CN101198656B - Granular white resin composition - Google Patents
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- CN101198656B CN101198656B CN200680021052.0A CN200680021052A CN101198656B CN 101198656 B CN101198656 B CN 101198656B CN 200680021052 A CN200680021052 A CN 200680021052A CN 101198656 B CN101198656 B CN 101198656B
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Abstract
A particulate chromatic resin composition comprising an unused thermoplastic resin component, a chromatic pigment and a white pigment, or particulate white resin composition comprising an unused thermoplastic resin component, a white pigment and a black pigment, capable of forming a sheet whose luminosity (L*) and light transmittance satisfy the relationship of the formula: 1300 <= (L*B) <= 4000 wherein L* is the luminosity of 3 mm thick sheet produced from the resin composition, and B is the total light transmission ratio (%) of 50 [mu]m thick sheet produced from the resin composition.
Description
Technical field
The present invention relates to granular white resin composition and granular, white resin combination, this resin combination can be advantageously used in the synthetic resin of electric product; The synthetic resin of accommodating container; The synthetic resin of office equipment; The manufacture of the various colouring resin products formeds such as synthetic resin and white resin products formed for the automobiles such as bumper, automotive trim and automobile exterior.
Background technology
At the casing of outdoor as room conditioning, the fan blade of room conditioning, the pedestal of washing machine, rinse bath, static organ, balustrade exterior panelling, the bottom lattice plate of refrigerator, the handle of carrying use, furnace pot, food Article holding box, the upper pedestal of small refrigerator, the panel of duplicating machine, shell and paper feed tray, bumper, in the synthetic resin that the constituent material of the various parts such as automotive trim and automobile exterior is used, colouring resin products formed is following manufacture conventionally: in the thermoplastic resins such as the polyolefin resin not used or ABS resin, add colored pigment and filler as required, the added ingredientss such as elastomer resin, for example, by thermoplastic resin composition's's (feedstock composition that contains the above-mentioned material not used is commonly called virgin material) of preparation saccharoid (powder, long grain, sheet, particle, crushed material) heating and melting, import molding port mould, then cooling.
In the synthetic resin using at the constituent material as various mentioned components, the synthetic resin of white is in the thermoplastic resins such as the polyolefin resin not used or ABS resin, to add as required the added ingredientss such as filler, elastomer resin and white pigment, use the saccharoid of this white hot thermoplastic resin composition of preparing, prepare after the same method.
In the manufacturing processed of above-mentioned saccharoid or the moulding process of products formed, form sometimes the painted resin sex change thing due to resin melt local superheating, and be blended in products formed, in addition, the fine solid impurity that swims in air or be attached on forming machine also can be sneaked in material resin saccharoid or resin melt sometimes, mixes in products formed.These resin sex change things or solid impurity surpass certain level in synthetic resin sneaks into, and the existence meeting of this pigmentary resin sex change thing or solid impurity manifests on the surface of products formed.Particularly above-mentioned pigmentary resin sex change thing or solid impurity mostly are dark-coloured, obvious especially in the time of therefore in sneaking into the more shallow colouring resin products formed of color or white resin products formed.
The synthetic resin that the sneaking into of pigmentary resin sex change thing or solid impurity of usining manifests on surface as the electric product of component parts assembling, take in goods, office appliance or trolley part, its commodity value reduces, not preferred.Therefore, on the face that the synthetic resin that the sneaking into of pigmentary resin sex change thing or solid impurity manifests on surface normally manifests at this impurity, implement application, adventitia by application covers hiding impurity, or as substandard products waste treatment, or sneaking into it as above-mentioned resin sex change thing or solid impurity manifests the raw material re-using of also no problem resin forming article on products formed surface.
In recent years, the recycle of various materials requires to increase, form electric product, the synthetic resin of trolley part or office appliance etc. also requires to have the recycle of height, therefore, electric product, the manufacturer of trolley part and office appliance, at electric product, the manufacturer of the synthetic resin assembling on automobile and office appliance, supply with the material manufacturer of the material of these synthetic resins, and to the electric product after using, the Deng Ge enterprise of enterprise that automobile and office appliance carry out waste treatment has all taked the recycle measure to various resin materials.The object of these recycles is roughly divided into: the substandard products (being commonly referred to operation substandard products) that produce when above-mentioned synthetic resin is manufactured; Products formed is used by human consumer at actual electric product, trolley part or the office appliance etc. made, then the recovery article of separation from electric product, trolley part or the office appliance etc. of waste treatment.
A kind of method of preparing coloured regenerating resin saccharoid is disclosed in patent documentation 1, the method is mixture of white pigment and colored pigment heating in the crushed material of the mixture of the crushed material of the thermoplastic articles that contains black pigment, the crushed material of thermoplastic articles that contains black pigment and the crushed material of the thermoplastic articles that contains colored pigment or the thermoplastic articles that contains the mutually different two or more colored pigments of color, prepare heating and melting thing, then convert this heating and melting thing to solid particulate thing.
2 of patent documentations are open: being mixed with a small amount of resin cured matter, contain in black pigment or colored pigment, the thermoplastic articles crushed material as regeneration object and mix the Opacifying pigments such as one or more white pigments, black pigment, colored pigment, prepare heating and melting thing, then convert this heating and melting thing to solid particulate thing, thus without removing the surperficial tunicle with tunicate thermoplastic articles etc. such as bumper, can be made into can many-sided recycling regenerating resin saccharoid.
Patent documentation 1:WO03/095531 A1 communique
Patent documentation 2:WO03/089500 A1 communique
Summary of the invention
The resin crushed material that the thermoplastic articles that contains black pigment or colored pigment is recovered, pulverizes after use, as recorded in above-mentioned patent documentation 1 and 2, while implementing regenerative operation by utilization, append and add the method that opacifying property pigment is regenerated, can recycle.
But, in above-mentioned known method, when the thermoplastic articles crushed material enforcement regenerative operation to as regeneration object, must hold one by one the pollution situation of solid impurity in its object thermoplastic articles crushed material, determine kind or the addition of the opacifying property pigment that will add simultaneously, comparatively numerous and diverse.
Main purpose of the present invention is to provide a kind of technology that causes producing the bad order products formed that was in the past used as the waste treatment of operation substandard products of sneaking into that can suppress due to the formation of pigmentary resin sex change thing or solid impurity, the formation of wherein said pigmentary resin sex change thing or solid impurity sneak into be will coloured or white hot thermoplastic resin composition (virgin material) moulding, occur while manufacturing the coloured or white resin products formed of the component parts that is used as electric product, trolley part or office appliance etc.
The present invention also aims to provide when the crushed material recycling to used coloured or white thermoplastic articles, without adding new opacifying property pigment, or the technology of carrying out delicate adjusting without the addition of the opacifying property pigment to new.
The present inventor finds: when adding filler and colored pigment in the thermoplastic resin composition not used to polyolefin resin or ABS resin etc. in preparation and preparing granular resin composition, by white pigment (preferably with a small amount of black pigment combination) is existed under given conditions, even if sneak into a small amount of pigmentary resin sex change thing or solid impurity in the products formed of preparing through heating and melting, also can prevent that sneaking into of these materials is emerging on gained synthetic resin surface (hiddenization).
The present inventor also finds: when adding filler and white pigment preparing granular, white resin combination in the thermoplastic resin composition that do not used to polyolefin resin or ABS resin etc. of preparation, by a small amount of black pigment is existed under given conditions, even if sneak into a small amount of pigmentary resin sex change thing or solid impurity in the products formed of preparing through heating and melting, also can prevent that sneaking into of these materials is emerging on synthetic resin surface (hiddenization).
The invention still further relates to granular white resin composition, it is characterized in that: this granular white resin composition contains thermoplastic resin composition, colored pigment and the white pigment not used, the brightness (L of the sheet material of being made by this resin combination
*) and the relation of transparence meet following formula:
1300≤(L
*×B)≤4000
L
*be the brightness of the sheet material of the thickness 3mm that made by above-mentioned resin combination, B is the total light transmittance (%) of the sheet material of the thickness 50 μ m that made by above-mentioned resin combination.
Granular white resin composition of the present invention refers to that whiteness is lower than 55 resin combination.
The invention still further relates to above-mentioned granular white resin composition heating and melting, colouring resin products formed that then moulding obtains.
The invention still further relates to granular, white resin combination, it is characterized in that: this granular, white resin combination contains thermoplastic resin composition, white pigment and the black pigment not used, the brightness (L of the sheet material of being made by this resin combination
*) meet following formula with the relation of transparence:
1300≤(L
*×B)≤4000
L
*be the brightness of the sheet material of the thickness 3mm that made by above-mentioned resin combination, B is the total light transmittance (%) of the sheet material of the thickness 50 μ m that made by above-mentioned resin combination.L
*the scope of preferred 55-90, the scope of further preferred 60-90, the further scope of preferred 70-90, the particularly preferably scope of 80-90.
Granular, white resin combination of the present invention refers to that whiteness is more than 55 resin combination typically.Whiteness is that the resin combination of 50-60 scope can utilize the combination of colored pigment and white pigment or the combination of white pigment and black pigment.
The invention still further relates to above-mentioned granular, white resin combination heating and melting, follow the white resin products formed that moulding obtains.
The preferred version of granular white resin composition of the present invention is as follows.
(1) granular white resin composition further contains black pigment.
(2) granular white resin composition contains filler.
(3) thermoplastic resin composition be take polyolefine as main component (more than 50% quality).
(4) scope that the total light transmittance representing with B of the sheet material of being made by granular white resin composition is 15-60% (the more preferably scope of 18-55, further preferably the scope of 20-50, the particularly preferably scope of 25-48).
(5) content of white pigment (the more preferably scope of 1-20% quality that is that 1% quality is above, 20% quality following in granular white resin composition, the scope of further preferred 1.5-18% quality, the particularly preferably scope of 2-15% quality, the most preferably scope of 3-12% quality).
(6) in granular white resin composition, contained white pigment is titanium dioxide.
(7) content of black pigment (the more preferably scope of 0.05-0.8% quality that is that 0.01% quality is above, 1.0% quality following in granular white resin composition, the scope of further preferred 0.01-0.5% quality, the scope of 0.012-0.3% quality particularly preferably), the content of black pigment is fewer than the content of white pigment.
(8) black pigment containing in granular white resin composition is for iron black.
(9) whiteness of the sheet material of the thickness 3mm being made by granular resin composition is lower than 55.
(10) (L
** B) be (preferred 1500-4000, further preferred 1800-4000, particularly preferably 2000-3800) more than 1300, below 4000.
The preferred version of granular, white resin combination of the present invention is as follows.
(1) granular, white resin combination contains filler.
(2) thermoplastic resin composition be take polyolefine as main component (more than 50% quality).
(3) sheet material of being made by granular, white resin combination of the present invention use L
*the scope that the brightness representing is 55-90 (the more preferably scope of 60-90, further preferably the scope of 70-90, the particularly preferably scope of 80-90).
(4) scope that the total light transmittance representing with B of the sheet material of being made by granular, white resin combination is 15-60% (the more preferably scope of 18-55, further preferably the scope of 20-50, the particularly preferably scope of 25-48).
(5) content of white pigment (the more preferably scope of 1-20% quality that is that 1% quality is above, 20% quality following in granular, white resin combination, the scope of further preferred 1.5-18% quality, the particularly preferably scope of 2-15% quality, the most preferably scope of 3-12% quality).
(6) in granular, white resin combination, contained white pigment is titanium dioxide.
(7) content of black pigment (the more preferably scope of 0.05-0.8% quality that is that 0.01% quality is above, 1.0% quality following in granular, white resin combination, the scope of further preferred 0.01-0.5% quality, the scope of 0.012-0.3% quality particularly preferably), the content of black pigment is fewer than the content of white pigment.
(8) black pigment containing in granular, white resin combination is for iron black.
(9) whiteness of the sheet material of the thickness 3mm being made by granular, white resin combination is more than 55 (more preferably more than 65, further preferably more than 75, particularly preferably more than 80).
(10) (L
** B) be (preferred 1500-4000, further preferred 1800-4000, particularly preferably 2000-3800) more than 1300, below 4000.
The granular white resin composition of the application of the invention or granular, white resin combination, can suppress in the past when granular white resin composition (virgin material) hot briquetting is manufactured to synthetic resin, due to the generation producing, be used as the bad order products formed of operation substandard products waste treatment of sneaking into of the formation of pigmentary resin sex change thing or solid impurity.
Use white resin products formed prepared by granular white resin composition of the present invention or granular, white resin combination when use recycles the crushed material of this products formed afterwards, without adding new opacifying property pigment, or carry out delicate adjusting without the addition of the opacifying property pigment to new.
The best mode carrying out an invention
In granular resin composition of the present invention, first granular white resin composition is carried out to following detailed description.
Granular white resin composition of the present invention contains thermoplastic resin composition, colored pigment and the white pigment that the polyolefin resin that do not used or ABS resin etc. had not been used, and preferably further contains black pigment, also can contain filler.Thermoplastic resin composition can contain elastomer resin.
When polyolefin resin and elastomer resin are combined with, in thermoplastic resin composition, the ratio of mixture of polyolefin resin and elastomer resin is 100 according to mass ratio conventionally: 1-100: 80 scope (preferably 100: 1-100: 50 scope, further preferably 100: 5-100: 40 scope).
The example of thermoplastic resin has: polyolefin resin, polyamide-based resin, the polysulfones etc. such as the polyacrylic acid resinoids such as polyphenylene ether resin, the polymethylmethacrylates such as polyester resin, Noryl, polyphenylene sulfide, nylon 6, nylon 66, nylon 12, nylon 612 such as ABS resin, polycarbonate resin, polyurethanes resin, styrene resin, ABS resin (acrylonitrile-butadiene-styrene resin), polybutylene terephthalate, polyethylene terephthalate.
The example of polyolefin resin has: the mixture of the polyvinyl resins such as the acrylic resins such as crystalline polypropylene, high density polyethylene(HDPE) or Low Density Polyethylene and these resins.
Elastomer resin is the thermoplasticity amorphism elastomer resin that does not have the thermoplasticity low-crystalline elastomerics of clear and definite yield-point or do not have clear and definite fusing point and yield-point, can use elastomerics or the rubber at normal temperatures with caoutchouc elasticity.Operable elastomeric object lesson has: the thermoplastic elastomers such as styrenic elastomerics, olefin type elastomer, polyester elastomer, polyamide-based elastomerics, polyurethanes elastomerics.Elastomer resin can be used separately, also can be used in combination.
As required, when preparation granular white resin composition of the present invention, can in the thermoplastic resin composition (virgin material) not used, with relatively less amount mixed regeneration resinous principle, use.
The filler using while containing filler in granular white resin composition can be used organic filler and the mineral filler except pigment, preferably mineral filler.The filler of the preferred opacifying property of these fillers.Filler preferably adds with the amount below 40 mass parts with respect to 100 mass parts thermoplastic resin compositions.
Mineral filler can be used talcum powder, clay, mica, silicon-dioxide, diatomite, MOS HIGE (basic magnesium sulfate fiber), TISMO (potassium titanate fiber), wollastonite, montmorillonite, bentonite, rhombspar, dosonite, silicates, carbon fiber, glass fibre, barium ferrite, beryllium oxide, aluminium hydroxide, magnesium hydroxide, alkaline magnesium carbonate, calcium carbonate, magnesiumcarbonate, magnesium sulfate, calcium sulfate, barium sulfate, ammonium sulfate, calcium sulfite, Calucium Silicate powder, moly-sulfide, zinc borate, barium metaborate, lime borate, Sodium Tetraborate etc., or zinc, copper, iron, plumbous, aluminium, nickel, chromium, titanium, manganese, tin, platinum, tungsten, gold, magnesium, cobalt, the metals such as strontium and their metal oxide, stainless steel, scolding tin, the alloys such as brass, silicon carbide, silicon nitride, zirconium white, aluminium nitride, the powder of the metal species potteries such as titanium carbide etc., fibrous whisker and fiber etc.Particularly preferably talcum powder and mica.
Colored pigment is not so long as known can use has restriction, such as having: mineral dyes such as the oxide compound of metal, oxyhydroxide, sulfide, chromic salt, carbonate, vitriol, silicate; The pigment dyestuffs such as azo, diphenylmethyl alkanes, triphenylmethane, phthalocyanines, nitro class, nitrous base class, Anthraquinones, the red class of quinacridone, diphenyl amine, fused polycycle class etc.Also can be coloured fiber or the glossiness metallic particles of tool etc.Form and aspect to colored pigment are not particularly limited, and can use Huang, indigo plant, the form and aspect arbitrarily such as red, green.These pigment can two or morely be combined with.
The object lesson of the colored pigment that can use in the present invention has: the mineral dye such as red iron oxide, ultramarine, cobalt blue, titan yellow, Prussian blue, zinc sulphide, baryta yellow, cobalt blue, cobalt green; The pigment dyestuffs such as quinacridone is red, polyazo is yellow, anthraquinone is red, anthraquinone is yellow, polyazo is red, azo lake is yellow, perylene, phthalocyanine blue, phthalocyanine green, isoindolinone is yellow, Watchung is red, permanent red, Ba Lahong, toluidine maroon, diarylide yellow, fast sky blue, brilliant carmine 6B; Coloured fiber; The glossiness metallic particles of tool etc., these pigment can two or morely be combined with.
The median size of titan yellow is not particularly limited, preferred 0.1-1.5 μ m, and further preferred 0.5-1.3 μ m, more preferably 0.7-1.1 μ m, 0.8-1 μ m particularly preferably, because its dispersiveness, applicability and operability are excellent.The DOP oil number of titan yellow is not particularly limited, preferred 15-40 (cc/100g), further preferred 20-35 (cc/100g), the particularly preferably scope of 20-30 (cc/100g).The pH of titan yellow is not particularly limited, preferably 6-10, the particularly preferably scope of 7-9.
Ultramarine, so long as the ultramarine of using as pigment is not particularly limited in the past, all can be used.The median size of ultramarine is not particularly limited, preferred 0.1-5 μ m, and further preferred 0.5-4 μ m, more preferably 0.8-3.5 μ m, particularly preferably is 1-3 μ m, because its dispersiveness, applicability and operability are excellent.The DOP oil number of ultramarine is not particularly limited, preferred 20-50 (cc/100g), further preferred 25-40 (cc/100g), particularly preferably 30-35 (cc/100g).The pH of ultramarine is not particularly limited, preferred 5-11, further preferred 5.5-11, the particularly preferably scope of 7-11.
Phthalocyanine blue, so long as the phthalocyanine blue of using as pigment does not limit in the past, all can not used, for example, can use by Waller method or the standby phthalocyanine blue of benzene dicarbonitrile legal system.The particle shape of phthalocyanine blue is not particularly limited, and can use α shape, β shape etc.The median size of phthalocyanine blue is not particularly limited, and is preferably 0.01-2 μ m, further preferred 0.05-1.5 μ m, more preferably 0.1-0.4 μ m, the particularly preferably scope of 0.1-1 μ m.
Phthalocyanine green, so long as the phthalocyanine green of using as pigment does not limit in the past, all can not used, for example, can use by Waller method or the standby phthalocyanine green of benzene dicarbonitrile legal system.The particle shape of phthalocyanine green is not particularly limited, and can use α shape, β shape etc.The median size of phthalocyanine green is not particularly limited, and is preferably 0.01-2 μ m, further preferred 0.05-1.5 μ m, more preferably 0.1-0.4 μ m, the particularly preferably scope of 0.1-1 μ m.The pH of phthalocyanine green is not particularly limited, preferred 4-9, the scope of further preferred 4-8.
Red iron oxide, so long as the red iron oxide of using as pigment does not limit in the past, all can not used.The particle shape of red iron oxide is not particularly limited, and can use tesseral system etc.The median size of red iron oxide is not particularly limited, and is preferably 0.01-1 μ m, further preferred 0.05-0.5 μ m, more preferably 0.08-0.4 μ m, the particularly preferably scope of 0.1-0.3 μ m.The DOP oil number of red iron oxide is not particularly limited, preferred 10-50 (cc/100g), further preferred 12-40 (cc/100g), the particularly preferably scope of 15-30 (cc/100g).The pH of red iron oxide is not particularly limited, preferred 4-8, the scope of further preferred 5-7.
Quinacridone is red not to be limited so long as the quinacridone using as pigment is red in the past, all can use.The red particle shape of quinacridone is not particularly limited, and can use α shape, β shape, γ shape etc.The red median size of quinacridone is not particularly limited, and is preferably 0.01-2 μ m, further preferred 0.05-1.5 μ m, the particularly preferably scope of 0.1-1 μ m.Anthraquinone is red not to be limited so long as the anthraquinone using as pigment is red in the past, all can use.The red median size of anthraquinone is not particularly limited, and is preferably 0.01-2 μ m, further preferred 0.05-1.5 μ m, the particularly preferably scope of 0.1-1 μ m.The red pH of anthraquinone is not particularly limited, preferably the scope of 4-9.
White pigment can exemplify titanium dioxide, white lead, zinc oxide.Titanium dioxide particularly preferably.
Titanium dioxide can be used the titanium dioxide in the past using as pigment, for example, can use the titanium dioxide of preparing by chlorine method or sulfuric acid process.Preferably by the standby titanium dioxide of chlorine legal system.Particle shape is not particularly limited, and can use tetragonal system, rutile-type, Detitanium-ore-type etc., particularly preferably tetragonal system and rutile-type.Median size is not particularly limited, preferred 0.01-0.5 μ m, and further preferred 0.05-0.5 μ m, more preferably 0.1-0.4 μ m, the particle of 0.2-0.3 μ m particularly preferably, its dispersiveness, applicability and operability are excellent.The DOP oil number of titanium dioxide is not particularly limited, preferred 5-40 (cc/100g), further preferred 8-30 (cc/100g), more preferably 10-20 (cc/100g), particularly preferably 12-18 (cc/100g).White pigment can two or morely be combined with.
Black pigment can exemplify carbon black, iron oxide black etc.Black pigment can make synthetic resin have high opacifying property.Black pigment also can two or morely be combined with.
Carbon black can be used in the past the carbon black using as pigment, black etc. such as using the carbon black prepared by oven process or channel process, acetylene black, dim, furnace black, ketchen.Carbon black can also be used through oxide treatment gained.The carbon black furnace black that particularly preferably prepared by oven process, because its outward appearance excellent in uniformity, excellent dispersion, the degree of blackness of gained products formed, that gloss improves effect is also large.The median size of carbon black is not particularly limited, preferred 0.001-0.3 μ m, further preferred 0.005-0.2 μ m, more preferably 0.01-0.1 μ m, 0.01-0.03 μ m particularly preferably, because its dispersiveness, applicability and operability are excellent, aspect degree of blackness, gloss raising, also can bring into play large effect.
The iron black ferric oxide that can use the black being obtained by calcination method.Iron black particle shape is not particularly limited, and can use the octahedra polyhedron shape, spherical etc. that waits, particularly preferably octahedra.Iron black median size is not particularly limited, preferred 0.05-0.4 μ m, further preferred 0.15-0.35 μ m, particularly preferably 0.2-0.35 μ m.Iron black DOP oil number is not particularly limited, preferred 10-80 (cc/100g), and further preferred 15-50 (cc/100g), more preferably 20-40 (cc/100g), particularly preferably is the scope of 25-35 (cc/100g).Iron black pH is not particularly limited, preferably 9-11, particularly preferably 9-10.
The black pigment adding in granular white resin composition of the present invention is preferably compared the weak iron oxide black of black with carbon black, this is because appropriate brightness and the fine setting of transparence, by regulating addition, can easily be carried out in the iron oxide black with above-mentioned characteristic.
In granular white resin composition of the present invention, also can further add as required various resin additives (such as the dispersion agents such as calcium stearate, lubricant, static inhibitor, tensio-active agent, nucleator, UV light absorber, antioxidant, fire retardant).
Colored pigment, white pigment and other added ingredientss such as black pigment that add as required can directly add in the thermoplastic resin composition not used, or the method (masterbatch is allocated technology into) that also can utilize the previously prepared resin combination that contains high density pigment (masterbatch), then mix with the resin combination that does not add pigment.It is known using the masterbatch of various pigment and resinous principle to allocate technology into.
The preparation method's of granular white resin composition of the present invention example is as follows.
(1) to adding and be predicted as appropriate colored pigment and white pigment and black pigment as required in the saccharoid of the thermoplastic resin composition not used, add as required again filler or various resin additive, with the form acquisition granular white resin composition of mixture.
(2) by said mixture melting mixing, then directly or via saccharoid respectively for the preparation of the sheet test film of measuring brightness and transparence.
(3) measure brightness and the transparence of sheet test film, the condition that this measurement result and above-mentioned mathematical expression is represented compares, and judges colored pigment, white pigment and whether kind or the addition of the black pigment of use be appropriate as required.The brightness of test film and transparence (%) long-pending surpasses at 4000 o'clock or lower than 1300 o'clock, can appropriate change colored pigment, kind or the addition of white pigment and black pigment etc., then return to the step of above-mentioned (1).Amassing of the brightness of test film and transparence (%) be more than 1300,4000 when following, can be used as granular white resin composition utilization of the present invention.
By carrying out aforesaid operations, can prepare to there is required tone, granular white resin composition outward appearance transitivity, that can be used for moulding.
In the present invention, the saccharoid of thermoplastic resin composition and the blending means of each added ingredients, mixing device, the mixing equipment that had not used are not particularly limited, and can use tandem kneading device that known single axle extruding machine (mixing roll), biaxial extruder (mixing roll), biaxial extruder be connected in series with single axle extruding machine (mixing roll), rolling press, Banbury mixer, mixing roller, Brabender, Plastograph, kneader etc. to mix and/or kneading device etc.
Granular white resin composition of the present invention can adopt known moulding or the forming methods such as extrusion moulding, sheet forming, injection molding, injection compression molding, gas inject injection molding, blow molding, vacuum forming, for the manufacture of the colouring resin products formed of various uses.
By granular white resin composition of the present invention can obtain have glossy surface colouring resin products formed, there is the colouring resin products formed of embossing or pattern or there is the colouring resin products formed of the arbitrary surfaces states such as colouring resin products formed of smooth embossing or pattern.
Then, the granular, white resin combination in granular resin composition of the present invention is elaborated.
Granular, white resin combination of the present invention contains thermoplastic resin composition, white pigment and the black pigment that the polyolefin resin that do not used or ABS etc. had not been used.Also can further contain filler.And thermoplastic resin composition can contain elastomer resin.
The example of thermoplastic resin can exemplify as the thermoplastic resin described in granular white resin composition composition.
Elastomer resin can exemplify as the various elastomer resins described in granular white resin composition composition.
As required, when preparation granular, white resin combination of the present invention, in the thermoplastic resin composition (virgin material) not used, can use with relatively few amount mixed regeneration resinous principle.
While containing filler in granular, white resin combination, the filler of use can be as the various fillers described in granular white resin composition composition.
White pigment can be as the various white pigments described in granular white resin composition composition.
Black pigment can be as the various black pigments described in granular white resin composition composition.
The black pigment adding in granular, white resin combination of the present invention is also preferably compared the weak iron oxide black of black with carbon black.This is because the iron oxide black with above-mentioned characteristic is by regulating addition can easily carry out the fine setting of appropriate brightness and transparence.
As required, can in granular, white resin combination of the present invention, further add micro-colored pigment.The example of spendable colored pigment can exemplify as the various colored pigments described in granular white resin composition composition.Form and aspect to colored pigment are not particularly limited, and can use Huang, indigo plant, the form and aspect arbitrarily such as red, green.These pigment can two or morely be combined with.
In granular, white resin combination of the present invention, can further add as required various resin additives (such as the dispersion agents such as calcium stearate, lubricant, static inhibitor, tensio-active agent, nucleator, UV light absorber, antioxidant, fire retardant).
White pigment, black pigment and other added ingredients adding as required can directly add in the thermoplastic resin composition not used, or the method (masterbatch is allocated technology into) that also can utilize the previously prepared resin combination that contains high density pigment (masterbatch), then mix with the resin combination that does not add pigment.It is known using the masterbatch of various pigment and resinous principle to allocate technology into.
The preparation method's of granular, white resin combination of the present invention example is as follows.
(1) to adding and be predicted as appropriate white pigment and black pigment in the saccharoid of the thermoplastic resin composition not used, add as required again filler, colored pigment or various resin additive, with the form acquisition granular, white resin combination of mixture.
(2) by said mixture melting mixing, then directly or via saccharoid respectively for the preparation of the sheet test film of measuring brightness and transparence.
(3) measure brightness and the transparence of sheet test film, this measurement result and the represented condition of above-mentioned mathematical expression are compared, judge that whether the kind of white pigment and black pigment or addition be appropriate.The long-pending of the brightness of test film and transparence (%) surpasses at 4000 o'clock or at discontented 1300 o'clock, can appropriate change white pigment and kind or the addition of black pigment, then return to the step of above-mentioned (1).Amassing of the brightness of test film and transparence (%) be more than 1300,4000 when following, can be used as granular, white resin combination of the present invention utilization.
By carrying out aforesaid operations, can prepare to there is required tone, granular, white resin combination outward appearance transitivity, that can be used for moulding.
Available mixing device or shaped device in the preparation method of granular, white resin combination of the present invention and the method for white resin products formed of preparing various uses by granular, white resin combination, can be with reference to the record of relevant granular white resin composition.
By granular, white resin combination of the present invention can obtain have glossy surface products formed, there is the products formed of embossing or pattern or there is the products formed of the arbitrary surfaces states such as products formed of smooth embossing or pattern.The white of granular, white resin combination of the present invention conventionally means and comprises the color that is called as pale yellow or light grey etc. white color system.
Embodiment
Below provide embodiment and comparative example explanation the present invention, the present invention is not subject to the restriction of these embodiment.
(1) mensuration of whiteness and form and aspect
Using mold pressure is the injection moulding machine of 130 tons, at mould: square plate (100mm * 100mm * 3mm; Minute surface), mold temperature: C1-C2-C3-C4=180-190-200-210 ℃, injection pressure: P1-P2-P3-P4=108-98-88-78MPa, injection speed: V1-V2-V3-V4=30-30-20-20%, screw back pressure simultaneously: embossing, another side:: arbitrarily, screw rod revolution: 60%, die temperature: 40 ℃, cycle: inject under the injecting condition of 10 seconds, cooling 20 seconds resin particle is shaped to test film (thickness: 3mm).With the SM-4 color measurement instrument of Suga trier (strain), measure the L of embossing face one side of this test film
*, a
*, b
*, L, a, b, obtain in accordance with known methods whiteness, brightness and form and aspect.
(2) mensuration of transparence
Use mold pressure is the heat pressing forming machines of 40 tons, resin particle is clipped in the iron plate of photograph use (interval: 70 * 50 * 0.05mm), at 230 ℃ of temperature of heating plate, 2 minutes waste heat time, 1 minute deaeration treatment time, 1 minute clamping time (pressure: 100kg/cm
2), make the film of 50 ± 3 μ m under 20 ℃ of cooling temperatures, the condition of molding of 2 minutes cooling times, using this as test film of measuring total light transmittance and using.
Use turbidometer (turbidometer NDH2000 is manufactured in Japanese electric look industry) to measure the total light transmittance (%) of this test film, using total light transmittance (%) as transparence (%).Light source is used halogen lamp, and (rated specification 5V9W, light incident section opening diameter is 20mm
), measure 5 points of film, ask its mean value.
(3) the ocular estimate method of the preparation of test film and pull and stretch face
In 100 mass parts resin particles, add the iron powder that 0.05 mass parts median size is 0.3mm, the rotary drum that uses Platech company to manufacture, was dry mixed with 5 minutes.Then at above-mentioned injection molding condition compacted under test film (100mm * 100mm * 3mm, a surface is embossing, another surface is minute surface), whether the solid impurity (iron powder) that visual judgement gained test film surface exists is obvious in appearance.Visual observation result is evaluated with three grades according to following benchmark.
1: the existence of solid impurity all clearly (defective) on minute surface and embossing face
2: on minute surface the existence of solid impurity more obvious, on embossing face, (qualified) almost can't see in the existence of solid impurity
3: exist (qualified) that all can't see solid impurity on minute surface and embossing face
(A) preparation of granular white resin composition
< is used material >
(1) polyolefin resin: crystalline polypropylene (new resin, MFR=30g/10 minute, ethylene content be the ethylene/propylene alkene block copolymer of 7 quality %)
(2) white pigment: titanium dioxide (addition is the % quality with respect to polyolefin resin, is recorded in table 1)
(3) colored pigment: red iron oxide, ultramarine, isoindoline A (Ciba SpecialtyChemicals preparation, CROMOPHTAL ORANGE 2G), isoindoline B (CibaSpecialty Chemicals preparation, IRGAZIN YELLOW 3RLT-N) (addition is the % quality with respect to polyolefin resin, is recorded in table 1)
(4) black pigment: iron black (addition is the % quality with respect to polyolefin resin, is recorded in table 1)
(5) dispersion agent: calcium stearate (addition is the % quality with respect to polyolefin resin, is recorded in table 1)
(6) antioxidant: IRGAFOS 168 (addition is the % quality with respect to polyolefin resin, is recorded in table 1)
[embodiment A 1-A3, Comparative examples A 1-A3]
The preparation > of < resin particle
With respect to 100 weight part polyolefin resines, according to the amount described in table 1, add white pigment, black pigment, colored pigment, dispersion agent and antioxidant, the rotary drum that uses Platech company to manufacture is dry mixed, then use twin shaft mixing roll (UME40-48T, the emerging product of space portion (strain) preparation), melting mixing under the condition of 220 ℃ of barrel temperatures, treatment capacity 60kg/ hour, obtains resin particle.
[table 1]
As shown in Table 1, the light shielding ability of the solid impurity that granular white resin composition of the present invention is sneaked into for the products formed inside by this resin combination moulding is high, therefore, is applicable to the synthetic resin that preparation is used in various uses.
(B) preparation of granular, white resin combination
< is used material >
(1) polyolefin resin: crystalline polypropylene (new resin, MFR=30g/10 minute, ethylene content be the ethylene/propylene alkene block copolymer of 7 quality %)
(2) filler: 15 mass parts talcum powder (hydrous magnesium silicate, median size: 2.7 μ m)
(3) white pigment: titanium dioxide (addition is with respect to the % quality of the total amount of above-mentioned (1) and (2) composition, is recorded in table 2 and table 3)
(4) black pigment: iron black (addition is with respect to the % quality of the total amount of above-mentioned (1) and (2) composition, is recorded in table 2 and table 3)
(5) colored pigment: titan yellow and red iron oxide (addition is with respect to the % quality of the total amount of above-mentioned (1) and (2) composition, is recorded in table 2 and table 3)
[Embodiment B 1, comparative example B1]
The preparation > of < white resin particle
With respect to 100 weight part polyolefin resines, according to the amount described in table 2, add white pigment, black pigment and colored pigment, the rotary drum that uses Platech company to manufacture is dry mixed, then use twin shaft mixing roll, melting mixing under the condition of 220 ℃ of barrel temperatures, treatment capacity 60kg/ hour, obtains white resin particle.
[Embodiment B 2-B5, comparative example B2-B3]
The preparation > of < white resin particle
With respect to 90 weight part polyolefin resines and 10 weight part fillers, according to the amount described in table 3, add white pigment, black pigment and colored pigment, the rotary drum that uses Platech company to manufacture is dry mixed, then use twin shaft mixing roll, melting mixing under the condition of 220 ℃ of barrel temperatures, treatment capacity 60kg/ hour, obtains white resin particle.
[table 2]
[table 3]
From the result of table 2 and table 3, the light shielding ability of the solid impurity that granular, white resin combination of the present invention is sneaked into for the products formed inside by this resin combination moulding is high, is therefore applicable to the white resin products formed that preparation is used in various uses.
(C) preparation of granular, white resin combination (for the preparation of automobile synthetic resin)
< is used material >
(1) polyolefin resin: 65 mass parts crystalline polypropylenes (new resin, MFR=70g/10 minute, ethylene content be the ethylene/propene copolymer of 7% quality)
(2) elastomer resin: 20 mass parts ethylene-propylene copolymer resins (virgin material, mooney viscosity: MI1+4 (100 ℃)=35, ethylene content: 72% quality)
(3) filler: 15 mass parts talcum powder (hydrous magnesium silicate, median size: 2.7 μ m)
(4) white pigment: titanium dioxide (addition, with the % quality representation with respect to above-mentioned (1), (2) and (3) composition total amount, is recorded in table 4)
(5) black pigment: iron black (addition, with the % quality representation with respect to above-mentioned (1), (2) and (3) composition total amount, is recorded in table 4)
(6) tinting pigment: titan yellow and red iron oxide (addition, with the % quality representation with respect to above-mentioned (1), (2) and (3) composition total amount, is recorded in table 4)
(7) other additive: dispersion agent (calcium stearate, addition is 0.1% quality with respect to the total amount of above-mentioned (1), (2) and (3) composition), Irgafos 168:0 (addition is 0.1% quality with respect to the total amount of above-mentioned (1), (2) and (3) composition), Irganox 1010 (addition is 0.1% quality with respect to the total amount of above-mentioned (1), (2) and (3) composition)
[Embodiment C 1-C4, comparative example C1-C2]
The preparation > of < white resin particle
The rotary drum that uses Platech company to manufacture is dry mixed each composition, then uses twin shaft mixing roll, and melting mixing under the condition of 220 ℃ of barrel temperatures, treatment capacity 60 kg/ hour, obtains white resin particle.
[table 4]
As shown in Table 4, the light shielding ability of the solid impurity that granular, white resin combination of the present invention is sneaked into for the products formed inside by this resin combination moulding is high, is therefore applicable to preparing the white resin products formed that automobile is used.
Claims (15)
1. granular white resin composition, it is characterized in that: the white TiO 2 pigment that said composition contains thermoplastic resin composition, colored pigment and the 1-12% quality do not used, scope and its brightness L that the total light transmittance of the thickness 50 μ m sheet materials of being made by this resin combination is 15-60%
*meet following formula with the relation of transparence:
1300≤(L
*×B)≤4000
L
*for the brightness of the thickness 3mm sheet material made by above-mentioned resin combination, B is above-mentioned total light transmittance %.
2. the resin combination of claim 1, it is above but lower than the black pigment of 1.0% quality that this resin combination further contains 0.01% quality.
3. the resin combination of claim 1, this resin combination further contains filler.
4. the resin combination of claim 1, wherein, thermoplastic resin composition is usingd polyolefine as main component.
5. the resin combination of claim 1, wherein, the sheet material of being made by resin combination shows the whiteness lower than 55.
6. the resin combination of claim 2, wherein, black pigment is iron black.
7. synthetic resin, this synthetic resin is by the granular white resin composition heating and melting of claim 1, then obtained by molding.
8. granular, white resin combination, it is characterized in that: the white TiO 2 pigment that this resin combination contains the thermoplastic resin composition that do not used, 1-12% quality and 0.01% quality are above but lower than the black pigment of 1.0% quality, scope and its brightness L that the total light transmittance of the thickness 50 μ m sheet materials of being made by this resin combination is 15-60%
*meet following formula with the relation of transparence:
1300≤(L
*×B)≤4000
L
*for the brightness of the thickness 3mm sheet material made by above-mentioned resin combination, B is above-mentioned total light transmittance %.
9. the resin combination of claim 8, this resin combination contains filler.
10. the resin combination of claim 8, wherein, thermoplastic resin composition be take polyolefine as main component.
The resin combination of 11. claims 8, wherein, the sheet material of being made by resin combination shows more than 55 whiteness.
The resin combination of 12. claims 8, the sheet material of being made by this resin combination use L
*the brightness representing is in the scope of 55-90.
The resin combination of 13. claims 8, wherein, black pigment is iron black.
14. white resin products formeds, this white resin products formed is by the granular, white resin combination heating and melting of claim 8, then obtained by molding.
15. synthetic resins for automobile, this synthetic resin is by the granular, white resin combination heating and melting of claim 8, then obtained by molding.
Applications Claiming Priority (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP119016/2005 | 2005-04-15 | ||
| JP2005119018A JP4877569B2 (en) | 2005-04-15 | 2005-04-15 | Granular chromatic resin composition |
| JP2005119017A JP5051489B2 (en) | 2005-04-15 | 2005-04-15 | Granular white resin composition |
| JP119017/2005 | 2005-04-15 | ||
| JP119018/2005 | 2005-04-15 | ||
| JP2005119016A JP4870380B2 (en) | 2005-04-15 | 2005-04-15 | Granular white resin composition |
| PCT/JP2006/308074 WO2006112444A1 (en) | 2005-04-15 | 2006-04-17 | Particulate chromatic resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101198656A CN101198656A (en) | 2008-06-11 |
| CN101198656B true CN101198656B (en) | 2014-09-24 |
Family
ID=37467671
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200680021052.0A Expired - Fee Related CN101198656B (en) | 2005-04-15 | 2006-04-17 | Granular white resin composition |
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|---|---|
| JP (1) | JP4870380B2 (en) |
| CN (1) | CN101198656B (en) |
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| JP5536579B2 (en) * | 2010-07-23 | 2014-07-02 | ダイハツ工業株式会社 | Automotive seat member and resin composition for producing the sheet member |
| EP2692793B1 (en) * | 2011-03-31 | 2016-09-14 | UBE Industries, Ltd. | Polyolefin resin composition molded body having high scratch resistance |
| CN105153540A (en) * | 2015-08-31 | 2015-12-16 | 苏州莱特复合材料有限公司 | Car bumper composite material and preparation method thereof |
| WO2024135737A1 (en) * | 2022-12-21 | 2024-06-27 | Ｍｃｐｐイノベーション合同会社 | Airbag storage cover and thermoplastic elastomer composition for airbag storage cover |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1201712A1 (en) * | 2000-02-17 | 2002-05-02 | High Tech Chem Co., Ltd. | Colored resin composition for water pipe and colored water pipe |
| WO2003095531A1 (en) * | 2002-05-09 | 2003-11-20 | Ube Industries, Ltd. | Method for reusing crushed synthetic resin product |
| CN1529833A (en) * | 2001-05-15 | 2004-09-15 | 昭和电工株式会社 | Photosensitive coloring composition, colour filter using said composition and production method thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3907581A (en) * | 1972-03-23 | 1975-09-23 | Du Pont | Opalescent TiO{HD 2{B -containing compositions |
| JP2000169664A (en) * | 1998-12-04 | 2000-06-20 | Dainichiseika Color & Chem Mfg Co Ltd | Polypropylene coloring composition excellent in color development stability |
| JP4254280B2 (en) * | 2003-03-14 | 2009-04-15 | 東洋インキ製造株式会社 | Master batch for polypropylene resin and its use |
| CN1894341B (en) * | 2003-10-17 | 2011-09-14 | 宇部兴产株式会社 | Reclaimed resin composition produced from pulverized waste plastic material containing solid foreign materials |
-
2005
- 2005-04-15 JP JP2005119016A patent/JP4870380B2/en not_active Expired - Fee Related
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2006
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1201712A1 (en) * | 2000-02-17 | 2002-05-02 | High Tech Chem Co., Ltd. | Colored resin composition for water pipe and colored water pipe |
| CN1529833A (en) * | 2001-05-15 | 2004-09-15 | 昭和电工株式会社 | Photosensitive coloring composition, colour filter using said composition and production method thereof |
| WO2003095531A1 (en) * | 2002-05-09 | 2003-11-20 | Ube Industries, Ltd. | Method for reusing crushed synthetic resin product |
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| Publication number | Publication date |
|---|---|
| JP4870380B2 (en) | 2012-02-08 |
| JP2006298981A (en) | 2006-11-02 |
| CN101198656A (en) | 2008-06-11 |
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