CN1984966A - Thermoplastic resin composition - Google Patents
Thermoplastic resin composition Download PDFInfo
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- CN1984966A CN1984966A CNA2005800236649A CN200580023664A CN1984966A CN 1984966 A CN1984966 A CN 1984966A CN A2005800236649 A CNA2005800236649 A CN A2005800236649A CN 200580023664 A CN200580023664 A CN 200580023664A CN 1984966 A CN1984966 A CN 1984966A
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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
- C08L101/00—Compositions of unspecified macromolecular compounds
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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
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
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Abstract
A thermoplastic resin composition comprising a metallic soap and a thermoplastic resin, wherein said metallic soap is contained in an amount of 0.01 to 10 parts by mass relative to 100 parts by mass of said thermoplastic resin, and wherein the metallic soap is produced by a method comprising reacting 1 mole of a fatty acid having 6 to 24 carbon atoms with 0.90 to 0.99 moles of a mono-valent alkali compound to prepare an alkali compound salt of a fatty acid, and then reacting the alkali compound salt of a fatty acid with an salt of a divalent metal in an aqueous solution. The above composition is excellent in the dispersibility of a pigment, a filler and the like, and also is reduced in the decrease of the molecular weight of the resin.
Description
Technical field
The present invention relates to contain the thermoplastic resin composition of metallic soap and thermoplastic resin.
Background technology
In the past, the additive that thermoplastic resin is used, be in order to improve release property, to prevent that resin and shaper are melt bonded etc. and improve when the resin forming or improve pigment, weighting agent dispersiveness in resin etc. and use, for example, use ester cpds, amide compound, metallic soap, silicone compounds etc. according to above-mentioned purpose.
In these additives, metallic soap or silicone compounds use in order to improve pigment or the weighting agent dispersiveness in resin.For example, the spy opens and discloses the dispersing method that uses the titanium oxide of organopolysiloxane in the 2003-155405 communique.
But, metallic soap if with the phenol antioxidant that is widely used in thermoplastic resin (for example, 3,5-di-t-butyl-4-hydroxytoluene etc.) use together, this antioxidant xanthochromia and make coloring resin then, if use together, then there are problems such as resistance of oxidation forfeiture with Phosphorus antioxidant (for example, triphenyl etc.).In addition, as if dispersed metal soap when preparing the moulding product of vibrin such as polyethylene terephthalate or polycarbonate, then the molecular weight of resin reduces, and this becomes one of reason, has the problem of the intensity reduction of synthetic resin.
For silicone compounds, also there is the problem of the silicone compounds emersion that is free on resulting moulding product surface.
As mentioned above, when utilizing existing additive, the molecular weight that is difficult to not produce reduction, the resin of the painted or antioxidant effect of antioxidant reduce so that problem such as the emersion of the additive that moulding product are surperficial and in thermoplastic resin dispersed color or weighting agent.
Summary of the invention
The objective of the invention is to, the excellent dispersion of pigment, weighting agent etc. is provided, even contain antioxidant, also seldom produce, and the molecular weight of resin reduces less thermoplastic resin composition owing to the coloring resin that xanthochromia caused of antioxidant and the reduction of antioxidant effect.
Thermoplastic resin composition of the present invention is contained metallic soap and thermoplastic resin, and this metallic soap reacts the metal-salt of fatty acid alkali compound salt and divalent and obtains in the aqueous solution; Described fatty acid alkali compound salt make carbonatoms be the alkali cpd of 6～24 lipid acid and 1 valency with 1 mole: 0.90～0.99 mole ratio reacts and obtains, with respect to these thermoplastic resin 100 mass parts, the content of this metallic soap is 0.01 mass parts～10 mass parts.
Preferred embodiment, the metal that constitutes above-mentioned metallic soap is calcium or magnesium.
Preferred embodiment, among this thermoplastic resin composition, with respect to above-mentioned thermoplastic resin 100 mass parts, further contain the ester cpds (hereinafter being sometimes referred to as the tetramethylolmethane ester cpds) that tetramethylolmethane and carbonatoms are 14～24 1 valency saturated fatty acid with the ratio of 0.001 mass parts～5 mass parts.
Preferred embodiment, the acid number of above-mentioned ester cpds be 5.0 or below, hydroxyl value be 20.0 or below.
Preferred embodiment, above-mentioned thermoplastic resin is a vibrin.
The thermoplastic resin composition of the present invention of containing metallic soap and thermoplastic resin, the excellent dispersion of pigment, weighting agent etc., and the molecular weight reduction that is difficult for producing resin.Even when containing antioxidant among the thermoplastic resin composition of the present invention, do not hinder antioxidant effect yet, when particularly containing phenol antioxidant, compare with in the past thermoplastic resin composition, in resin, be difficult for producing painted.Further contain the thermoplastic resin composition under the situation of tetramethylolmethane ester cpds, each mixture of ingredients that contains composition is carried out heating and melting add the oilness in man-hour and be improved.
Embodiment
Thermoplastic resin composition of the present invention is contained metallic soap and thermoplastic resin, contains tetramethylolmethane ester cpds, additive etc. as required.Hereinafter they are described successively.
(1) metallic soap
Employed metallic soap among the present invention is to prepare by the double decomposition that makes fatty acid alkali compound salt and divalent reacting metal salt.This metallic soap is characterised in that it reacts the metal-salt of fatty acid alkali compound salt and divalent and obtains in the aqueous solution; Described fatty acid alkali compound salt make carbonatoms be the alkali cpd of 6～24 lipid acid and 1 valency with 1 mole: 0.90～0.99 mole ratio reacts and obtains.
For the lipid acid of the raw material of fatty acid alkali compound salt,, then do not limit especially so long as carbonatoms is 6～24 lipid acid.That is, can be any one of natural acid and synthetic fatty acid, can be any one of saturated fatty acid and unsaturated fatty acids, can be straight chain shape and catenate any one.Further, can contain hydroxyl, aldehyde radical, epoxy group(ing) etc. in the structure of lipid acid.Preferred carbonatoms is 10～22 straight chain fatty acid.Carbonatoms can not obtain the effect as the dispersion agent of resulting metallic soap less than 6 o'clock, and carbonatoms is difficult in industrial acquisition above 24 lipid acid.These lipid acid can use or make up at least 2 kinds of uses separately.
As above-mentioned lipid acid, for example can enumerate caproic acid, sad, capric acid, lauric acid, tetradecanoic acid, Oleomyristic acid, Palmiticacid, physetoleic acid, stearic acid, oleic acid, linolic acid, linolenic acid, eicosanoic acid, docosoic acid, erucic acid, oxystearic acid, montanic acid, Unimac 5680,2 ethyl hexanoic acid and epoxystearic acid.
As 1 valency alkali cpd of the raw material of fatty acid alkali compound salt, can enumerate the oxyhydroxide of basic metal (sodium, potassium etc.); With amines such as ammonia, monoethanolamine, diethanolamine, trolamine etc.Solubleness when forming fatty acid alkali compound salt water higher aspect consider, be preferably alkali-metal oxyhydroxide such as sodium, potassium.
Fatty acid alkali compound salt can be the alkali cpd that makes above-mentioned lipid acid and above-mentioned 1 valency by lipid acid: the alkali cpd of 1 valency=1 mole: 0.90～0.99 mole, preferably with 1 mole: 0.95～0.98 mole ratio reacts and the material that obtains.If with respect to 1 mole in lipid acid, the alkali cpd of 1 valency is less than 0.90 mole or above 0.99 mole, then use the fatty acid alkali compound salt of reaction gained to prepare metallic soap, and when using this metallic soap, might can not obtain desired synthetic resin resin forming.Particularly if use with respect to 1 mole in lipid acid, the alkali cpd of 1 valency is reacted and the fatty acid alkali compound salt that obtains prepares metallic soap with it with the amount that surpasses 0.99 mole, and this metallic soap added to when carrying out moulding in the thermoplastic resin, the molecular weight that produces resin reduces; Or the thermoplastic resin composition is when containing antioxidant, bad problems such as antioxidant effect reduction, coloring resin.
Employed fatty acid alkali compound salt among the present invention, be alkali cpd and the lipid acid that makes 1 valency, with above-mentioned ratio, generally in the fusing point of lipid acid or above and this lipid acid temperature of degree of decomposition not, preferably at 100 ℃ or following, more preferably at 50 ℃～100 ℃, further preferred the reaction at 80 ℃～95 ℃ obtains.
Employed metallic soap among the present invention reacts the metal-salt of fatty acid alkali compound salt and divalent and obtains in the aqueous solution.The metal-salt of above-mentioned divalent, specifically, be divalent inorganic metal and with mineral acid or organic acid salt.As the inorganic metal of divalent, can enumerate alkaline-earth metal such as magnesium, calcium, barium; Titanium, zinc, iron, manganese, cadmium, mercury, zirconium, lead, copper, cobalt, nickel etc.Wherein,, aspect industrial acquisition, consider easily, be preferably calcium, magnesium, barium and zinc from because the painted and decomposition that heating is caused is less.Consider from the pigment-dispersing aspect, be preferably calcium or magnesium especially.
As the metal-salt of divalent, for example can enumerate calcium chloride, lime acetate, magnesium chloride, sal epsom, copper sulfate, bariumchloride, zinc chloride, zinc sulfate etc.Particularly the muriate of calcium, magnesium etc., vitriol and nitrate react with carboxylate salt efficiently owing to the favorable solubility in water, thereby preferred.
Specifically, above-mentioned reaction is by after preparation in advance contains the aqueous solution of divalent metal-salt and contains the aqueous solution of fatty acid alkali compound salt respectively, then their mixing is carried out.For example, by in the aqueous solution that contains fatty acid alkali compound salt, dripping the aqueous solution that contains the divalent metal-salt; In the aqueous solution that contains the divalent metal-salt, drip the aqueous solution that contains fatty acid alkali compound salt; Or be added drop-wise to simultaneously in the reactive tank and carry out.
The concentration of the fatty acid alkali compound salt during the preparation metallic soap, from the productivity aspect of metallic soap and contain the aqueous solution of fatty acid alkali compound salt or the processing aspect of resulting metallic soap slurry is considered, be generally 1 quality %～20 quality %, be preferably 5 quality %～15 quality %.Fatty acid alkali compound salt concn is during less than 1 quality %, and the productive rate of metallic soap is low, and is not preferred in the practicality.When surpassing 20 quality %,, be difficult to carry out the reaction of homogeneous owing to contain the viscosity increase of the aqueous solution or the resulting metallic soap slurry of fatty acid alkali compound salt.In addition, the concentration that contains the divalent metal-salt in the solution of divalent metal-salt, from the productivity aspect of metallic soap and contain the aqueous solution of fatty acid alkali compound salt or the processing aspect of resulting metallic soap slurry is considered, be generally 1 quality %～50 quality %, be preferably 10 quality %～40 quality %.
The reaction of above-mentioned fatty acid alkali compound salt and divalent metal-salt, preferably according to respect to 1 mole of the 1 valency alkali cpd that uses in order to obtain fatty acid alkali compound salt, the metal-salt of divalent is that 0.45 mole～0.7 mole ratio carries out.More preferably the ratio of divalent metal-salt is 0.49 mole～0.6 mole, and further preferred ratio is 0.49 mole～0.55 mole.The divalent metal-salt is outside 0.45 mole～0.7 mole scope the time, as if being added to, resulting metallic soap carries out moulding in the thermoplastic resin, then the molecular weight of resulting resin might reduce, and when containing antioxidant, might produce bad problems such as antioxidant effect reduction, coloring resin.
The solubleness of fatty acid alkali compound salt is considered in the reaction of fatty acid alkali compound salt and divalent metal-salt, carries out under the temperature condition that those skilled in the art carry out usually.Be preferably 50 ℃～100 ℃, more preferably 70 ℃～95 ℃.
Obtain the metallic soap slurry by aforesaid method.These metallic soap slurries can not handled, or rotate through branch exsolution agent such as filter by centrifuge, pressure filter, vacuum, as required, wash, after removing by-product inorganic salts, carry out drying by Rotary drying device, Pneumatic drying device, aeration type drying installation, spraying type drying installation, fluidisation stratotype drying installation etc.Drying means can be any one under continous way or batch-type, normal pressure or the vacuum.So can obtain metallic soap of the present invention.
When the metallic soap that will so obtain with the concentration of 2 quality % was scattered in the water, pH was 5.0～7.5.Resulting metallic soap can use separately, or mixes the metallic soap that contains different metals and use.
(2) thermoplastic resin
Employed thermoplastic resin among the present invention is not limited especially, can enumerate for example following resin: the polymeric blends of chlorine-containing resins such as polyvinyl chloride, chlorinated polyvinyl chloride, chlorinatedpolyethylene, vinylchlorid/vinyl acetate copolymer and this chlorine-containing resins and other resin; The polymeric blends of polymeric blends, polyolefin resin and other resin of polyolefin resines such as new LDPE (film grade), high density polyethylene(HDPE), straight-chain low density polyethylene, polypropylene, polyolefin resin and constitute the monomer (alhpa olefin) of these resins and other monomeric multipolymer; The polymeric blends of the polymeric blends of polyamide resin, multiple polyamide resin, polyamide resin and other resin and the monomer and other the monomeric multipolymer that constitute polyamide resin; The polymeric blends of the polymeric blends of vibrin such as polycarbonate, polyethylene terephthalate, multiple vibrin, vibrin and other resin and the monomer and other the monomeric multipolymer that constitute vibrin; The polymeric blends of the polymeric blends of ABS resin, multiple ABS resin, ABS resin and other resin and the monomer and other the monomeric multipolymer that constitute ABS resin; The polymeric blends of the polymeric blends of polyacetal resin, multiple polyacetal resin, polyacetal resin and other resin and the monomer and other the monomeric multipolymer that constitute polyacetal resin.Wherein, particularly be preferably the polymeric blends of polymeric blends, vibrin and other resin of vibrin, multiple vibrin and monomer and other monomeric multipolymer, the more preferably vibrin that constitutes vibrin.
(3) tetramethylolmethane ester cpds
Thermoplastic resin composition of the present invention as required, is contained the tetramethylolmethane ester cpds.This tetramethylolmethane ester cpds is that tetramethylolmethane and carbonatoms are the ester of 14～24 1 valency saturated fatty acid.By containing this ester cpds, improve the oilness that adds man-hour and processing machine or mould.The acid number of this ester cpds be preferably 5.0 or below, more preferably 3.0 or below, hydroxyl value be preferably 20.0 or below, more preferably 15.0 or below.If acid number surpass 5.0 or hydroxyl value surpass 20.0, resulting thermoplastic resin composition is painted, might cause the reduction of intensity.
(4) additive
As the additive that contains as required among the thermoplastic resin composition of the present invention, for example, following compound or material are arranged: weighting agents such as talcum, mica, lime carbonate, potassium titanate, Calucium Silicate powder; Mineral dyes such as titanium oxide, carbon black, ferric oxide, ultramarine; Pigment dyestuffs such as phthalocyanine-like compound, quinoline a word used for translation ketone compounds, anthraquinone analog compound, azoles; Antioxidants such as phenolic compound, phosphite ester compound, hindered phenol compound, phosphite ester compound, phosphate compounds, aminated compounds; Exterior lubricant such as photostabilizers such as hindered amine compound, the aliphatic fatty acid ester compound except above-mentioned tetramethylolmethane ester cpds, paraffin class compound, organic aliphatic acid; Fire retardant, releasing agent, static inhibitor etc.
(5) thermoplastic resin composition
Thermoplastic resin composition of the present invention as mentioned above, is contained above-mentioned metallic soap and thermoplastic resin, as required, can contain tetramethylolmethane ester cpds and other additive.
The content of above-mentioned metallic soap with respect to above-mentioned thermoplastic resin 100 mass parts, is 0.01 mass parts～10 mass parts, is preferably 0.1 mass parts～5 mass parts.The content of metallic soap can not be brought into play sufficient colo(u)rant dispersion power during less than 0.01 mass parts.When surpassing 10 mass parts, metallic soap causes outward appearance to reduce at the resin surface emersion.Content to above-mentioned tetramethylolmethane ester cpds does not limit especially.Preferably with respect to thermoplastic resin 100 mass parts, above-mentioned tetramethylolmethane ester cpds is 0.001 mass parts～5 mass parts.The content of above-mentioned ester cpds is during less than 0.001 mass parts, resulting thermoplastic resin composition's oilness deficiency, might produce with processing machine adhere to or the outward appearance of moulding product bad.When surpassing 5 mass parts, ester cpds might produce the reduction of bad order and intensity etc. at the resin surface emersion.In addition, employed metallic soap among the present invention makes above-mentioned ester cpds painted hardly.
Each composition of above-mentioned thermoplastic resin composition, be thermoplastic resin, metallic soap and the additive that contains as required, by the normally used method of mixing of those skilled in the art of the present technique, for example, ribbon blender, Henschel mixer, Banbury mixer, drum roller, single screw extrusion machine, twin screw extruder, common kneading machine, multiple screw extruder etc. mix.Then, can pass through the normally used forming method of those skilled in the art of the present technique, for example, moulding is carried out in injection molding, compressed moulding, calendering formation, rotoforming etc., be used for various moulding product, for example, the manufacturing of various moulding product such as automotive field, OA field of components.
Embodiment
The present invention will be described in more detail hereinafter to enumerate embodiment.
(preparation example 1: the preparation of metallic soap)
In detachable (the セ パ テ Block Le) flask of 3L glass, add mixed fatty acid (containing 2.5 quality % tetradecanoic acids, 30.0 quality % Palmiticacid, 66.4 quality % stearic acid, 0.8 quality % eicosanoic acid and 0.3 quality % docosoic acid) 250g (0.90 mole) and water 2500g, and be warming up to 90 ℃.Then, add 48% aqueous sodium hydroxide solution 72.5g (0.87 mole), and stirred 1 hour down in identical temperature (90 ℃).Then, remaining under 90 ℃ the state, with dripping 25% magnesium sulfate solution 221g (0.46 mole) in 1 hour.After dripping off, further stirred 1 hour down at 90 ℃.In resulting mixed fatty acid magnesium slurries, add entry 1500g, be cooled to 65 ℃ or following.Then, filter with suction filter, with the water washing of 1000g 2 times, use blast drier 65 ℃ dry 48 hours down, obtain metallic soap.
Free fatty acid content, metal content, fusing point, moisture and pH for resulting metallic soap analyze with following method.The result is as shown in table 1.
(1) free fatty acids
Accurately take by weighing metallic soap 5g and put into beaker, add ether mixed solvent 50ml, stir the back and placed 30 minutes.Then, use 5B filter paper to filter, carry out titration, calculate the free fatty acids amount according to following formula with 1/10N potassium hydroxide-ethanol solution.In the formula, MW represents the molecular weight of lipid acid, and A represents the dripping quantity of potassium hydroxide titrating solution, and f represents the coefficient of potassium hydroxide titrating solution.
Free fatty acids (%)=MW * A (ml) * f/100
(2) metal content
Accurately take by weighing metallic soap 0.1g, organism was removed in heating in 4 hours under 650 ℃ in magnetic system crucible.In residue, add hydrochloric acid 1ml and dissolve, add entry to 100ml.With this solution as sample, by atom Their Determination by Spectrophotometry metal content.
(3) fusing point
Measure with the method for putting down in writing among the JIS-K0064.
(4) moisture
Measure with the method for putting down in writing among the JIS-K0067.Drying is to use the 2g metallic soap to carry out under 105 ℃ as sample.
(5)pH
Use contains the aqueous solution of 0.2 quality % nonionic class tensio-active agent (NOF Corp's system, ノ ニ オ Application NS-210), and preparation contains the aqueous dispersions of 2 quality % metallic soaps, measures pH down for 25 ℃.
(preparation example 2: the preparation of metallic soap)
In the detachable flask of 3L glass, add the mixed fatty acid 250g (0.90 mole) and the water 2500g of preparation example 1, and be warming up to 90 ℃.Then, add 48% aqueous sodium hydroxide solution 73g (0.87 mole), stirred 1 hour down at uniform temp (90 ℃).Then, remaining under 90 ℃ the state, with dripping 25% zinc sulfate solution 291g (0.45 mole) in 1 hour.Resulting mixed fatty acid zinc slurries are filtered with suction filter, and the water washing of usefulness 1000g 3 times uses blast drier to descend dry 30 hours at 80 ℃, obtains metallic soap.For free fatty acid content, metal content, fusing point, moisture and the pH of resulting metallic soap, use the method identical to analyze with preparation example 1.The result is as shown in table 1.
(preparation example 3: the preparation of metallic soap)
In the detachable flask of 5L glass, add lauric acid 250g (1.25 moles) and water 2500g, be warming up to 90 ℃.Then, add 48% aqueous sodium hydroxide solution 99g (1.19 moles), stirred 1 hour down at uniform temp (90 ℃).Then, be warming up to 95 ℃.Remaining under 95 ℃ the state, with 1 hour Dropwise 35 % calcium chloride water 200g (0.63 mole).After dripping off, further stirred 1 hour down at 95 ℃.Be cooled to 60 ℃ or following while stirring resulting calcium laurate slurries.Then, use chamber space to be 75cm
3Desk-top pressure filter filter, with the water washing of 1000g 3 times, use blast drier 70 ℃ dry 48 hours down, obtain metallic soap.For free fatty acid content, metal content, fusing point, moisture and the pH of resulting metallic soap, use the method identical to analyze with preparation example 1.The result is as shown in table 1.
(preparation example 4: the preparation of metallic soap)
In the removable isolating flask of 5L glass, add the mixed fatty acid 250g (0.90 mole) and the water 2500g of preparation example 1, and be warming up to 90 ℃.Then, add 48% aqueous sodium hydroxide solution 71.7g (0.86 mole), and stirred 1 hour down at uniform temp (90 ℃).Then, remaining under 90 ℃ the state, with dripping 10% barium chloride solution 917g (0.44 mole) in 1 hour.After dripping off, further stirred 1 hour down at 90 ℃.Resulting mixed fatty acid barium slurries are filtered with suction filter, and the water washing of usefulness 1000g 3 times uses blast drier to descend dry 30 hours at 80 ℃, obtains metallic soap.For free fatty acid content, metal content, fusing point, moisture and the pH of resulting metallic soap, use the method identical to analyze with preparation example 1.The result is as shown in table 1.
(preparation example 5: the preparation of metallic soap)
In the detachable flask of 5L glass, add the mixed fatty acid 250g (0.90 mole) and the water 2500g of preparation example 1, and be warming up to 90 ℃.Then, add 48% aqueous sodium hydroxide solution 73g (0.87 mole), stirred 1 hour down at uniform temp (90 ℃).Then, remaining under 90 ℃ the state, with 1 hour Dropwise 35 % calcium chloride water 146g (0.46 mole).After dripping off, further stirred 1 hour down at 90 ℃.In resulting slurries, add entry 1500g, and be cooled to 65 ℃ or following.Then, filter with suction filter, with the water washing of 1000g 2 times, use blast drier 65 ℃ dry 48 hours down, obtain metallic soap.For free fatty acid content, metal content, fusing point, moisture and the pH of resulting metallic soap, use the method identical to analyze with preparation example 1.The result is as shown in table 1.
(comparative preparation example 1)
In the detachable flask of 5L glass, add the mixed fatty acid 250g (0.90 mole) and the water 2500g of preparation example 1, and be warming up to 90 ℃.Then, add 48% aqueous sodium hydroxide solution 77g (0.92 mole), stirred 1 hour down at uniform temp (90 ℃).Then, remaining under 90 ℃ the state, with dripping 25% zinc sulfate solution 355g (0.55 mole) in 1 hour.After dripping off, further stirred 1 hour down at 90 ℃.Resulting mixed fatty acid zinc slurries are filtered with suction filter, and the water washing of usefulness 1000g 3 times uses blast drier to descend dry 30 hours at 80 ℃, obtains metallic soap.For free fatty acid content, metal content, fusing point, moisture and the pH of resulting metallic soap, use the method identical to analyze with preparation example 1.The result is as shown in table 1.
(comparative preparation example 2)
In the detachable flask of 5L glass, add the mixed fatty acid 250g (0.90 mole) and the water 2500g of preparation example 1, and be warming up to 90 ℃.Then, add 48% aqueous sodium hydroxide solution 77g (0.92 mole), stirred 1 hour down at uniform temp (90 ℃).Then, remaining under 90 ℃ the state, with dripping 25% magnesium sulfate solution 211g (0.46 mole) in 1 hour.After dripping off, further stirred 1 hour down at 90 ℃.In resultant slurry, add 1500g water, and be cooled to 65 ℃ or following.Then, filter with suction filter, with the water washing of 1000g 2 times, use blast drier 65 ℃ dry 48 hours down, obtain metallic soap.For free fatty acid content, metal content, fusing point, moisture and the pH of resulting metallic soap, use the method identical to analyze with preparation example 1.The result is as shown in table 1.
(comparative preparation example 3)
In the detachable flask of 5L glass, add the mixed fatty acid 250g (0.90 mole) and the water 2500g of preparation example 1, and be warming up to 90 ℃.Then, add 48% aqueous sodium hydroxide solution 77g (0.92 mole), stirred 1 hour down at uniform temp (90 ℃).Then, remaining under 90 ℃ the state, with 1 hour Dropwise 35 % calcium chloride water 152g (0.46 mole).After dripping off, further stirred 1 hour down at 90 ℃.In resultant slurries, add 1500g water, and be cooled to 65 ℃ or following.Then, filter with suction filter, with the water washing of 1000g 2 times, use blast drier 65 ℃ dry 48 hours down, obtain metallic soap.For free fatty acid content, metal content, fusing point, moisture and the pH of resulting metallic soap, use the method identical to analyze with preparation example 1.The result is as shown in table 1.
Table 1
| Raw fatty acid alkali cpd salt | Metallic soap | Measurement result | |||||||
| The carbonatoms of lipid acid | Alkali/lipid acid *1(mol ratio) | Free fatty acid content (%) | Metal content (%) | Fusing point (℃) | Moisture (%) | pH | |||
| Preparation example | 1 | 18 | 0.97 | Mixed fatty acid magnesium | 1.2 | 4.1 | 122 | 5.7 | 6.7 |
| 2 | 18 | 0.98 | Mixed fatty acid zinc | 0.2 | 10.3 | 122 | 0.1 | 7.2 | |
| 3 | 12 | 0.95 | Calcium laurate | 3.5 | 8.6 | 155 | 3.9 | 6.6 | |
| 4 | 18 | 0.96 | Mixed fatty acid barium | 2.5 | 20.3 | ≥200 | 0.2 | 6.8 | |
| 5 | 18 | 0.97 | Mixed fatty acid calcium | 0.8 | 6.6 | 153 | 2.7 | 6.9 | |
| The comparative preparation example | 1 | 18 | 1.02 | Mixed fatty acid zinc | 0.2 | 10.4 | 122 | 0.1 | 7.7 |
| 2 | 18 | 1.02 | Mixed fatty acid magnesium | 0.3 | 4.2 | 122 | 5.7 | 9.6 | |
| 3 | 18 | 1.02 | Mixed fatty acid calcium | 0.1 | 6.8 | 155 | 2.7 | 9.8 | |
* the mol ratio of the alkali cpd of 1...1 valency and lipid acid
(embodiment 1～5 and comparative example 1～4: thermoplastic resin composition's preparation and evaluation)
To mix by each metallic soap 1 mass parts, polycarbonate resin particle (the system ユ of the エ of Mitsubishi Application ヅ ニ ア リ Application グ プ テ ス チ Star Network Co., Ltd. one ピ ロ Application) 100 mass parts, titanium oxide (the former industry system of stone イ ペ one Network) 10 mass parts and carbon black (the system ト of East Sea カ one ボ Application Co., Ltd. one カ Block テ Star Network) 1 mass parts that preparation example 1～5 and comparative preparation example 1～3 obtain with drum roller.Then, use internal diameter to mix 280 ℃ of following fusions and extrude, make particle with tablets press as the biaxial extruder of 20mm.After resulting each particle thorough drying, use vertical type injection molding machine, injection molding under 280 ℃ mold temperatures, 90 ℃ die temperature, the POLYCARBONATE SHEET of preparation 70mm * 70mm * 2mm (with them according to the order of preparation example 1～5 and comparative preparation example 1～3 respectively as test film 1～8).In addition, except not making particle, preparation POLYCARBONATE SHEET (as test film 9) with above-mentioned operation similarly the containing metal soap.For resulting test film 1～9, use gel permeation chromatography (GPC, eastern Application one Co., Ltd.'s system) to measure number-average molecular weight, as described below outward appearance and shock strength are estimated.The result is as shown in table 2.
(1) outward appearance (having or not irregular colour)
For test film, visual inspection has or not the generation of irregular colour.Be not made as zero with what find irregular colour fully; To near injection port, find to have the △ that is made as of irregular colour; With find on the whole to have being made as of irregular colour *.
(2) shock strength
The test film that is obtained by injection molding is sheared, made the izod impact test that has otch and measure shock strength with test film.
Table 2
| Raw material | The thermoplastic resin composition | Test-results | ||||||
| Metallic soap (A) (title) | Thermoplastic resin (B) *1 | A/B *2(mass ratio) | pC *1Molecular-weight average (Mn) | Outward appearance | Shock strength | |||
| Embodiment | 1 | Preparation example 1 (mixed fatty acid magnesium) | PC | 1/100 | Test film 1 | 32600 | ○ | 48 |
| 2 | Preparation example 2 (mixed fatty acid zinc) | PC | 1/100 | Test film 2 | 31500 | △ | 50 | |
| 3 | Preparation example 3 (calcium laurate) | PC | 1/100 | Test film 3 | 32400 | ○ | 45 | |
| 4 | Preparation example 4 (mixed fatty acid barium) | PC | 1/100 | Test film 4 | 33100 | △ | 51 | |
| 5 | Preparation example 5 ((mixed fatty acid calcium) | PC | 1/100 | Test film 5 | 31800 | ○ | 46 | |
| Comparative example | 1 | Comparative preparation example 1 (mixed fatty acid zinc) | PC | 1/100 | Test film 6 | 25100 | △ | 25 |
| 2 | Comparative preparation example 2 ((mixed fatty acid magnesium) | PC | 1/100 | Test film 7 | 22300 | ○ | 12 | |
| 3 | Comparative preparation example 3 (mixed fatty acid calcium) | PC | 1/100 | Test film 8 | 19500 | ○ | 8 | |
| 4 | Do not use | PC | 1/100 | Test film 9 | 34000 | × | 52 | |
* 1...PC: polycarbonate
* 2... metallic soap/thermoplastic resin (mass ratio)
As shown in Table 2, the test film (test film 1～5) that contains the metallic soap of preparation example, compare with the test film (test film 6～8) of the metallic soap that contains comparative preparation example 1～3, the reduction of the molecular-weight average of polycarbonate is less, and the reduction of shock strength is also less.In addition, do not contain the test film 9 (comparative example 4) of metallic soap, find to have irregular colour, extreme difference aspect outward appearance on the whole.
(embodiment 6～10 and comparative example 5～7: also use the deterioration preventing effect that produces) with phenol antioxidant
Use テ ボ プ テ ス ト ミ Le (the smart mechanism of Japan is done made), will stir 5 minutes by each metallic soap 1 mass parts, polypropylene GRANULES (the system Mitsui Port リ プ ロ of Mitsui Chemicals, Inc) 100 mass parts and butylhydroxy toluene (エ of Co., Ltd. one ピ one ア イ コ one Port レ one シ ヨ Application system ヨ シ ノ Star Network ス) 0.1 mass parts that preparation example 1～5 and comparative preparation example 1～3 obtain down at 180 ℃.Then, carry out extrusion forming, prepare the polypropylene test film (with them according to the order of preparation example 1～5 and comparative preparation example 1～3 respectively as test film 10～17) of wide 200mm, long 200mm and thick 2mm.Then, these test films are put into blast drier, and preserved 10 days down, estimate painted (xanthochromia of resin) after preserving at 60 ℃.Visual inspection is estimated, and painted is not made as zero with seeing fully; With discovery have painted being made as *.The result is as shown in table 3.
Table 3
| Raw material | The thermoplastic resin composition | Test-results | ||||
| Metallic soap (A) (title) | Thermoplastic resin (B) *1 | A/B *2(mass ratio) | The xanthochromia of resin | |||
| Embodiment | 6 | Preparation example 1 (mixed fatty acid magnesium) | PP | 1/100 | Test film 10 | ○ |
| 7 | Preparation example 2 (mixed fatty acid zinc) | PP | 1/100 | Test film 11 | ○ | |
| 8 | Preparation example 3 (calcium laurate) | PP | 1/100 | Test film 12 | ○ | |
| 9 | Preparation example 4 (mixed fatty acid barium) | PP | 1/100 | Test film 13 | ○ | |
| 10 | Preparation example 5 (mixed fatty acid calcium) | PP | 1/100 | Test film 14 | ○ | |
| Comparative example | 5 | Comparative preparation example 1 (mixed fatty acid zinc) | PP | 1/100 | Test film 15 | × |
| 6 | Comparative preparation example 2 (mixed fatty acid magnesium) | PP | 1/100 | Test film 16 | × | |
| 7 | Comparative preparation example 3 (mixed fatty acid calcium) | PP | 1/100 | Test film 17 | × | |
* 1...PP: polypropylene (particle)
* 2... metallic soap/thermoplastic resin (mass ratio)
As shown in Table 3, use in the test film (test film 10～14) of metallic soap of preparation example, do not find xanthochromia fully, and use test film (test film 15～17) yellowing all of the metallic soap of comparative preparation example 1～3.
(reference example: whether metallic soap causes the painted of tetramethylolmethane ester cpds)
The mixing of in vinyl bag, will vibrating by metallic soap (mixed fatty acid magnesium) 5g, pentaerythritol stearate (acid number is 2.5 for NOF Corp's system, ユ ニ ス one H-476, and hydroxyl value the is 14.0) 5g that preparation example 1 obtains.This mixture is transferred in the aluminum oxide cup that diameter is 6cm, and 200 ℃ were heated 60 minutes down in blast drier.After the cooling,, use colour examining colour-difference-metre ZE-2000 type (Japanese electric look Industrial Co., Ltd system), to try to achieve yellow chromaticity (YI) by following formula according to the value that JIS Z-8722 tries to achieve X, Y and Z for the color on the surface of mixture:
Yellow chromaticity (YI)=100 (1.28X-1.06Z)/Y
The above results is as shown in table 4.
Except using the metallic soap (mixed fatty acid magnesium) that obtains by comparative preparation example 2 to replace trying to achieve yellow chromaticity with above-mentioned operation similarly the above-mentioned metallic soap that obtains by preparation example 1.The result is as shown in table 4.
Table 4
| Yellow chromaticity (YI) when using separately | Yellow chromaticity behind the mixed ester (YI) | |
| The metallic soap of preparation example 1 (mixed fatty acid magnesium) | 17.1 | 5.9 |
| The metallic soap of comparative preparation example 2 (mixed fatty acid magnesium) | 18.2 | 35.5 |
| Pentaerythritol stearate | -4.9 | --- |
As shown in Table 4, with the metallic soap of preparation example 1 and the situation of pentaerythritol stearate Hybrid Heating, and the metallic soap of comparative preparation example 2 is compared with the situation of above-mentioned ester Hybrid Heating, (YI) is lower for yellow chromaticity.Because the yellow chromaticity of the metallic soap of the metallic soap of preparation example 1 and comparative preparation example 2 does not have bigger difference before mixing,, be difficult for making the tetramethylolmethane ester cpds painted so employed metallic soap among the present invention is as can be known compared with other metallic soap.
(embodiment 11～12 and comparative example 8: anti-coloring effect and surface luster effect)
Each metallic soap, titanium oxide (the former industry system of stone that will obtain by preparation example 1 and comparative preparation example 2 with the described ratio of table 5 with drum roller, イ ペ one Network), employed pentaerythritol stearate mixes in polycarbonate resin particle (the system ユ of the worker of Mitsubishi Application ジ ニ ア リ Application グ プ テ ス チ Star Network Co., Ltd. one ピ ロ Application) and the reference example.Then, use internal diameter under 280 ℃, to carry out fusion and mix and extrude, make particle with tablets press as the biaxial extruder of 20mm.After resulting each particle thorough drying, use vertical type injection molding machine, injection molding under 280 ℃ mold temperatures, 90 ℃ die temperature, the POLYCARBONATE SHEET of preparation 70mm * 70mm * 2mm (with them respectively as test film 18～20).For these test films 18～20, the painted and surface luster to resin as described below is estimated.The result is as shown in table 5.
(1) resin is painted
For test film, use color computer to measure yellow chromaticity (YI).If the value of YI be 10.0 or below, then be judged to be unsubstantial paintedly, surpass at 10.0 o'clock, it is painted significantly to be judged to be existence.
(2) surface luster
The surface of visual inspection test film has the glossy situation of homogeneous to be made as zero on the surface; The situation that the part on surface is tarnished is made as △; Will be from the teeth outwards do not see fully the glossy situation be made as *.
Table 5
| Raw material | The thermoplastic resin composition | Test-results | |||||||
| Metallic soap | Polycarbonate resin particle (mass parts) | Titanium oxide (mass parts) | Ester (mass parts) | Yellow chromaticity (Y1) | Surface luster | ||||
| Use metallic soap (title) | Mass parts | ||||||||
| Embodiment | 11 | Preparation example 1 (mixed fatty acid magnesium) | 0.1 | 100 | 1.0 | 0.1 | Test film 18 | 8.9 | ○ |
| 12 | Preparation example 1 (mixed fatty acid magnesium) | 0.1 | 100 | 1.0 | - | Test film 19 | 8.4 | △ | |
| Comparative example | 8 | Comparative preparation example 2 (mixed fatty acid magnesium) | 0.1 | 100 | 1.0 | 0.1 | Test film 20 | 16.4 | ○ |
* 1... pentaerythritol stearate
As shown in Table 5, contain the test film 18 of the metallic soap of preparation example 1 and tetramethylolmethane ester cpds and only to contain the test film 19 of metallic soap of preparation example 1 painted hardly.Further, because test film 18 contains ester cpds, excellence aspect surface luster.On the contrary, contain the metallic soap of comparative preparation example 2 and test film 20 xanthochromias of tetramethylolmethane ester cpds.
Industrial applicibility
Thermoplastic resin composition of the present invention is excellent aspect pigment, filler etc. dispersed, and is difficult for producing the reduction of the molecular weight of resin. Further, even when containing antioxidant among the thermoplastic resin composition of the present invention, do not hinder antioxidant effect yet. When particularly containing phenol antioxidant, compare with the thermoplastic resin composition of containing metallic soap in the past, because phenol antioxidant is difficult for decomposing, be difficult for producing painted at resin. Therefore, can in resin combination, stably contain phenol antioxidant. Further, when containing the pentaerythrite ester compounds, the lubricity that adds man-hour further improves. And, even when containing the pentaerythrite ester compounds, be difficult for to produce because the painted resin that causes of this ester compounds painted. Thermoplastic resin composition of the present invention is used in such as automotive field, OA field of components etc.
Claims (5)
1. thermoplastic resin composition, it is to contain metallic soap and thermoplastic resin, wherein, this metallic soap reacts the metal-salt of fatty acid alkali compound salt and divalent and obtains in the aqueous solution; Described fatty acid alkali compound salt make carbonatoms be the alkali cpd of 6～24 lipid acid and 1 valency by 1 mole: 0.90～0.99 mole ratio reacts and obtains,
With respect to these thermoplastic resin 100 mass parts, the content of this metallic soap is 0.01 mass parts～10 mass parts.
2. the described thermoplastic resin composition of claim 1, wherein, the metal that constitutes described metallic soap is calcium or magnesium.
3. claim 1 or 2 described thermoplastic resin compositions, wherein, with respect to described thermoplastic resin 100 mass parts, further contain the ester cpds that tetramethylolmethane and carbonatoms are 14～24 1 valency saturated fatty acid with the ratio of 0.001 mass parts～5 mass parts.
4. the described thermoplastic resin composition of claim 3, wherein, the acid number of described ester cpds be 5.0 or below, hydroxyl value be 20.0 or below.
5. any described thermoplastic resin composition in the claim 1～4, wherein, described thermoplastic resin is a vibrin.
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| ATE485335T1 (en) * | 2007-07-19 | 2010-11-15 | Ticona Llc | STABILIZED THERMOPLASTIC COPOLYESTER |
| JP5125736B2 (en) * | 2008-05-02 | 2013-01-23 | コニカミノルタビジネステクノロジーズ株式会社 | Toner for developing electrostatic image and image forming method |
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| JP2004083880A (en) * | 2002-06-28 | 2004-03-18 | Mitsui Chemicals Inc | Polyamide resin composition and molded product of the same |
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