CN1871310A - Colorant for thermoplastic resin and uses thereof - Google Patents
Colorant for thermoplastic resin and uses thereof Download PDFInfo
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- CN1871310A CN1871310A CN 200480031191 CN200480031191A CN1871310A CN 1871310 A CN1871310 A CN 1871310A CN 200480031191 CN200480031191 CN 200480031191 CN 200480031191 A CN200480031191 A CN 200480031191A CN 1871310 A CN1871310 A CN 1871310A
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Abstract
A colorant for thermoplastic resins which is excellent in dispersibility, transparency, ultraviolet-shielding properties, etc.; a thermoplastic resin composition containing the colorant; and a thermoplastic resin molding having a satisfactory dispersion state, transparency, ultraviolet-shielding properties, stretchability, and surface smoothness. The colorant for thermoplastic resins comprises: surface-treated alpha-ferric oxide (A) obtained by coating non-acicular alpha-ferric oxide having an average particle diameter of 0.01 to 0.06 mum and an aspect ratio of 0.2 to 1.0 with a polyhydric alcohol and an organopolysiloxane; and a dispersant (B) comprising a metal hydroxycarboxylate (B1). It optionally further contains a methine dye (C). The thermoplastic resin composition and the molding are obtained by using the colorant for thermoplastic resins. Also provided is a molding obtained by coating the molding with a carbon film.
Description
Technical field
The present invention relates to colorant for thermoplastic resin and thermoplastic resin composition.Specifically, relating to when having the transparency can shielding ultraviolet rays, surface smoothing thermoplastic resin excellent forming composition.The present invention relates to further to shield near the visible light of 550nm, and have the thermoplastic resin molded article of gas occluding.
Background technology
Thermoplastic resin because thermotolerance, have excellent weather resistance and cost also low, so be used for various forming composition such as film, hollow molded body.Especially condensed type thermoplastic resins such as vibrin, styrene resin, polycarbonate resin, acrylic resin, bring into play favourable characteristics such as its transparency, appearance design, light weight, replace vial and be used for purposes such as food product pack, toiletry bag packaging container more and more.
The vial that is used for beer, drinks etc. has the tone of brown system.Polyester resin bottle is carried out when painted, consider stripping property to goods, thermotolerance etc., the general use is called as the alpha-ferric oxide (with reference to special fair 5-81623 communique) of the median size of particulate oxide iron smaller or equal to 0.1 μ m.Especially beer container, stable in order to make content, need 420nm or following ultra-violet region shielding 96% or more than, near the shielding of the visible region the 550nm 70% or more than, in addition, also need gas occluding.That is, with light penetration, if not in 420nm or following ultra-violet region less than 4%, and near the visible region 550nm is smaller or equal to 30%, then the protection of content will have problems.But but there are problems such as aggegation in above-mentioned alpha-ferric oxide in production process, bad dispersibility and insufficient.
In addition, though also disclosed the relevant comparatively technology of agglutinophilic alpha-ferric oxide (opening flat 8-59398 communique) not with reference to the spy, but be difficult to satisfy above-mentioned characteristic.
And then usually also there is the gas occluding difference in thermoplastic resin molded article and problem that content is worsened.As the method that solves, disclosed technology to forming composition coating carbon film (with reference to the spy open flat 8-53116 communique, the spy opens the 2000-309324 communique),, though gas occluding is abundant, but ultraviolet screener is abundant inadequately.And, the particulate oxide iron that discloses in the fair 5-81623 communique of above-mentioned spy is because the thermal thermocoagulation height, so when machine-shaping, produce the pigment aggegation, the transparency descends, produce particle (Block Star) and make bad order, and around particulate oxide iron, generate the space, and make gas occluding become insufficient.
Summary of the invention
Purpose of the present invention is for providing the transparency, dispersed, ultraviolet-shielding type thermoplastic resin excellent with tinting material and the thermoplastic resin composition that uses this tinting material.In addition, purpose of the present invention is for providing a kind of thermoplastic resin molded article, and this forming composition is the transparency, surface smoothing excellence not only, and the maskable ultraviolet ray, and then goes back near the visible light the maskable 550nm as required.And then purpose of the present invention is to be provided at the forming composition with gas occluding that the coating carbon film forms on the above-mentioned forming composition.
The present invention is a kind of colorant for thermoplastic resin, it contains surface treatment alpha-ferric oxide (A) and as the hydroxyl carboxylic metallic salt (B1) of dispersion agent (B), and surface treatment alpha-ferric oxide (A) is by being that 0.01～0.06 μ m and breadth-length ratio are that 0.2～1.0 non-needle-like alpha-ferric oxide forms with polyvalent alcohol and organopolysiloxane coating median size.
In addition, the present invention is aforesaid colorant for thermoplastic resin, and wherein, hydroxyl carboxylic metallic salt (B1) is a 12-oxystearic acid metal-salt.
And the present invention is aforesaid colorant for thermoplastic resin, and wherein, 12-oxystearic acid metal-salt is a 12-oxystearic acid calcium.
The present invention is a kind of colorant for thermoplastic resin, it contains surface treatment alpha-ferric oxide (A) and as the higher fatty acid metal-salt (B2) of dispersion agent (B), and surface treatment alpha-ferric oxide (A) is by being that 0.01～0.06 μ m and breadth-length ratio are that 0.2～1.0 non-needle-like alpha-ferric oxide forms with polyvalent alcohol and organopolysiloxane coating median size.
And the present invention is aforesaid colorant for thermoplastic resin, and wherein, polyvalent alcohol or organopolysiloxane are handled alpha-ferric oxide (A) with respect to all surfaces, are respectively 0.01～10 weight %.
In addition, the present invention is aforesaid colorant for thermoplastic resin, and wherein, polyvalent alcohol is TriMethylolPropane(TMP) or trimethylolethane.
In addition, the present invention is aforesaid colorant for thermoplastic resin, and wherein, organopolysiloxane is dimethyl polysiloxane or hydrogenated methyl polysiloxane.
In addition, the present invention is aforesaid colorant for thermoplastic resin, wherein, with respect to surface treatment alpha-ferric oxide (A) 100 weight parts, cooperates the dispersion agent (B) of 40～150 weight parts.
Also have, the present invention is for containing the colorant for thermoplastic resin of methyne based dye (C) in above-mentioned colorant for thermoplastic resin.
In addition, the present invention is aforesaid colorant for thermoplastic resin, and wherein, above-mentioned methyne based dye (C) is a C.I. solvent brown 53.
In addition, the thermoplastic resin composition of the present invention for cooperating above-mentioned colorant for thermoplastic resin, methyne based dye (C), thermoplastic resin to form.
In addition, the present invention is aforesaid thermoplastic resin composition, and wherein, above-mentioned methyne based dye (C) is a C.I. solvent brown 53.
In addition, the thermoplastic resin composition of the present invention for cooperating above-mentioned colorant for thermoplastic resin, thermoplastic resin to form.
In addition, the present invention is aforesaid thermoplastic resin composition, and wherein, thermoplastic resin is a vibrin.
And the present invention is aforesaid thermoplastic resin composition, and wherein, thermoplastic resin is a Biodegradable resin.
Also have the forming composition of the present invention for using above-mentioned colorant for thermoplastic resin to obtain.
In addition, the forming composition of the present invention for using above-mentioned thermoplastic resin to obtain with composition.
In addition, the present invention is the forming composition at the surperficial coating carbon film of above-mentioned forming composition.
The application's spy open and that apply on October 24th, 2003 is willing to that the spy who reaches for 2003-364429 number in application on November 27th, 2003 is willing to that the theme of 2003-397093 number record is relevant, and its disclosure here is cited.
Embodiment
Colorant for thermoplastic resin of the present invention contains surface treatment alpha-ferric oxide (A) and dispersion agent (B).
Surface treatment alpha-ferric oxide (A) is with polyvalent alcohol and organopolysiloxane coating alpha-ferric oxide and form.
The alpha-ferric oxide of Shi Yonging in the present invention, median size is 0.01～0.06 μ m, is preferably 0.03～0.05 μ m.If median size is less than 0.01 μ m, then may produce particles aggregate, disperse badly, if surpass 0.06 μ m, then the surfaceness of forming composition will be too big, cause surface smoothing, the transparency to descend, alpha-ferric oxide aggegation and cause the bad order of forming composition.Here said median size be meant with minor axis, major diameter on average as particle diameter, show the peaked value of size-grade distribution.
In addition, the alpha-ferric oxide of Shi Yonging is in the present invention, and breadth-length ratio is 0.2～1.0 and is non-needle-like, can open the method that discloses in the flat 8-59398 communique according to the spy and obtain.At this, so-called breadth-length ratio is meant the ratio (minor axis/major diameter) of the minor axis that arrives according to electron microscope observation and major diameter.In order to obtain the forming composition of the transparency, favorable dispersity, especially preferably just spherical (minor axis/major diameter=1.0).
In the present invention, as the surface treatment agent of alpha-ferric oxide, use polyvalent alcohol and organopolysiloxane simultaneously.
Adopting polyvalent alcohol that alpha-ferric oxide is carried out the surface-treated purpose is to realize the low polar of particle surface and prevent particle aggegation again.
As the concrete example of polyvalent alcohol, can enumerate alkane glycol such as ethylene glycol, propylene glycol, 1,3 butylene glycol, tetramethylene glycol; Perhaps polyether polyols such as Diethylene Glycol, triethylene glycol, polyoxyethylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol; Perhaps glycerine, TriMethylolPropane(TMP), trimethylolethane, tetramethylolmethane, Sorbitol Powder, 1,2, polyvalent alcohols such as 6-hexanetriol, inositol, polyvinyl alcohol.Preferred TriMethylolPropane(TMP) (TMP), trimethylolethane (TME).These polyvalent alcohols can use a kind of, perhaps mix and use two or more.
Adopting organopolysiloxane that alpha-ferric oxide is carried out the surface-treated purpose is, realizes that the hydrophobization of particle surface, wettability, the inhibition molecular resin amount that improves between particle and the resin descend, keep rerum natura.
As the concrete example of organopolysiloxane, can enumerate dimethyl polysiloxane or polydimethylsiloxanes such as hydrogenated methyl polysiloxane, methyl phenyl silicone and various modified polyorganosiloxanes, pure modified polyorganosiloxane, ether modified polyorganosiloxane, fluorine modified polyorganosiloxane etc.These organopolysiloxanes can use a kind of, perhaps mix and use two or more.Preferable methyl hydrogenation polysiloxane, dimethyl polysiloxane.
In addition, the hydrogenated methyl polysiloxane of giving an example in the above, the material shown in the preferred following formula.
(in the formula, n represents positive integer, preferably smaller or equal to 12.)
The amount of polyvalent alcohol and organopolysiloxane is handled alpha-ferric oxide (A) with respect to all surfaces, is respectively 0.01～10 weight %.If surpass 10 weight %, then except uneconomical, in manufacturing process, exist polyvalent alcohol or organopolysiloxane self that tendencies such as decomposition take place, the forming composition that produces can foam or produce particle etc.If less than 0.01 weight %, then polyvalent alcohol or the organopolysiloxane coating amount on iron oxide surface is insufficient, exists in the tendency of the bad dispersibility in the resin, can cause forming composition to produce bad rerum natura.And then preferred 0.1～2 weight %, especially preferred 0.5～1 weight %.
Method with above-mentioned surface treatment agent coating alpha-ferric oxide can adopt known method such as wet processed or dry process.
Can enumerate as wet processed, in the polar solvent of alcohol such as water or ethanol, add alpha-ferric oxide and surface treatment agent and flood, use high shear force mixing machines such as Henschel agitator, flash mixer to mix equably after, with solvent evaporation, drying and the method for removal; After perhaps in solvent, dispersing or dissolving surface treatment agent, with itself and alpha-ferric oxide blended method etc.
In the wet processed, consider preferably in surface treatment process or after processing, the operation of heat drying alpha-ferric oxide particle is arranged from reducing the grade angle of the water content that causes of planar water significantly.The ferric oxide of the low water content that so obtains owing to when resin being mixed dispersion, can suppress the resin deterioration, is suppressing the decline of molecular resin amount or is keeping the aspects such as mechanical properties of forming composition to have advantage.
In the dry process, when pulverizing alpha-ferric oxide, add surface treatment agent with fluids such as micro grinder, injector-type mill energy pulverizer or stirrers such as flash mixer, Henschel agitator.Fluid as described fluid energy pulverizer uses pressurized air, heated compressed air, steam etc. usually.In addition, when polyvalent alcohol when normal temperature is solid, the polyhydric alcohol solutions that is dissolved in solvent is used for above-mentioned treatment process gets final product.For example, can enumerate the ethanolic soln of trimethylolethane or water-ethanol (1: 1) solution etc.
In the surface treatment of alpha-ferric oxide, preferred wet processed when adopting polyvalent alcohol to carry out coating, preferred dry is handled when adopting organopolysiloxane to carry out coating.And if after surface treatment, use air grinding machine etc. is pulverized agglutinative particle when surface treatment procedure by force, then can further improve dispersiveness.
The surface treatment of alpha-ferric oxide can be used polyvalent alcohol and organopolysiloxane simultaneously, perhaps also can use organopolysiloxane earlier, and polyvalent alcohol is used in the back.
One of reason of alpha-ferric oxide particles aggregate is a moisture.Because the wetting ability of alpha-ferric oxide particle surface is higher, so prevent the effect of operation adsorption moisture in the back by handling with polyvalent alcohol the hydrophilic group of particle surface being carried out coating at the beginning, just can having.In addition, the alpha-ferric oxide after polyvalent alcohol is handled can reduce the water content that planar water is graded and caused significantly by carrying out heat drying.
If with the hydrophobicity organopolysiloxane coating of the alpha-ferric oxide after the polyvalent alcohol processing, the aggegation again that then can access particle is suppressed and the surface treatment alpha-ferric oxide (A) of favorable dispersity.
And surface treatment alpha-ferric oxide (A) also can suppress thermal thermocoagulation in the operation of mixing with thermoplastic resin fusions such as polyester, so can be dispersed in well in the thermoplastic resin molded article, help improving the transparency of forming composition.
And then, if the surface water component of surface treatment alpha-ferric oxide (A) is few, then can suppress the influence for thermoplastic resin such as hydrolysis, be preferred therefore.More preferably amount of moisture is less than 0.3%.
Here, the coating amount of above-mentioned surface treatment agent can be according to known method, and the processing weight by changing alpha-ferric oxide and the supply concentration of surface treatment agent or supply flow rate are regulated and become the coating of regulation amount.
As the dispersion agent in the colorant for thermoplastic resin of the present invention (B), can use hydroxyl carboxylic metallic salt (B1) or higher fatty acid metal-salt (B2).These can use separately, also can and use two or more.
Hydroxyl carboxylic acid as in the hydroxyl carboxylic metallic salt (B1) so long as have the compound of carboxyl and hydroxyl, then is not particularly limited, and can enumerate aliphatics or aromatic hydroxyl carboxylic acid.According to hydroxyl carboxylic metallic salt (B1), the dispersiveness of alpha-ferric oxide will improve, therefore when accessing the high forming composition of the transparency, especially when using vibrin such as polyethylene terephthalate (PET), polycarbonate, poly(lactic acid) etc., can keep limiting viscosity (IV) value of resin.IV represents the state of resin deterioration (hydrolysis), and it is low more to be worth high more explanation resin degradation, excellence aspect processibility.
As aliphatics hydroxyl carboxylic acid, the material of preferred carbonatoms 10～30 for example can be enumerated Alpha-hydroxy tetradecanoic acid, Alpha-hydroxy palmitinic acid, Alpha-hydroxy stearic acid, Alpha-hydroxy 20 acid, Alpha-hydroxy twenty diacid, Alpha-hydroxy lignoceric acid, Alpha-hydroxy cerin, the acid of Alpha-hydroxy 28, Alpha-hydroxy triacontanoic acid, beta-hydroxy tetradecanoic acid, 10-hydroxydecanoic acid, 15-hydroxy-pentadecanoic acid, 16-hydroxy-palmitic acid, 12-oxystearic acid, ricinoleic acid etc.These can use separately, also can and use two or more.Especially preferred 12-oxystearic acid is considered in the aspect of raw material of being easy to get calmly.
In addition, as other aliphatics hydroxyl carboxylic acids, can enumerate oxyacetic acid, lactic acid, hydrogenation vinylformic acid, α-hydroxybutyric acid, Alpha-hydroxy isobutyric acid, δ-hydroxycaproic acid, Alpha-hydroxy n-Dotriacontanoic acid, Alpha-hydroxy gheddic acid, Alpha-hydroxy ceroplastic scid, Alpha-hydroxy octatriacontanoic acid, the acid of Alpha-hydroxy tetracontane, R-Glyceric acid, tartronic acid, oxysuccinic acid, citric acid etc.And,, can enumerate Whitfield's ointment, resorcylic acid, p-hydroxybenzoic acid, gallic acid, amygdalic acid, tropic acid etc. as aromatic series hydroxyl carboxylic acid.
Metal in the hydroxyl carboxylic metallic salt (B1), preferred as alkali lithium, alkaline-earth metal magnesium, calcium.And, be the situation of 12-oxystearic acid metal-salt, preferably have magnesium or calcium that FAD approves this advantage.These metal-salts can use a kind of, also can and use two or more.
The preferred micropowder of 12-oxystearic acid metal-salt.And the method for making of 12-oxystearic acid metal-salt has double decomposition precipitation method, dry type direct method etc., can use.If adopt the direct rule of dry type can obtain the low 12-oxystearic acid metal-salt of water ratio, thus can be suppressed at the influences such as molecular weight and molecular weight of thermoplastic resin when mixing with the thermoplastic resin fusion, thereby be preferred.
As the higher fatty acid in the higher fatty acid metal-salt (B2), can enumerate the aliphatic carboxylic acid of carbonatoms 10～30.
Specifically, can enumerate stearic acid, oleic acid, lauric acid, docosoic acid, behenic acid, tetradecanoic acid, montanic acid etc.Metal-salt as aliphatic carboxylic acid can be enumerated calcium, magnesium, lithium, aluminium, zinc, sodium, potassium etc.Especially preferred potassium stearate, Magnesium Stearate.
In colorant for thermoplastic resin of the present invention, the methyne based dye (C) that uses is the material that thermotolerance is good, sublimability is little as required.Specifically, can enumerate Colour Index (C.I.) solvent brown 53, C.I. solvent yellow 133, C.I. solvent violet 49, C.I. pigment orange 70 etc.These can use separately, also can and use.Especially, tone is brown C.I. solvent brown 53, owing to be FDA registration product, therefore preferred the use.
As the thermoplastic resin that in the thermoplastic resin composition, is used as matrix resin or in forming composition, is used as moulding resin of the present invention, can enumerate the resin that had the transparency in the known in the past resin, specifically vibrin, styrene resin, polycarbonate resin, acrylic resin etc.Specifically can enumerate and have transparent vibrin, styrene resin, polycarbonate resin, acrylic resin etc.Especially preferred polyester resin.
As vibrin, can pass through terephthalic acid, m-phthalic acid, 2,6-naphthalene dicarboxylic acids, 4, aromatic carboxylic acid such as 4-diphenyldicarboxylic acid or its ester and ethylene glycol, propylene glycol, 1, aliphatic dihydroxy alcohol polycondensations such as 4-butyleneglycol, Diethylene Glycol, 1,4 cyclohexane dimethanol and obtaining.Representational material has PET and polybutylene terephthalate.
These vibrin can be with the material after multiple carboxylic acid composition and the combination of multiple diol component.That is, described vibrin is, except the homopolymer (main composition composition) that is made of above-mentioned aromatic carboxylic acid composition and aliphatic dihydroxy alcohol composition, can also be to add the multipolymer that the 3rd composition carries out copolymerization.As the 3rd composition, when for example the main composition composition is ethylene glycol terephthalate, can enumerate glycol such as Diethylene Glycol, propylene glycol, neopentyl glycol, polyalkylene glycol, 1,4 cyclohexane dimethanol; Succsinic acid, hexanodioic acid, sebacic acid, phthalic acid, m-phthalic acid, 2, di-carboxylic acid such as 6-naphthalene dicarboxylic acids; Polyfunctional group such as trimellitic acid, Pyromellitic Acid polycarboxylic acid etc.In addition, when the main composition composition is 2, during the 6-(ethylene naphthalate), can enumerate above-mentioned the 3rd composition (just with 2, the 6-naphthalene dicarboxylic acids replaces terephthalic acid).
The thermoplastic resin of Shi Yonging can also use Biodegradable resin in the present invention.Specifically, the aliphatic polyester based resin that obtains as raw material except poly(lactic acid), polycaprolactone or with aliphatic dicarboxylic acid and polyvalent alcohol, can also enumerate vibrin by microorganism or phytosynthesis etc.Especially preferred poly(lactic acid).
Specifically can enumerate on market and to sell or the clear and polymer company of trial-production makes or Japanese catalyst company makes polybutylene succinate, polydiethylene glycol succinate, poly-succsinic acid tetramethylene adipate; The poly(lactic acid) that Mitsui Chemicals company makes, カ one ギ Le company makes or Tianjin, island company makes; Poly-(3-hydroxybutyric acid-CO-3-hydroxypentanoic acid) (P (3HB-3HV)) that the polycaprolactone that ダ イ セ Le company makes, モ Application サ Application ト company make or poly-(3-hydroxybutyric acid-CO-4-hydroxybutyric acid) (P (3HB-4HB)) or poly-(3-hydroxybutyric acid-CO-3-hydroxy propionate) (P (3HB-3HP)) etc.Can enumerate レ イ シ ア H100J (Mitsui Chemicals, Inc) as the goods name, Off ロ Application IVB 2500 (Idemitsu Petrochemical Co., Ltd.), テ オ Na イ ト TN8065S (Teijin Ltd) etc.
Thermoplastic resin composition's the matrix resin and the moulding resin of forming composition preferably use same resin or have the resin of intermiscibility.
By Henschel agitator, flash mixer, container alternate form stirrer etc. surface treatment alpha-ferric oxide (A) and dispersion agent (B) are mixed, can produce colorant for thermoplastic resin of the present invention.Especially preferably with respect to surface treatment alpha-ferric oxide (A) 100 weight parts, with the ratio cooperation of dispersion agent (B) 40～150 weight parts.
In addition, matching surface is handled alpha-ferric oxide (A), dispersion agent (B), methyne based dye (C), can similarly produce colorant for thermoplastic resin of the present invention.At this moment, can be in the mixture of alpha-ferric oxide (A) and dispersion agent (B), to add methyne based dye (C), also can be to mix alpha-ferric oxide (A), dispersion agent (B), methyne based dye (C) simultaneously.
Colorant for thermoplastic resin by surface treatment alpha-ferric oxide (A) and dispersion agent (B) constitute by reinstating single shaft, double-shafted extruder extruding with thermoplastic resin one, can produce thermoplastic resin composition of the present invention (masterbatch or mixture).
And, colorant for thermoplastic resin by above-mentioned surface treatment alpha-ferric oxide (A) and dispersion agent (B) formation, by reinstating single shaft, double-shafted extruder extruding, can produce thermoplastic resin composition of the present invention with methyne based dye (C) and thermoplastic resin one.
In addition, the colorant for thermoplastic resin by surface treatment alpha-ferric oxide (A) and dispersion agent (B) and methyne based dye (C) formation by pushing with thermoplastic resin, can produce thermoplastic resin composition of the present invention.
In these thermoplastic resin compositions, with respect to thermoplastic resin 100 weight parts, the content of surface treatment alpha-ferric oxide (A) is preferably, and is 0.01～60 weight part when masterbatch, is 0.01～3 weight part when mixture.And when containing methyne based dye (C), its content is preferably, and is 0.001～4 weight part when masterbatch, is 0.001～0.2 weight part when mixture.
Forming composition of the present invention can be above-mentioned colorant for thermoplastic resin directly to be coated on moulding make with carrying out fusion to mix also moulding on the thermoplastic resin.
In addition, forming composition of the present invention, also can be to cooperate above-mentioned colorant for thermoplastic resin and thermoplastic resin and after making thermoplastic resin composition's (masterbatch), mix this thermoplastic resin composition and moulding resin (moulding thermoplastic resin), carry out mix also moulding and making of fusion again.And, also can be to cooperate above-mentioned colorant for thermoplastic resin and thermoplastic resin and after making thermoplastic resin composition's (mixture), directly carry out moulding and make with this composition.
As the shape of forming composition, can enumerate bottle, thin slice, film, flat board etc.
Forming composition of the present invention has the transparency, and can shield 420nm or following ultra-violet region.In addition, when containing methyne based dye (C), can further shield near the visible light of 550nm.
But the degree of shielding can change according to each component content in the forming composition and the thickness of forming composition.Enumerate the words of one example, for the forming composition that in 100 weight part thermoplastic resins, contains 0.22 weight part or above surface treatment alpha-ferric oxide (A), when thickness is 0.3mm, have the transparency, and can shield 420nm or following ultra-violet region 99% or more than.
And then, in the example of above-mentioned forming composition, when containing 0.01 weight part or the methyne based dye (C) more than it, can shield near the visible light of 550nm and surpass 70%.
As condition with above-mentioned characteristic, the content of mentioned component in the forming composition, if thickness is thinner than 0.3mm, then needing increases its content, if thick then can reduce its content.
Here, the light shielding rate is the value that is obtained by (100%-light penetration).
Colorant for thermoplastic resin of the present invention, thermoplastic resin composition and forming composition can be used pigment or dyestuff according to the tone of expectation.Specifically, can enumerate pigment dyestuffs such as azo system, anthraquinone system, perylene Xi, perylene quinone (perynone) are, quinoline a word used for translation ketone system, phthalocyanine system, iso-dihydro-indole system, dioxazines system, indanthrene system, quinophthalone system; Coloured mineral dyes such as zinc oxide, titanium oxide, ultramarine, cobalt blue, carbon black, titan yellow; Extender pigments such as barium sulfate, kaolin, talcum; Oil-soluble colourant, dispersed dye such as anthraquinone system, perylene Xi, perylene quinone system, monoazo system, other methyne systems, heterocycle system, lactone system, phthalocyanine system.
In addition,, can use metallic soap, i.e. the metal-salt of the metal-salt of higher fatty acid or hydroxyl carboxylic acid as lubricant.For example, calcium stearate, Magnesium Stearate, barium stearate, Zinic stearas, aluminum stearate, lithium stearate, calcium laurate, zinc laurate, Magnesium monolaurate are as the metal-salt of the Alpha-hydroxy tetradecanoic acid of hydroxyl carboxylic metallic salt, Alpha-hydroxy palmitinic acid, Alpha-hydroxy stearic acid, Alpha-hydroxy 20 acid, Alpha-hydroxy twenty diacid, Alpha-hydroxy lignoceric acid, Alpha-hydroxy cerin, the acid of Alpha-hydroxy 28, Alpha-hydroxy triacontanoic acid, beta-hydroxy tetradecanoic acid, 10-hydroxydecanoic acid, 15-hydroxy-pentadecanoic acid, 16-hydroxy-palmitic acid, 12-oxystearic acid, ricinoleic acid etc.
And then, can cooperate additives such as the oxidation inhibitor that generally is used for thermoplastic resin molded article, UV light absorber, photostabilizer, metal inert agents.As oxidation inhibitor, can use phenol system, phosphorous acid ester system etc.As phenol system, can enumerate for example diethyl [[3, two (1, the 1-dimethyl ethyl) the 4-hydroxy phenyls of 5-] methyl] phosphonic acid ester, octadecyl-3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester etc.As phosphorous acid ester system, can enumerate for example three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester, two (2,6-di-t-butyl-4-aminomethyl phenyl) pentaerythritol diphosphites etc.
Prevent agent as ultraviolet ray, can use benzotriazole system, triazine system etc.As benzotriazole be, for example can enumerate 2, [4-(1 for the 2-methylene-bis, 1,3,3-tetramethyl butyl) phenol 6[(2H-benzotriazole-2-yl)]], 2-(2H-benzotriazole-2-yl)-4-(1,1,3,3-tetramethyl butyl) phenol, 2-[5-chlorine (2H)-benzotriazole-2-yl]-4-methyl-6-(tertiary butyl) phenol etc.As triazine system, can enumerate for example 2-(4,6-phenylbenzene-1,3,5-triazines-2-yl)-5-[(hexyl) oxygen] phenol etc.
As photostabilizer, can use hindered amine system etc.As hindered amine system, for example can enumerate two (2,2,6,6-tetramethyl--4-piperidyl) sebate, it is poly-that [{ 6-(1,1,3, the 3-tetramethyl butyl) amino-1,3,5-triazine-2,4-two bases } { (2,2,6,6-tetramethyl--4-piperidyl) imino-} hexa-methylene { (2,2,6,6-tetramethyl--4-piperidyl) imino-}], dibutylamine 1,3,5-triazine N, N-two (2,2,6,6-tetramethyl--4-piperidyl)-1,6-hexamethylene-diamine N-(2,2,6,6-tetramethyl--4-piperidyl) polycondensate of butylamine etc.As the metal inert agents, for example can enumerate 2,3-two [[3-[3,5-di-tert-butyl-hydroxy phenyl] propionyl]] the propionyl hydrazine etc.
On the surface of forming composition of the present invention, apply carbon film as required.As the unstripped gas of carbon film, can use at normal temperature to be the aliphatic hydrocarbon of gas or liquid, aromatic hydrocarbons, oxygen-containing hydrocarbon, nitrogenous hydrocarbon etc.Especially preferred acetylene, benzene, toluene, o-Xylol, m-xylene, p-Xylol, hexanaphthene etc.These unstripped gases can be used separately, and the mixed gas that also can be used as two or more uses.And then, also can be to dilute these gases and use with rare gas such as argon gas or helium.
The carbon film of Shi Yonging is i carbon film that is made of quasi-diamond (DLC) film or the hard carbon films that is called as hydrogenated amorphous attitude carbon film (a-C:H) in the present invention, preferably based on the amorphous carbon film of SP3 key.
The kinds of pressure, supply gas flow, plasma generation time, self-bias and the raw material of the output of the thickness of carbon film and high frequency, unstripped gas etc. are relevant, but for the absorption that takes into account low-molecular-weight organic compound suppresses effect and the raising effect of gas barrier and adaptation, weather resistance and the transparency etc. of condensed type moldable resin, the scope of preferred 50～1000 .Especially preferred 200～300 .The system film of DLC film is subject to the smoothness as the forming composition surface of the coating object of film.That is, if the forming composition surface smoothing, then coating equably, but if the jut coating then very the difficulty, coating equably.Thereby, if less than 50 , then coating and make gas occluding abundant inadequately fully.
Carbon film membranous relevant with the kind of pressure, supply gas flow, plasma generation time, self-bias and the raw material of high frequency output, unstripped gas etc. similarly, the following degradation of the carbonatoms of the flow minimizing of the increase that high frequency is exported, the minimizing of the pressure of unstripped gas, supply gas, the increase of self-bias and raw material all can become the sclerosis of DLC film, density raising, stress under compression increase and fragility cause of increased.Therefore, for under the condition of keeping with the adaptation of resin surface and film weather resistance, bring into play the gas occluding effect to greatest extent, then need to be set at, the flow 50～150ml/min of high frequency output 50～2000W, feedstock gas pressures 0.1～0.8torr, supply gas, self-bias-200～-about 1～8 of 1000V, unstripped gas carbonatoms.
Here, in order further to improve the adaptation of DLC film and resin surface, also can before forming the DLC film, adopt inorganic gass such as argon gas or oxygen to carry out Cement Composite Treated by Plasma, with the surface of activated resin forming composition.
Coating of the present invention the gas permeation amount of forming composition of carbon film, though also relevant with the thickness of carbon film, for example the situation of oxygen is preferably less than 24 hours atm of 0.0030ml/ bottle.Especially preferably less than 24 hours atm of 0.0010ml/ bottle.
Colorant for thermoplastic resin of the present invention, contain wide long surface treatment alpha-ferric oxide (A) and as the hydroxyl carboxylic metallic salt (B1) of dispersion agent (B), and surface treatment alpha-ferric oxide (A) is to be that 0.01～0.06 μ m and breadth-length ratio are that 0.2～1.0 non-needle-like alpha-ferric oxide forms by polyvalent alcohol and organopolysiloxane coating median size, therefore surface treatment alpha-ferric oxide (A) can disperse well, as resin formed product the time, not only can suppress the resin deterioration, and have the transparency, and can shielding ultraviolet rays.
In addition, colorant for thermoplastic resin of the present invention, preferred hydroxyl carboxylic metallic salt (B1) is a 12-oxystearic acid metal-salt, therefore can disperse surface treatment alpha-ferric oxide (A) more well, obtains the high resin formed product of the transparency.
And, colorant for thermoplastic resin of the present invention, preferred 12-oxystearic acid metal-salt is a 12-oxystearic acid calcium, therefore can use more aptly.
Colorant for thermoplastic resin of the present invention, contain surface treatment alpha-ferric oxide (A) and as the higher fatty acid metal-salt (B2) of dispersion agent (B), and surface treatment alpha-ferric oxide (A) is to be that 0.01～0.06 μ m and breadth-length ratio are that 0.2～1.0 non-needle-like alpha-ferric oxide forms by polyvalent alcohol and organopolysiloxane coating median size, therefore surface treatment alpha-ferric oxide (A) can disperse well, as resin formed product the time, have the transparency, and can shielding ultraviolet rays.
In the colorant for thermoplastic resin of the present invention, handle alpha-ferric oxide (A) with respect to all surfaces, preferred polyol or organopolysiloxane are respectively 0.01～10 weight %, and therefore, surface treatment alpha-ferric oxide (A) can aggegation and excellent dispersion.
Colorant for thermoplastic resin of the present invention, preferred polyol are TriMethylolPropane(TMP) or trimethylolethane, and therefore, surface treatment alpha-ferric oxide (A) can aggegation and excellent dispersion.
In addition, colorant for thermoplastic resin of the present invention, preferred organopolysiloxane is dimethyl polysiloxane or hydrogenated methyl polysiloxane, therefore, surface treatment alpha-ferric oxide (A) can aggegation and excellent dispersion.
In addition, colorant for thermoplastic resin of the present invention with respect to surface treatment alpha-ferric oxide (A) 100 weight parts, preferably cooperates 40～150 weight part dispersion agents (B), therefore, and the excellent dispersion of surface treatment alpha-ferric oxide (A).
Colorant for thermoplastic resin of the present invention further contains methyne based dye (C) as required, therefore as resin formed product the time, can also shield visible light.
And preferred methyne based dye (C) is a C.I. solvent brown 53, therefore can be with the painted tone that becomes dark brown system of forming composition.
Thermoplastic resin composition of the present invention, can be by cooperating colorant for thermoplastic resin and the thermoplastic resin that does not contain methyne based dye (C), the colorant for thermoplastic resin and methyne based dye (C) and the thermoplastic resin that do not contain methyne based dye (C), the colorant for thermoplastic resin and the thermoplastic resin that perhaps contain methyne based dye (C), easily produce the operability excellence of production process aspect.
Therefore thermoplastic resin among the thermoplastic resin composition of the present invention is preferably vibrin, can obtain having the transparency, the forming composition of extensibility, surface smoothing excellence.
Therefore and the thermoplastic resin among the thermoplastic resin composition of the present invention is preferably Biodegradable resin, can access that environmental pressure is few, the forming composition of extensibility, surface smoothing excellence.
In addition, forming composition of the present invention, because the surface smoothing excellence, therefore when surperficial coating carbon film, can be by coating equably.Thereby gas occluding is very high.
Embodiment
Specifically describe the present invention according to embodiment, but the present invention is not limited to these embodiment.Below, abbreviate weight part as part.
The material that uses in the present embodiment is shown in table 1, and surface treatment alpha-ferric oxide (A) is shown in table 2, and colorant for thermoplastic resin is shown in table 3, and the composition of thermoplastic resin composition and forming composition etc. is shown in table 4, and the result of evaluation test then is shown in table 5.
Table 1
| Alpha-ferric oxide (A) | FRO-3, median size 0.03 μ m, breadth-length ratio 0.9, Sakai chemical industry (strain) |
| Polyvalent alcohol | TriMethylolPropane(TMP) |
| Trimethylolethane | |
| Organopolysiloxane | The hydrogenated methyl polysiloxane |
| Dimethyl polysiloxane | |
| Hydroxyl carboxylic metallic salt (B1) | 12-oxystearic acid calcium, chemistry industry (strain) in big day |
| 12-oxystearic acid magnesium wins field chemical industry (strain) | |
| Higher fatty acid metal-salt (B2) | Calcium stearate, Application Na Application chemistry (strain) |
| Magnesium Stearate wins field processing (strain) | |
| Methyne based dye (C) | Port リ シ Application ス レ Application Block ラ ウ Application R, C.I. solvent brown 53, Network ラ リ ア Application ト Japan (strain) |
| Other ultraviolet screening agents | TINUVIN 234, UV light absorber, the different chemical of vapour Bart (strain) |
| NOVAPEX U-110, ultraviolet-shielding type resin, Mitsubishi Chemical's (strain) | |
| Polyethylene terephthalate (PET) | ミ Star イ ペ Star ト SA-135, Mitsui Chemicals (strain) |
| Polycarbonate | ュ one ピ ロ Application S-3000 (Natural color), Mitsubishi's engineering plastics (strain) |
| Polystyrene | A﹠M polystyrene HF77, A﹠M vinylbenzene (strain) |
| Poly(lactic acid) | レ イ シ ア H100J, Mitsui Chemicals (strain) |
The surface treatment alpha-ferric oxide
(use fluid: alpha-ferric oxide pressurized air) Yi Bian add surface treatment agent, obtains ferric oxide (1)～(6) with the injector-type mill pulverizing on one side.When also with polyvalent alcohol and organopolysiloxane is to add simultaneously.Each surface treatment agent is, by adopting known method, changes the processing weight of ferric oxide and the supply concentration or the supply flow rate of treatment agent, and regulating becomes regulation coating amount as shown in table 2.Here, TriMethylolPropane(TMP) is to be scattered in ethanol to use.
Table 2 surface treatment alpha-ferric oxide
| Alpha-ferric oxide | Polyvalent alcohol | Organopolysiloxane | |||
| FRO-3 | TriMethylolPropane(TMP) | Trimethylolethane | Dimethyl polysiloxane | The hydrogenated methyl polysiloxane | |
| Ferric oxide (1) | 100 | 0.5 | - | - | 0.5 |
| Ferric oxide (2) | 100 | 1 | - | - | 0.5 |
| Ferric oxide (3) | 100 | - | 0.5 | 0.5 | - |
| Ferric oxide (4) | 100 | 0.5 | - | - | - |
| Ferric oxide (5) | 100 | - | - | 0.5 | - |
| Ferric oxide (6) | 100 | - | - | - | - |
(unit: part)
Colorant for thermoplastic resin
For each 100 parts of ferric oxide (1)～(6), add the dispersion agent shown in the table 3, mix and make colorant for thermoplastic resin (1)～(8) with the mobile vibrating mixer (super floater) that suspends.
Table 3 colorant for thermoplastic resin
| Ferric oxide | Dispersion agent | ||||
| 12-oxystearic acid Ca | 12-oxystearic acid Mg | Stearic acid Ca | Stearic acid Mg | ||
| Tinting material (1) | Ferric oxide (1) | 100 | - | - | - |
| Tinting material (1) | Ferric oxide (1) | - | 100 | - | - |
| Tinting material (1) | Ferric oxide (2) | - | - | 100 | - |
| Tinting material (1) | Ferric oxide (3) | - | - | - | 100 |
| Tinting material (1) | Ferric oxide (4) | 100 | - | - | - |
| Tinting material (1) | Ferric oxide (5) | 100 | - | - | - |
| Tinting material (1) | Ferric oxide (6) | 100 | - | - | - |
| Tinting material (1) | Ferric oxide (6) | - | - | - | - |
(unit: part)
The thermoplastic resin composition
Embodiment 1～10, comparative example 1～4
As shown in the table 4, for 100 parts of resins, add colorant for thermoplastic resin (1)～(8) respectively, mix with the Henschel agitator, form bead with the extruding of single shaft extrusion machine, obtain thermoplastic resin composition (1)～(14).
Comparative example 5
In 99.76 parts of PET, add as 0.24 part of the TINUVIN 234 (the different chemical company manufacturing of vapour Bart) of UV light absorber, mix, form bead, obtain thermoplastic resin composition (15) with the extruding of single shaft extrusion machine with the Henschel agitator.
Comparative example 6
In 99.76 parts of PET, add ultraviolet-shielding type resin NOVAPEX U-110 (Mitsubishi Chemical Ind's manufacturings) 0.24 part, mix,, obtain thermoplastic resin composition (16) with single shaft extrusion machine extruding formation bead with the Henschel agitator.
Forming composition
As shown in table 4, cylinder is blended in 6 parts of 100 parts of matrix resins thermoplastic resin composition (1)～(14) separately using and above-mentioned thermoplastic resin compositions, and the twin shaft that the STRETCH BLOW shaper that uses Nissei ASB Machine Co., Ltd. to make is made capacity 500ml extends bottle.
And, use in 4 hours thermoplastic resin composition of 160 ℃ of dryings (15), (16), similarly make twin shaft respectively and extend bottle.
Table 4
| The thermoplastic resin composition | Forming composition | |||||||||||
| Thermoplastic resin | Colorant for thermoplastic resin | The methyne based dye | The thermoplastic resin composition | Thermoplastic resin | The thermoplastic resin composition | |||||||
| PET | Polycarbonate | Polystyrene | Poly(lactic acid) | PET | Polycarbonate | Polystyrene | Poly(lactic acid) | |||||
| Embodiment 1 | 100 | - | - | - | (1)8.5 | - | Resin combination (1) | 100 | - | - | - | (1)6 |
| Embodiment 2 | 100 | - | - | - | (1)8.5 | 0.2 | Resin combination (2) | 100 | - | - | - | (2)6 |
| Embodiment 3 | 100 | - | - | - | (1)8.5 | 0.7 | Resin combination (3) | 100 | - | - | - | (3)6 |
| Embodiment 4 | 100 | - | - | - | (1)8.5 | 1.5 | Resin combination (4) | 100 | - | - | - | (4)6 |
| Embodiment 5 | - | 100 | - | - | (1)8.5 | - | Resin combination (5) | - | 100 | - | - | (5)6 |
| Embodiment 6 | - | - | 100 | - | (1)8.5 | - | Resin combination (6) | - | - | 100 | - | (6)6 |
| Embodiment 7 | - | - | - | 100 | (1)8.5 | - | Resin combination (7) | - | - | - | 100 | (7)6 |
| Embodiment 8 | 100 | - | - | - | (2)8.5 | - | Resin combination (8) | 100 | - | - | - | (8)6 |
| Embodiment 9 | 100 | - | - | - | (3)8.5 | - | Resin combination (9) | 100 | - | - | - | (9)6 |
| Embodiment 10 | 100 | - | - | - | (4)8.5 | - | Resin combination (10) | 100 | - | - | - | (10)6 |
| Comparative example 1 | 100 | - | - | - | (5)8.5 | - | Resin combination (11) | 100 | - | - | - | (11)6 |
| Comparative example 2 | 100 | - | - | - | (6)8.5 | - | Resin combination (12) | 100 | - | - | - | (12)6 |
| Comparative example 3 | 100 | - | - | - | (7)8.5 | - | Resin combination (13) | 100 | - | - | - | (13)6 |
| Comparative example 4 | 100 | - | - | - | (8)8.5 | - | Resin combination (14) | 100 | - | - | - | (14)6 |
| Comparative example 5 | 99.76 | - | - | - | TINUVIN 0.24 | - | Resin combination (15) | - | - | - | - | (15)100 |
| Comparative example 6 | 99.76 | - | - | - | NOVAPEX 0.24 | - | Resin combination (16) | - | - | - | - | (16)100 |
The system film of DLC film
At bottle DLC film forming apparatus, use argon gas as assist gas, use acetylene as unstripped gas, import internal tank, under the condition of high frequency output 500W, feedstock gas pressures 0.3torr, supply gas flow 75ml/min, the inner face of each bottle with the thickness of 300 equably coating DLC (mensuration of DLC film thickness is, cover with formation such as marking inks in advance at the bottle inner face and to film, behind the coating DLC, cover with removals such as Anaesthetie Ethers and to film, the surface shape measuring device DECTACK3 that makes with Vecco company measures).
Estimate
(1) thermoplastic resin composition's limiting viscosity (η) and limiting viscosity conservation rate
Make the thermoplastic resin composition of containing resin 0.1g, 0.3g, 0.5g respectively, be used as sample.
Limiting viscosity (η): the mixed solvent 100ml that uses phenol/tetrachloroethane=50/50 (weight ratio), resinous principle in the solution heat thermoplastic resin composition, after the alpha-ferric oxide particle is removed in centrifugation, measure each resin solution 30 ℃ viscosity, draw the curve of viscosity/concentration value according to conventional methods, concentration 0 extrapolation is obtained limiting viscosity (η) for concentration.Here, blank sample only uses resin.
Limiting viscosity is represented the state of resin deterioration (hydrolysis), and the high more explanation resin deterioration of its value is low more.
Limiting viscosity conservation rate: the value of obtaining (limiting viscosity of the resin among the thermoplastic resin composition/barren limiting viscosity) * 100.This value illustrates that more near 100 (limiting viscosities of the approaching more blank sample of the limiting viscosity of the resin among the thermoplastic resin composition) the resin deterioration among the thermoplastic resin composition is few more.
(2) the light shielding and the transparency of forming composition
Cut bottle body portion 0.3mm thickness part as sample, carry out following evaluation test.
The light shielding rate: at four kinds of wavelength 380,400,420,550nm, as blank sample (100%), the UV-265FW that makes with Shimadzu Seisakusho Ltd. measures with air.
◎: shielding rate is more than or equal to 99%
Zero: shielding rate is more than or equal to 96%
△: shielding rate is more than or equal to 70%
*: shielding rate is less than 70%
The transparency: as blank sample (0), the ヘ イ ズ ガ one De プ ラ ス that makes with PVC Star Network ケ ミ one Japanese firm measures with air.Only making the situation of forming composition of moulding resin, is about 1 value roughly.The high more value of being somebody's turn to do of the transparency is low more, and the high more value of being somebody's turn to do of turbidity is high more.When haze value more than or equal to 15 the time, naked eyes just can be confirmed remarkable muddiness.
◎: smaller or equal to 4
Zero: smaller or equal to 6
△: smaller or equal to 10
*: greater than 10
(3) surface smoothing and the gas barrier of the forming composition of DLC have been implemented
Cut implemented DLC bottle body portion 0.3mm thickness part as sample, estimate the surface smoothing of bottle inner face.And, use bottle to estimate gas-premeable.
The evaluation of the surface smoothing of bottle inner face:
Use AFM (manufacturing of NSK company) to observe the surface, measure the maximum height of projection, according to following standard evaluation.
◎: less than 0.5 μ m
Zero: less than 0.8 μ m
△: less than 1 μ m
*: more than or equal to 1 μ m
Gas occluding:
For bottle, the OX-TRANT100 that uses MODERN CONTROL company to make is at 25 ℃ of transit doses of measuring oxygen, according to following standard evaluation.Here for the bottle that obtains at embodiment 1, when not making film DLC film for *.
◎: less than 24 hours atm of 0.0010ml/ bottle
Zero: less than 24 hours atm of 0.0030ml/ bottle
△: less than 24 hours atm of 0.0050ml/ bottle
*: more than or equal to 24 hours atm of 0.0050ml/ bottle
Table 5
| The thermoplastic resin composition | Forming composition | ||||||||
| Limiting viscosity (η) | The limiting viscosity conservation rate | Light shielding rate (%) | The transparency | Surface smoothing | Gas occluding | ||||
| 380nm | 400nm | 420nm | 550nm | ||||||
| Embodiment 1 | 0.75 | 91 | ◎ | ◎ | ◎ | × | ◎ | ◎ | ◎ |
| Embodiment 2 | 0.75 | 91 | ◎ | ◎ | ◎ | △ | ◎ | ◎ | ◎ |
| Embodiment 3 | 0.75 | 91 | ◎ | ◎ | ◎ | △ | ◎ | ◎ | ◎ |
| Embodiment 4 | 0.75 | 91 | ◎ | ◎ | ◎ | ○ | ◎ | ◎ | ◎ |
| Embodiment 5 | - | - | ◎ | ◎ | ◎ | × | ◎ | ◎ | ◎ |
| Embodiment 6 | - | - | ◎ | ◎ | ◎ | × | ○ | ◎ | ◎ |
| Embodiment 7 | 1.7 | 90 | ◎ | ◎ | ◎ | × | ○ | ◎ | ◎ |
| Embodiment 8 | 0.72 | 88 | ◎ | ◎ | ◎ | × | ○ | ◎ | ◎ |
| Embodiment 9 | 0.6 | 73 | ◎ | ◎ | ◎ | × | ○ | ◎ | ◎ |
| Embodiment 10 | 0.66 | 80 | ◎ | ◎ | ◎ | × | ○ | ◎ | ◎ |
| Comparative example 1 | 0.75 | 91 | ◎ | ◎ | ◎ | × | ○ | ○ | ○ |
| Comparative example 2 | 0.75 | 91 | ◎ | ◎ | ◎ | × | ○ | △ | △ |
| Comparative example 3 | 0.75 | 91 | ◎ | ◎ | ◎ | × | × | × | × |
| Comparative example 4 | 0.55 | 67 | △ | △ | △ | × | × | × | × |
| Comparative example 5 | 0.75 | 91 | ○ | × | × | × | ○ | ◎ | ○～× # |
| Comparative example 6 | 0.75 | 91 | ○ | × | × | × | ○ | ◎ | ○～× # |
#: if ultraviolet screening agents etc. ooze out, then gas occluding disappearance.
Industrial applicability
Colorant for thermoplastic resin of the present invention and use the thermoplastic resin composition of this colouring agent can needing be used for the article shaped of the excellent transparency, surface smoothness, ultraviolet-shielding type aptly.
Article shaped of the present invention, effective with the food stability (fresh-keeping) of food containers such as the storage stability of the content in the bottle container etc., pallet etc. for drinks such as beer containers, and can be applicable to the purposes such as packaging for foodstuff, cosmetic package. Also be expected to be applied to adopt the ultraviolet screener of the carport etc. of acrylic resin or polycarbonate resin, perhaps by ultraviolet ray and the visible light of shielding to film for agricultural use and thin slice, improve the productivity ratio of crops. And then article shaped of the present invention so can be used for aptly the DLC masking, owing to have gas occluding, is applicable to the purposes such as packaging for foodstuff, toiletry bag packaging container because surface smoothness is excellent again so can replace vial.
And, when article shaped of the present invention is film when (comprising shrinkable film), by coming the package object thing with this article shaped, when having the transparency, can easily realize shielding ultraviolet rays, shielding visible light and blocking-up gas.
Claims (18)
1. colorant for thermoplastic resin, it contains surface treatment alpha-ferric oxide (A) and as the hydroxyl carboxylic metallic salt (B1) of dispersion agent (B), and described surface treatment alpha-ferric oxide (A) is by being that 0.01～0.06 μ m and breadth-length ratio are that 0.2～1.0 non-needle-like alpha-ferric oxide forms with polyvalent alcohol and organopolysiloxane coating median size.
2. the described colorant for thermoplastic resin of claim 1, wherein, hydroxyl carboxylic metallic salt (B1) is a 12-oxystearic acid metal-salt.
3. the described colorant for thermoplastic resin of claim 2, wherein, 12-oxystearic acid metal-salt is a 12-oxystearic acid calcium.
4. colorant for thermoplastic resin, it contains surface treatment alpha-ferric oxide (A) and as the higher fatty acid metal-salt (B2) of dispersion agent (B), and described surface treatment alpha-ferric oxide (A) is by being that 0.01～0.06 μ m and breadth-length ratio are that 0.2～1.0 non-needle-like alpha-ferric oxide forms with polyvalent alcohol and organopolysiloxane coating median size.
5. the described colorant for thermoplastic resin of each in the claim 1～4, wherein, polyvalent alcohol or organopolysiloxane are handled alpha-ferric oxide (A) with respect to all surfaces, are respectively 0.01～10 weight %.
6. the described colorant for thermoplastic resin of each in the claim 1～5, wherein, polyvalent alcohol is TriMethylolPropane(TMP) or trimethylolethane.
7. the described colorant for thermoplastic resin of each in the claim 1～6, wherein, organopolysiloxane is dimethyl polysiloxane or hydrogenated methyl polysiloxane.
8. the described colorant for thermoplastic resin of each in the claim 1～7 wherein, with respect to surface treatment alpha-ferric oxide (A) 100 weight parts, cooperates the dispersion agent (B) of 40～150 weight parts.
9. the colorant for thermoplastic resin that contains methyne based dye (C) in the described colorant for thermoplastic resin of each in claim 1～8.
10. the described colorant for thermoplastic resin of claim 9, wherein, methyne based dye (C) is a C.I. solvent brown 53.
The thermoplastic resin composition who forms 11. cooperate each described colorant for thermoplastic resin in the claim 1～8, methyne based dye (C), thermoplastic resin.
12. the described thermoplastic resin composition of claim 11, wherein, methyne based dye (C) is a C.I. solvent brown 53.
The thermoplastic resin composition who forms 13. cooperate each described colorant for thermoplastic resin in the claim 1～10, thermoplastic resin.
14. the described thermoplastic resin composition of each in the claim 11～13, wherein, thermoplastic resin is a vibrin.
15. the described thermoplastic resin composition of each in the claim 11～14, wherein, thermoplastic resin is a Biodegradable resin.
The forming composition that obtains 16. use each the described colorant for thermoplastic resin in the claim 1～10.
17. the forming composition of using each the described thermoplastic resin in the claim 11～15 to obtain with composition.
18. forming composition at the surperficial coating carbon film of claim 16 or 17 described forming composition.
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| CN104105741B (en) * | 2012-02-03 | 2017-06-16 | 乐天尖端材料株式会社 | The molded plastics for showing the colored resin composition of pleochroism and being manufactured using it |
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