol (B) are dosed in reactor, make it carry out the method etc. of common esterification.In addition, in order to promote this esterification, preferably esterifying catalyst is used.
As aforementioned esterifying catalyst, metal or organometallic compound can be used.Specifically, at least one metal, the organometallic compound that are selected from by the group of periodictable 2 race, 4 races, 12 races, 13 races and 14 group compositions can be enumerated.More specifically, such as, can enumerate: the metals such as titanium, tin, zinc, aluminium, zirconium, magnesium, hafnium, germanium; The metallic compounds etc. such as titanium tetraisopropylate, four butanols titaniums, methyl ethyl diketone oxygen titanium, stannous octoate, 2 ethyl hexanoic acid tin, zinc acetylacetonate, zirconium tetrachloride, zirconium tetrachloride tetrahydrofuran complex, hafnium tetrachloride, hafnium tetrachloride tetrahydrofuran complex, germanium oxide, tetraethoxy germanium.Wherein, good from the viewpoint of reactive, easily operation, the storage stability of ester cpds that obtained by esterification, the Titanium alkoxides such as preferred titanium tetraisopropylate, four butanols titaniums, methyl ethyl diketone oxygen titanium.
In addition, for the consumption of aforementioned esterifying catalyst, as long as can esterification be controlled and can suppress the amount of the painted scope of the ester cpds obtained, relative to the total amount of aforementioned fragrance race polycarboxylic acid (A) and aforementioned monohydroxy-alcohol (B), be preferably the scope of 10 ~ 2000ppm, be more preferably the scope of 20 ~ 1000ppm.
When manufacturing aforementioned ester cpds, for the moment of adding aforementioned esterifying catalyst, can add while aforementioned fragrance race polycarboxylic acid (A) and aforementioned monohydroxy-alcohol (B) are dosed in reactor, also can add in intensification way, can also by esterifying catalyst portion-wise addition.
In described esterification, for the feed ratio of foregoing polycarboxylic acids (A) and aforementioned monohydroxy-alcohol (B), relative to the alcohol hydroxyl group of aforementioned monohydroxy-alcohol (B), polycarboxylic acid (A) is not particularly limited, such as, relative to alcohol hydroxyl group 1.00 equivalent of aforementioned monohydroxy-alcohol (B), preferably to make the carboxyl of polycarboxylic acid (A) be that scope, the more preferably mode of the scope of 0.90 ~ 1.10 equivalent of 0.80 ~ 1.20 equivalent regulates.
For temperature of reaction during the aforementioned ester cpds of manufacture, from the viewpoint of promoting reaction while can suppressing each raw materials evaporate or distillation and the ester cpds thermolysis that can suppress to be generated by reaction, painted, be preferably the scope of 60 ~ 300 DEG C, be more preferably the scope of 100 ~ 250 DEG C.
The ester cpds obtained by above-mentioned manufacture method is stable, is also less likely to occur hydrolysis, is less likely to occur to overflow because of good with the consistency of aromatic polycarbonate resin under hot and humid.In addition, can improve the Xie Xuxing's of target coloration agent from the viewpoint of by the surface treatment state adjustment acid number according to pigment, hydroxyl value, adjustment affinity, preferably have less than 30 hydroxyl value and have less than 15 acid number, more preferably have less than 20 hydroxyl value and have less than 10 acid number, particularly preferably have less than 15 hydroxyl value and have less than 5 acid number.
As the form of the ester cpds obtained thus (ester system additive), be not particularly limited, such as, powdery, granular, pellet, tabular, flake etc. can be enumerated.Their making method is also not particularly limited, following method can be enumerated: the travelling belt ester cpds of molten state being taken out to stainless steel tubbing or band refrigerating unit, utilizes pulverizer etc. to make the method for powder, plate, thin slice etc.; Solidification pulverized product is carried out the method for granulation by compress or heating etc.; By molten state directly with the method that particle, pellet are taken out; Using certain proportion with as the mixing and method etc. that is that take out after carrying out masterbatch of the aromatic polycarbonate resin of vector resin.
For the content of ester system additive in dye compositions obtained thus, relative to aromatic polycarbonate resin 100 parts, be preferably 0.1 ~ 235 mass parts, be more preferably 0.5 ~ 120 mass parts, more preferably 0.8 ~ 100 mass parts.
Aforementioned ester system additive is demonstrated to the mechanism of action of the Xie Xuxing (solution colloidality) of excellent pigment, not clear at present, can think, by having aromatic backbone, compared with the material of aliphatics skeleton in the past, excellent heat resistance, even if be also less likely to occur under the high temperature when melting mixing to decompose, can continue display original plasticizing effect, interfacial activity effect, its result, even if also can reduce melt viscosity in the dye compositions comprising pigment with high density.In addition, can think, also high with the affinity of the aromatic polycarbonate resin as vector resin because of its structure, aforementioned ester system additive acts on vector resin and pigment effectively, can improve melting effect.As a result, can think and also produce following effect: the Xie Xuxing improving the pigment in dye compositions, decrease the formation of the big particles such as non-dispergation thing, thus reduce the filter pressure of the strainer be arranged on melting mixing machine.So, aforementioned ester system additive suitably can be used for aromatic polycarbonate resin as the dispersion agent of softening agent or pigment.
Above-mentioned aromatic polycarbonate resin, pigment and ester system additive are obtained by mixing by dye compositions of the present invention, are not particularly limited the order by merging of these materials.Such as, can be (method 1): mixing aromatic polycarbonate resin, pigment and ester system additive simultaneously; Also can be (method 2): after obtaining the mixing thing of pigment and ester system additive in advance, carry out mixing with aromatic polycarbonate resin.More specifically, such as, when method 1, also can by aromatic polycarbonate resin, after pigment and ester system additive mix in the mode making material fully mix each other in advance, at the temperature of the scope of 220 ~ 300 DEG C, melting mixing is carried out with singe screw or twin screw extruder, in addition, when method 2, also can by pigment and ester system additive at the temperature of the scope of 80 ~ 150 DEG C, melting mixing is carried out with singe screw or twin screw extruder, then, the mixing thing obtained and aromatic polycarbonate resin one are reinstated forcing machine etc. and carries out melting mixing.
The dye compositions obtained thus can be used as Masterbatch, as its form, is not particularly limited, and such as, can enumerate pellet, tabular, flake etc.
It should be noted that, for dye compositions of the present invention, also can add other any compositions except mentioned component as required, the additives such as such as lubricant, antistatic agent, UV light absorber, antioxidant.
The dye compositions of the present invention obtained thus is mixing and obtain through painted aromatic copolycarbonate resin composition with the aromatic polycarbonate resin (being called dilution aromatic polycarbonate resin in the present invention) of dilution.More specifically, carry out melting mixing by the dilution aromatic polycarbonate resin of the scope of the scope of 100 ~ 1000000 mass parts, preferably 200 ~ 100000 mass parts and dye compositions of the present invention 100 mass parts at the temperature more than the fusing point of dilution aromatic polycarbonate resin, under the heating of the scope of such as 250 ~ 300 DEG C, can aromatic copolycarbonate resin composition be obtained.
As the content of the ester system additive in the aromatic copolycarbonate resin composition now obtained, such as relative to total 100 mass parts of the aromatic polycarbonate resin in dye compositions and dilution aromatic polycarbonate resin, be preferably 0.00001 weight part ~ 0.14 mass parts, be more preferably 0.00008 weight part ~ 0.10 mass parts.
Then, by by shaping for aromatic copolycarbonate resin composition of the present invention, thus the products formed of aromatic polycarbonate resin can be formed.Specifically, use various forcing machine, injection moulding machine etc. that aromatic copolycarbonate resin composition of the present invention is carried out injection molding, T-shaped mould film forming etc., thus the products formed of different shape can be obtained.For dilution aromatic polycarbonate resin, such as can enumerate the aromatic polycarbonate resin same with the aromatic polycarbonate resin used in dye compositions, the aromatic polycarbonate resin of the aromatic polycarbonate resin identical type that preferably combination uses and uses in dye compositions.Except forming method as above, also can enumerate and in advance dye compositions and dilution aromatic polyester resins after mixing, be dropped into the method etc. of carrying out melting mixing and straight forming in injection moulding machine in mixing machine, stirrer etc.
Aforementioned fragrance adoption polycarbonate resin composition is carried out shaping forming by products formed of the present invention.As such products formed, such as, can enumerate: with appliances parts such as TV part, VTR parts, blower enclosure, iron components, electromagnetic oven parts, various CDs; The electronic communication parts such as relay shell, LED, computer architecture parts; The lighting fixtures parts such as the housing of illuminating cover, torch light; The automobile parts such as head lamp lens, door handle, instrument mask, bike windsheild, window shutter; Optical-mechanical components such as photography fuselage and parts etc.; The OA equipment unit such as structure unit, FDD parts, Personal Computer parts of duplicating machine, printer; The products formed towards electric/electronic device purposes that the mechanical part such as pump part, electric power tool shell etc. are representative;
With daily necessities such as toy, stroller components, water channel device component, kettle, combs; The stationery such as fountain pen, pencil-knife; The Sport & Casual articles for use such as fin keel, pinball game parts, the helmet of skiing goggles, sword-play protector, board sailing are the products formed towards groceries related utilities of representative;
With the products formed towards medical treatment security personnel purposes that artificial kidney case, medicament for the eyes container, the engineering helmet, protective spectacles, extinguisher parts etc. are representative;
Be the products formed etc. towards sheet thin film application of representative with optical thin film etc. with packaging film, capacitor film, FPD (flat-panel monitor).
Embodiment
, enumerate embodiments of the invention below, compare while describe the present invention in detail with comparative example.In example, unless otherwise specified, then " part ", " % " are quality criteria.
Embodiment 1 (preparation of aromatic polycarbonate resin softening agent)
In the four-hole boiling flask of inner capacities 3L that thermometer, agitator, nitrogen ingress pipe and fractionation still head are housed, feed intake after Tetra hydro Phthalic anhydride (hereinafter referred to as " PA ") 176.8g, V-1326 (product containing V-1326 98%) 847.6g, toluene 51g and titanium tetraisopropylate (hereinafter referred to as " TiPT ") 0.31g, while be blown into nitrogen with the scope of 100 ~ 500ml/ minute to maintain less than 100 DEG C to make tower top temperature, be warming up to 230 DEG C.Then, the moisture generated at 230 DEG C is removed, while carry out dehydration esterification reaction.When the acid number of reaction product reaches below 2, feed intake 85% phosphate aqueous solution 0.25g, starts decompression, under the state of 230 DEG C, be decompressed to below 0.67kPa, removes toluene and unreacting alcohol.After no longer flowing out toluene and unreacting alcohol, remove and reduce pressure and lower the temperature, take out after reaction product diatomite filtration, obtain aromatic polycarbonate resin softening agent (1).The number-average molecular weight (Mn) of softening agent (1) is 1090, weight-average molecular weight (Mw) is 1160, acid number is 2.2, hydroxyl value is 3.3.In addition, the outward appearance of softening agent (1) is white solid.
Embodiment 2 (the same)
In the four-hole boiling flask of inner capacities 3L that thermometer, agitator, nitrogen ingress pipe and fractionation still head are housed, feed intake after trimellitic acid 1,2-anhydride (hereinafter referred to as " TMA ") 220.8g, V-1326 (product containing V-1326 98%) 534.2g, stearyl alcohol (product containing stearyl alcohol 98%) 442.5g, toluene 60g and TiPT 0.36g, while be blown into nitrogen with the scope of 100 ~ 500ml/ minute to maintain less than 100 DEG C to make tower top temperature, be warming up to 230 DEG C.Then, the moisture generated at 230 DEG C is removed, while carry out dehydration esterification reaction.When the acid number of reaction product reaches below 2, feed intake 85% phosphate aqueous solution 0.29g, starts decompression, under the state of 230 DEG C, be decompressed to below 0.67kPa, removes toluene.After no longer flowing out toluene, remove and reduce pressure and lower the temperature, liquid temperature is maintained 100 DEG C while be taken out in metal SUS bucket, obtain aromatic polycarbonate resin softening agent (2).The number-average molecular weight (Mn) of softening agent (2) is 1850, weight-average molecular weight (Mw) is 1930, acid number is 3.3, hydroxyl value is 4.5.In addition, the outward appearance of softening agent (2) is white solid.
Embodiment 3 (the same)
In the four-hole boiling flask of inner capacities 3L that thermometer, agitator, nitrogen ingress pipe and fractionation still head are housed, feed intake after TMA 192.0g, V-1326 (product containing V-1326 98%) 929.1g, toluene 56g and TiPT 0.33g, while be blown into nitrogen with the scope of 100 ~ 500ml/ minute to maintain less than 100 DEG C to make tower top temperature, be warming up to 230 DEG C.Then, the moisture generated at 230 DEG C is removed, while carry out dehydration esterification reaction.When the acid number of reaction product reaches below 2, feed intake 85% phosphate aqueous solution 0.27g, starts decompression, under the state of 230 DEG C, be decompressed to below 0.67kPa, removes toluene.After no longer flowing out toluene, remove and reduce pressure and lower the temperature, liquid temperature is maintained 100 DEG C while be taken out in metal SUS bucket, obtain aromatic polycarbonate resin softening agent (3).The number-average molecular weight (Mn) of softening agent (3) is 1670, weight-average molecular weight (Mw) is 1750, acid number is 2.0, hydroxyl value is 7.3.In addition, the outward appearance of softening agent (3) is white solid.
Embodiment 4 (the same)
In the four-hole boiling flask of inner capacities 3L that thermometer, agitator, nitrogen ingress pipe and fractionation still head are housed, after the pyromellitic acid that feeds intake (hereinafter referred to as " PMA ") 218.4g, stearyl alcohol (product containing stearyl alcohol 98%) 882.4g, toluene 55g and TiPT 0.33g, while be blown into nitrogen with the scope of 100 ~ 500ml/ minute to maintain less than 100 DEG C to make tower top temperature, be warming up to 230 DEG C.Then, the moisture generated at 230 DEG C is removed, while carry out dehydration esterification reaction.When the acid number of reaction product reaches below 2, feed intake 85% phosphate aqueous solution 0.26g, starts decompression, under the state of 230 DEG C, be decompressed to below 0.67kPa, removes toluene.After no longer flowing out toluene, remove and reduce pressure and lower the temperature, liquid temperature is maintained 100 DEG C while be taken out in metal SUS bucket, obtain aromatic polycarbonate resin softening agent (4).The number-average molecular weight (Mn) of softening agent (4) is 1900, weight-average molecular weight (Mw) is 1970, acid number is 5.5, hydroxyl value is 4.1.In addition, the outward appearance of softening agent (4) is white solid.
Embodiment 5 (the same)
In the four-hole boiling flask of inner capacities 3L that thermometer, agitator, nitrogen ingress pipe and fractionation still head are housed, after the pyromellitic acid that feeds intake (hereinafter referred to as " PMA ") 190.5g, V-1326 (product containing V-1326 98%) 929.1g, toluene 56g and TiPT 0.34g, while be blown into nitrogen with the scope of 100 ~ 500ml/ minute to maintain less than 100 DEG C to make tower top temperature, be warming up to 230 DEG C.Then, the moisture generated at 230 DEG C is removed, while carry out dehydration esterification reaction.When the acid number of reaction product reaches below 2, feed intake 85% phosphate aqueous solution 0.27g, starts decompression, under the state of 230 DEG C, be decompressed to below 0.67kPa, removes toluene.After no longer flowing out toluene, remove and reduce pressure and lower the temperature, liquid temperature is maintained 100 DEG C while be taken out in metal SUS bucket, obtain aromatic polycarbonate resin softening agent (5).The number-average molecular weight (Mn) of softening agent (5) is 2260, weight-average molecular weight (Mw) is 2390, acid number is 4.1, hydroxyl value is 8.1.In addition, the outward appearance of softening agent (5) is white solid.
Comparative example 1 (preparation of compare aromatic polycarbonate resin softening agent)
In the four-hole boiling flask of inner capacities 3L that thermometer, agitator, nitrogen ingress pipe and fractionation still head are housed, feed intake after tetramethylolmethane 108.8g, stearic acid 908.8g, toluene 51g and TiPT 0.31g, while be blown into nitrogen with the scope of 100 ~ 500ml/ minute to maintain less than 100 DEG C to make tower top temperature, be warming up to 230 DEG C.Then, the moisture generated at 230 DEG C is removed, while carry out dehydration esterification reaction.When the acid number of reaction product reaches below 2, feed intake 85% phosphate aqueous solution 0.24g, starts decompression, under the state of 230 DEG C, be decompressed to below 0.67kPa, removes toluene.After no longer flowing out toluene, remove and reduce pressure and lower the temperature, liquid temperature is maintained 100 DEG C while be taken out in metal SUS bucket, obtain compare aromatic polycarbonate resin softening agent (1 ').The number-average molecular weight (Mn) of this softening agent (1 ') is 1620, weight-average molecular weight (Mw) is 1680, acid number is 1.9, hydroxyl value is 15.0.In addition, the outward appearance of softening agent (1 ') is white solid.
The raw material used in the preparation of aromatic polycarbonate resin softening agent (1) ~ (5) and compare aromatic polycarbonate resin softening agent (1 ') and characteristic value are shown in the 1st table and the 2nd to show.
[table 1]
1st table
The footnote of the 1st table
PA: Tetra hydro Phthalic anhydride
TMA: trimellitic acid 1,2-anhydride
PMA: pyromellitic acid
[table 2]
2nd table
Embodiment 6 (preparation of dye compositions)
By carbon black 700 parts, aromatic polycarbonate resin (dihydroxyphenyl propane, p-tert-butylphenol (molecular weight regulator) and obtained by ordinary method by carbonyl chloride, the granular aromatic polycarbonate resin of viscosity-average molecular weight 21500) 1265g part and aromatic polycarbonate resin softening agent (1) 35g put into poly bag, closes the mouth of bag.Afterwards, the mode mixed each other with material is fully vibrated bag, obtains mixture.
Then, twin screw extruder is used, said mixture is mixing, obtain dye compositions of the present invention (1).Twin screw extruder uses screw diameter 32mm and L/D value is the forcing machine of 52, and jacket temperature set is 270 ~ 280 DEG C.In the preparation of coloring resin agent composition (1), the rotating speed being determined at screw rod is current value when carrying out mixing under the condition of 200rpm, according to value during its current stabilization of following benchmark evaluation.This value is lower, represents that the melt viscosity of melting mixing thing is lower, means that mixing property is excellent and productivity is also excellent.Evaluation result is shown in the 3rd table.
The metewand > of electric current when < is mixing
◎: be less than 30A (ampere)
○：30～32A
×: more than 32A
And then, above-mentioned dye compositions (1) and dilution aromatic polycarbonate resin single screw extrusion machine are carried out melting mixing, prepares through painted aromatic copolycarbonate resin composition (1).During preparation said composition, by the following method, carry out the evaluation of the Xie Xuxing (solution colloidality) of dye compositions (1).It should be noted that, as dilution polycarbonate, use the aromatic polycarbonate resin used in the preparation of above-mentioned dye compositions.
< separates the confirmation method > of colloidality (=Xie Xuxing)
Screw diameter be 30mm and the outlet side that L/D value is the single screw extrusion machine of 30 be provided with filter pressure trier trier in, make dye compositions (1) and dilution aromatic polycarbonate resin by quality ratio for the blending ratio of 9.52/90.48 circulates, finally press trier to extrude by above-mentioned filter, obtain aromatic copolycarbonate resin composition (1).Here, the jacket temperature set of single screw extrusion machine is at 280 DEG C.The formation making the strainer be arranged on filter pressure trier is #80 μm × roasting 40 μm × #80 μm.
When pressing trier to extrude by above-mentioned filter aromatic copolycarbonate resin composition (1), pressure (resin pressure) when mensuration makes aromatic copolycarbonate resin composition (1) inflow filter inlet side and pressure when being discharged by filter outlet side, obtain its difference (filter pressure.MPa), be set to filter pressure trial value, evaluated according to following benchmark.Filter pressure trial value is lower, and mean that the formation of the big particles such as non-dispergation thing is also fewer, " Xie Xuxing (solution colloidality) " is more excellent.
◎: filter pressure is less than 6MPa
Zero: filter pressure 6 ~ 9MPa
△: filter pressure is more than 9MPa
×: test interruption due to blocking
Embodiment 2 ~ 5
Use the aromatic polycarbonate resin softening agent shown in the 3rd table, in addition, obtain dye compositions of the present invention (2) ~ (5) similarly to Example 1.Obtain through painted aromatic copolycarbonate resin composition (2) ~ (5).Carry out evaluation similarly to Example 1, the results are shown in the 3rd table.
Comparative example 2 ~ 4
Use the compare aromatic polycarbonate resin softening agent shown in the 4th table, in addition, obtain compare dye compositions (1 ') ~ (3 ') similarly to Example 1.Obtain through painted aromatic copolycarbonate resin composition (1 ') ~ (3 ').Carry out evaluation similarly to Example 1, the results are shown in the 3rd table.
[table 3]
3rd table
[table 4]
4th table
The footnote of the 4th table
Compare polycarbonate softening agent (2 '): montanic acid ester type waxes (Clariant K.K. system, Licolub WE4.〕
Compare polycarbonate softening agent (3 '): modified polyethylene wax (EVONIK INDUSTRIES system, TEGOMER E 525.〕
Cannot measure: cannot measure due to filter stoppage.
Claims (10)
1. a dye compositions, it is characterized in that, it is the dye compositions containing aromatic polycarbonate resin, pigment and ester system additive, and this ester system additive is the alkyl ester of aromatic polycarboxylic acid, and the alkyl chain of this alkyl ester is the straight-chain alkyl chain of carbonatoms 16 ~ 26.
2. dye compositions according to claim 1, wherein, described ester system additive makes aromatic polycarboxylic acid or its acid anhydrides (A) carry out esterification with the monohydroxy-alcohol (B) of the straight-chain alkyl chain with carbonatoms 16 ~ 26 to obtain.
3. dye compositions according to claim 1, wherein, described monohydroxy-alcohol (B) is for being selected from more than a kind monohydroxy-alcohol in the group that is made up of eicosanol, heneicosane alcohol, V-1326, tricosanol and Tetracosyl alcohol.
4. the dye compositions according to any one in claims 1 to 3, wherein, described aromatic polycarboxylic acid or its acid anhydrides (A) are aromatic polycarboxylic acid or its acid anhydrides of more than 3 yuan.
5. the dye compositions according to any one in claims 1 to 3, wherein, described aromatic polycarboxylic acid or its acid anhydrides (A) are for being selected from more than a kind in the group that is made up of trimellitic acid, pyromellitic acid and their acid anhydrides.
6. the dye compositions according to any one in Claims 1 to 5, wherein, described pigment is carbon black.
7. the dye compositions according to any one in claim 1 ~ 6, wherein, relative to described aromatic polycarbonate resin 100 mass parts, comprises the pigment of 10 ~ 150 mass parts and comprises the ester system additive of 0.8 ~ 100 mass parts.
8. an aromatic copolycarbonate resin composition, is characterized in that, the dye compositions described in any one in claim 1 ~ 7 and dilution aromatic polycarbonate resin are carried out melting mixing and obtain by it.
9. a products formed, is characterized in that, aromatic copolycarbonate resin composition according to claim 8 is carried out shaping forming by it.
10. an aromatic polycarbonate resin softening agent, it is the alkyl ester of aromatic polycarboxylic acid, and the alkyl chain of this alkyl ester is the straight-chain alkyl chain of carbonatoms 16 ~ 26.
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| PCT/JP2013/071392 WO2014027593A1 (en) | 2012-08-16 | 2013-08-07 | Coloring agent composition, aromatic polycarbonate resin composition, molded article, and plasticizer for aromatic polycarbonate resin |
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| CN109642032A (en) * | 2016-08-23 | 2019-04-16 | 胜技高分子株式会社 | The manufacturing method of thermoplastic aromatic polyester and resin composition and the manufacturing method and thermal shock resistance of insert molding product reduce suppressing method |
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| WO2014027593A1 (en) | 2014-02-20 |
| JPWO2014027593A1 (en) | 2016-07-25 |
| KR20150044873A (en) | 2015-04-27 |
| TWI575019B (en) | 2017-03-21 |
| TW201412870A (en) | 2014-04-01 |
| KR102071326B1 (en) | 2020-01-30 |
| CN104583318B (en) | 2016-10-05 |
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