CN1235927C - Polyacrylonitrile polymer fine particles - Google Patents
Polyacrylonitrile polymer fine particles Download PDFInfo
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- CN1235927C CN1235927C CNB021540543A CN02154054A CN1235927C CN 1235927 C CN1235927 C CN 1235927C CN B021540543 A CNB021540543 A CN B021540543A CN 02154054 A CN02154054 A CN 02154054A CN 1235927 C CN1235927 C CN 1235927C
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
- C08J3/14—Powdering or granulating by precipitation from solutions
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/42—Nitriles
- C08F20/44—Acrylonitrile
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/18—Homopolymers or copolymers of nitriles
- C09D133/20—Homopolymers or copolymers of acrylonitrile
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/18—Homopolymers or copolymers of nitriles
- C08J2333/20—Homopolymers or copolymers of acrylonitrile
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/18—Homopolymers or copolymers of nitriles
- C08L33/20—Homopolymers or copolymers of acrylonitrile
Abstract
To provide fine particles of a polyacrylonitrile based polymer useful as an additive for paints mainly for the purpose of improving decorative characteristics such as matte effect. There are provided fine particles of a polyacrylonitrile based polymer in which acrylonitrile is copolymerized in an amount of 80 wt.% or more, an average particle size is 3-200 mu m, a spherical degree is 30-90 and an intra-particle porosity is 0.1-0.4; a paint composition obtained by mixing the above polymer fine particles in an amount of 1-60 wt.% relative to a sold content of a paint; and a paint film having improved decorative characteristics and/or a resistance to weather obtained by applying and baking the said paint composition.
Description
Technical field
The present invention relates to mainly that to represent the aesthetic property of extinction effect or give weathering resistance be purpose to improve, be suitable for the polyacrylonitrile based polymer particles of paint additive and contain the coating composition of this particulate and by filming that said composition makes.
Background technology
The generalized aesthetic property that comprises delustring with raising with in the coating composition, is generally wanted the particulate of the organic or inorganic of mixed number micron～hundreds of microns as the internal and external ornament of purpose.(is that oil system, fragrant family, alcohol system, ester are, ketone is organic solvent in the general coating composition in order to make these particulates at the contained solvent of coating composition, in the aqueous coating composition water, do not contain solvent in the powder coating composition) in do not dissolve (in powder coating composition, melting), and also must be present in the surface after the formation of filming, therefore, the general employing with the suspension polymerization of cross-linkable monomer copolymerization or seeding polymerization of organic fine particles made.Inorganic particles generally can use silicon oxide particle, ferric oxide, titanium oxide etc.
Mix this particulate and find that its reason that improves aesthetic properties such as delustring mainly is because as principal elements such as the refringence of the coating of base-material and this particulate, tonal differences, otherwise, composition by changing particulate, median size, size-grade distribution, particle shape, tone etc. in theory might the wide aesthetic properties of expression range.
Yet, the organic fine particles that suspension polymerization at present or seeding polymerization are made, its specific refractory power does not have big difference with coating as base-material, and particle shape generally is a spheroidal.In order to bring into play aesthetic property, compare with the inorganic particulate of silicon oxide etc., must improve blend level to coating composition.On the other hand, inorganic particles such as silicon oxide owing to generally be organic compound as the coating of base-material, with the poor adhesion that is coated with film component, be easy to generate and make the weathering resistance of filming or the shortcoming of clagging deterioration.Like this, still, can not provide has adhesivity with coating and just gives aesthetic property or satisfy the particulate of weathering resistance in coating composition by mixed with little amount.
Summary of the invention
In order to solve aforementioned problems, the present invention is made up of following constituting.That is, a kind of polyacrylonitrile based polymer particles is characterized in that, contain more than the vinyl cyanide 80 weight %, and median size is that 3～200 microns, spherical degree are 30～90, particle internal pore rate is 0.1～0.4.The polymkeric substance that the monomer more than a kind of acrylate, methacrylic ester, vinylbenzene, vinyl acetate, glycidyl methacrylate, methacrylic acid 2-glycidyl ester, Vinylstyrene, polyethylene glycol dimethacrylate (n=1～9) carries out copolymerization is recommended and be selected to this polymer particles.The more preferably polyacrylonitrile based polymer particles of the swelling capacity less than 10 volume % in oil system, fragrant family, pure series solvent.The present invention also comprises in addition, and mixed phase is for the coating composition of this particulate 1～60 weight % of the solid formation branch in the coating composition, and raising is with this coating composition coating, the aesthetic property of baking back formation and/or filming of weathering resistance.
The embodiment of invention
The chemical constitution of polymer particles of the present invention must contain more than the vinyl cyanide 80 weight %.During the copolymerization ratio less than 80 weight % of vinyl cyanide and since its in coating composition general use as the oil system of dispersion medium, fragrant family, alcohol system, ester be, ketone is swelling or dissolving and be not used in the organic solvent.
If copolymerization ratio less than 20 weight % can be used as comonomer with the various monomers of acrylonitrile compolymer and use.Wherein preferred and the monomer copolymerization more than a kind that is selected from acrylate, methacrylic ester, vinylbenzene, vinyl acetate between to for plastic, glycidyl methacrylate, methacrylic acid 2-glycidyl ester, Vinylstyrene, polyethylene glycol dimethacrylate (n=1～9).As ester with acrylate, methacrylic acid example, can enumerate it～methyl esters ,～ethyl ester ,～n-propyl ,～isopropyl ester ,～positive butyl ester ,～secondary butyl ester ,～tert-butyl ester ,～cyclohexyl ,～the 2-ethylhexyl ,～lauryl ,～stearyl ester etc.By selecting these comonomers or combined, can adjust the specific refractory power or the morphological character of particulate with polymerization process.
The necessary median size of polyacrylonitrile based polymer particles is that 3～200 microns, spherical degree are 30～90, particle internal pore rate is 0.1～0.4.The characterizing method of median size can be enumerated dimension criteria or number standard, and the present invention adopts volume as standard, uses the particle diameter that is converted into the ball particle.3 microns of median size less thaies and surpass 200 microns particulates are not used owing to can not improve the aesthetic property of the extinction effect of filming or aesthetical perception etc.Median size is more than 5 microns and when being lower than 25 microns, and the extinction effect of filming is very high.Can obtain to be rich in filming of aesthetical perception below 200 microns the time more than 25 microns.When surpassing 200 microns, then the additive use with respect to coating composition more likely uses as framework material, but the present invention does not adopt.
So-called spherical degree is the index of expression particulate form, is its major diameter of fine grain measurement and minor axis to any number of selecting at random under shining in the electron micrograph, with the value of following (formula 1) calculating.
Spherical degree=∑ (minor axis)/∑ (major diameter) * 100 (formula 1)
Therefore, spherical degree 100 expressions are balls.During spherical degree less than 30, the compressive strength of particulate adopts inadequately and not.In addition, spherical degree surpasses at 90 o'clock, owing to do not have difference basically with spherical shape, it is also little that aesthetic property improves effect, and the present invention does not adopt.
So-called particle internal pore rate is and the paired notion of inter-particle voids rate, in the environment of estimating particle internal pore rate, be that to be counted as 1 particulate be to have the one-level particle of the emptying aperture that is communicated with perforate or the secondary particle that middle solid one-level particle coacervation forms on the surface in expression, the substantial degree of this particle ... particularly, the index of representing the degree that departs from real density of this particulate matter.The evaluation of relevant particle internal pore rate is adopted " pharmaceutical journal " 88 (11) 1375～1382 (1968) described methods is done some amended methods.
That is, the sample particulate left standstill 1 day in 20 ℃ deionized water after, the sedimentation volume Vs (rice of per unit particulate weight when measuring sedimentation equilibrium
3/ kilogram), utilize (formula 2) to measure the relation of inter-particle voids rate ε ' (-) in particle internal pore rate ε (-) and the particle precipitation layer, or utilization is measured the up and down pressure difference Δ P (kilogram/rice of particle precipitation layer by the filtration experiment of the deionized water of aforementioned particles settled layer
2) and the filtration velocity Q (rice of the water by the particle precipitation layer
3/ second), obtain specific surface area Sw (rice with (formula 3)
2/ kilogram) with the relation of inter-particle voids rate ε '.Then, obtain the radius R (rice) of particulate median size of aftermentioned method actual measurement and the relation of specific surface area Sw and particle internal pore rate ε with (formula 4), because it is above to three unknown number (Sw, ε, ε ') three stand alone types is arranged, by with this as simultaneous equations, under the condition of 0≤ε＜1.0 (ε ' too), solve an equation, can obtain the particle internal pore rate ε that separates as numerical approximation.
ρ
2Vs=1/{ (1-ε) (1-ε ') (formula 2)
R=3/{ ρ
2(1-ε) Sw} (formula 4)
Vs: per unit particulate weight sedimentation volume V s (rice
3/ kilogram), its mensuration is, make dry weighing (the sample particle of * (kilogram) is dispersed in 20 ℃ the deionized water, move on to sectional area (A) (meter
2) pillar in, the height L (rice) by leaving standstill particle precipitation layer after 24 hours calculates with the calculating formula of Vs=A * L ÷ x.
The Δ P: (kilogram/rice of pressure difference up and down of particle precipitation layer in the filtration experiment
2), it is determined as, and at the pillar bottom connection traffic pressure warning unit that has formed the particle precipitation layer through the sample particulate of measuring above-mentioned sedimentation volume, the pressure warning unit height when attracting water with vent fan is calculated.
Q: the filtration velocity Q of water (rice by the particle precipitation layer in the filtration experiment
3/ second), it is determined as, the elution time of 2 milliliters to 7 milliliters initial filtrate when attracting water from the pillar bottom with aforesaid vent fan, promptly filter 5 milliliters time, and in the same pillar of the particle precipitation layer that does not have the sample particulate to form, only filter the difference of the time of 5 ml deionized water and calculate.
R: be assumed to the radius R (m) of spheric particulate, use by the equivalent footpath actual measurement of laser diffraction formula particle size measurement device, that represent with dimension criteria divided by 2 value.
ρ
2: expression constitutes the real density of the material of particulate, and polyacrylonitrile based particulate of the present invention uses 1180 kilograms/meter
3
η: the viscosity of expression medium, the value 1.005 * 10 of 20 ℃ of water of use
-7(kilogram/rice second).
G: expression universal gravity constant, use 9.8 (meter per seconds
2).
L: the height (rice) of expression particle precipitation layer.
A: the sectional area (rice of expression particle precipitation layer
2).This also is the sectional area of pillar.
During particle internal pore rate less than 0.1, the field of particulate and UA solid one-level particle is approaching, owing to there is not diffuse effect not bring into play the extinction of filming, can not realize the present invention.And particle internal pore rate surpasses at 0.4 o'clock, particulate compression intensity especially a little less than, coating strength is also not enough as a result, the present invention does not adopt.
As the manufacture method of the polyacrylonitrile based polymer particles of above explanation, can enumerate following method for making.As first method, can adopt the deionized water, the dispersion agent that in reactive tank, add specified amount, add the monomer that contains the vinyl cyanide that is dissolved with catalyzer again, make solution temperature be raised to 40～90 ℃ method while stirring.
As dispersion agent, can use nonionic is tensio-active agent, soluble celluloses such as polyvinyl alcohol or methylcellulose gum, Natvosol, carboxymethyl cellulose, the combination more than a kind or 2 kinds of polyacrylic acid, polymethyl acrylic acid etc.
As catalyzer, can enumerate 2,2 '-Diisopropyl azodicarboxylate, 2,2 '-azo two (2-methyl valeronitrile), 2,2 '-azo two (2, the 4-nitrile dimethyl), 2,2 '-azo two (the own nitrile of 2-methyl), 2,2 '-azo two (2,3,3-trimethylammonium butyronitrile), 2,2 '-azo two (2,4,4-trimethylammonium valeronitrile), 2,2 '-azo (2, the 4-methyl pentane nitrile), 2,2 '-azo two (2,4-dimethyl-4-oxyethyl group valeronitrile), 2,2 '-azo two (2,4-dimethyl-4-n-butoxy valeronitrile) azo series catalysts such as, or acetyl peroxide, the peroxidation propionyl, the peroxidation isobutyryl, the peroxidation decoyl, decanoyl peroxide, lauroyl peroxide, peroxidation 3,5, the 5-trimethyl acetyl, benzoyl peroxide, di-isopropyl peroxydicarbonate, peroxidation two acyls such as peroxy dicarbonate two-2-ethylhexyl, the peroxidation tert-butyl isobutyrate, the peroxidation trimethylacetic acid tert-butyl ester, the new dodecylic acid tert-butyl ester of peroxidation, lipophilicity catalyzer such as peroxyester such as peroxidation lauric acid uncle butyric acid.
In addition, for stop aqueous phase the molten monomer polymerization of depositing, can mix water-soluble salts such as Sodium Nitrite, copper sulfate, iron(ic) chloride or water-soluble stopper (for example Sumitomo Chemical system ス ミ ラ イ ザ-BHT etc.).
As the 2nd kind of method, can adopt the deionized water that adds specified amount and add dispersion agent as required, make solution temperature be raised to 40～90 ℃ while stirring, restir, limit keep the temperature limit to add the method for the monomer and the catalyzer that contain vinyl cyanide simultaneously concurrently continuously.
With above-mentioned same, it is tensio-active agent that dispersion agent uses nonionic, soluble celluloses such as polyvinyl alcohol or methylcellulose gum, Natvosol, carboxymethyl cellulose, polyacrylic acid, polymethyl acrylic acid etc. a kind or with the combination more than 2 kinds, perhaps form and do not use also passable fully according to the monomer that contains vinyl cyanide.
Catalyzer can be enumerated oxidative catalysts such as ammonium persulphate, Potassium Persulphate, or with acid S-WAT etc. and oxidative catalyst blended redox catalyst, the wetting ability catalyzer of azo series catalysts such as azo two valeric acids etc.
As everyone knows, general acrylonitrile compolymer is than the easy cohesion of high water system polymerization and be difficult to the control reaction, but in above-mentioned each method, by experiment property ground select vinyl cyanide copolymerization ratio, with the monomeric selection of acrylonitrile compolymer, contain the monomer of vinyl cyanide with to the ratio of reactive tank inlet amount, the whipped state of reactive tank, the selection of selection of catalysts, dispersion agent, also has the combination of polymerization temperature etc., can obtain to have the median size of purpose, spherical degree, the particulate of particle internal pore rate.
The polyacrylonitrile based polymer particles of aforesaid method manufacturing is the state that is dispersed in the water, but also can extract as solid powder by solid-liquid separation, drying, fractionated operation.In addition, in aqueous coating composition etc., mix when using, also can not carry out solid-liquid separation and directly use.In addition, when adjusting median size, also can be by breaking methods such as mechanical type, air-flowing type, wet types.
Particulate of the present invention uses by mixing in existing coating composition, brings into play the action effect that it has ... especially aesthetic property or weathering resistance.Yet in order to give full play to its action effect, preferably this particulate specifically, has the swelling capacity of less than 10 volume % to having solvent resistance as normal oil system, fragrant family, the pure series solvent that uses of coating composition composition.This is because particulate of the present invention is blended in the coating composition; because arriving different its degree of swelling of elapsed time that form of filming according to purposes might be different, when covering with paint, lacquer, colour wash, etc. since the speed of desolventizing difference use different swelling capacity fix or and coating and other additives between adhesivity variation etc.; the stability of aesthetic property appears in influence; the perhaps viscosity of the coating composition thickness that changes and to obtain stipulating because of degree of swelling; perhaps coating composition produces caking etc., the cause that user's operation might worsen.Vinyl cyanide be the above height of 80 weight % contain rate particulate of the present invention because water tolerance is very good, do not produce such problem in the aqueous coating composition.
Polyacrylonitrile based polymer particles of the present invention mixes with 1～60 weight %, preferred 5～50 weight % with respect to the solids component in the said composition in coating composition, becomes and can give aesthetic property or the good coating composition of filming of weathering resistance.During blended quantity not sufficient 1 weight %, enough effects do not appear on filming, when surpassing 60 weight %, sometimes at the shelf-stability of composition self or film and the aspects such as adhesivity that are coated with jewelry have problems.Then, said composition can obtain aesthetic property and/or filming of having excellent weather resistance through coating, baking.As the object coating composition, no matter be that water system, solvent system all can use.In addition, even polyacrylonitrile based polymer particles of the present invention is also insoluble because of being heated to about 200 ℃, so might use as the additive of powder coating.As covering with paint, lacquer, colour wash, etc. subject material, timber such as resin board, veneer sheet, glued board such as the metal foil that can enumerate that cold-rolled steel sheet, aluminium sheet, zinc and zinc system electroplates etc., ABS, particulate of the present invention is owing to there is high vinyl cyanide to contain rate, has the effect that the weather resisteant of filming is improved especially, from then on, be suitable for roof Material, the purposes of aspects such as outer wall building materials.
[embodiment]
Below, be described more specifically the present invention by representational embodiment and comparative example, but the present invention is not limited to these embodiment.In addition, the part described in the following embodiment, short of specified otherwise then is a weight part, % is a weight percent.Method below each assessment item among the embodiment adopts is measured and is judged.
[median size (micron)]
Make this material microparticulate in 20 ℃ deionized water, with laser diffraction formula particle size measurement device (the system SALD2000 of Shimadzu Seisakusho Ltd.), specific refractory power 1.60～0.10i directly is defined as median size (micron) to the equivalent of standard test by volume, calculating.
[spherical degree (-)]
Measure its major diameters, minor axis, calculate for any 20 to the sample particulate under shining in electron microscope (SEM) photo with aforesaid (formula 1).
[particle internal pore rate (-)]
In 16.5 millimeters of diameters, long 1 meter glass pillar with 20 ℃ deionized water as dispersion medium, to the sample particulate of sedimentation equilibrium, adopt the method described in " pharmaceutical journal " 88 (11) 1375～1382 (1968) is estimated as the amended method of having stated.The pressure difference Δ P up and down, water that measures per unit particulate weight sedimentation volume V s, particle precipitation layer thus by the particle precipitation layer filtration velocity Q and by the median size 2R of aforesaid method actual measurement, employing (formula 2)～(formula 4) calculated particle internal pore rate.
[swelling capacity (volume %)]
In 25 milliliters of graduated cylinders, add about 20 milliliters of solvent under the normal temperature, add sample particulate 3～5 grams again and make it sedimentation, measure the i.e. particle volume of solvent swelling state not of firm sedimentation.
Be determined at the volume after 1 week of placement under the normal temperature again, calculate with (formula 5).Swelling capacity (volume %)={ (placed 1 week after particle volume/(firm settled particle volume)-1) } * 100 (formulas 5)
As solvent types, alcohol system uses Virahol, and oil system uses pimelinketone, Selvesso 150 (a kind of high solvent of aromatic hydrocarbons amount that contains), and fragrant family uses dimethylbenzene (Solvesso150 is go-De-solvent system, and other are 1 grade of reagent)
[extinction]
Aesthetic property is estimated with the extinction of filming.Promptly 2 parts of recombined sample particulates in Northwest coating system varnish colour composition (painted carbon black) 40 parts (nonvolatile component 50%) are coated on the steel plate galvanized with 200 microns spreading device of thin-layer, 70 ℃ of bakings 60 minutes.The extinction of this steel plate that formation is filmed is estimated with the glossiness that angle 60 is spent with Grossmeters (hole field system IG-310) then.Numerical value more hangs down and more has extinction.As judgement criteria, the glossiness of extinction excellence be lower than 10 be designated as ◎, good be lower than more than 10 20 be designated as zero, bad being designated as more than 20 *.
[coating weatherability]
With Japanese NSC system tackiness agent (ョ De ゾ one Le AA-76), adopt the electrostatic applications method sample particulate 150g to be coated on the ABS resin plate of 5 * 12 centimeter square, 70 ℃ of bakings 30 minutes.Then, the test board that formation is filmed, with ultraviolet fadeometer (ス ガ test system FAL-AU type), under the environment of 63 ℃ of temperature, relative humidity 65%, handled 800 hours, with the variation of color colour-difference meter (Minolta system 74181007 types) evaluate color.It is higher that aberration changes (Δ E) the little weathering resistance that heals.As judgement criteria, the Δ E that has excellent weather resistance is lower than 2 and is designated as ◎, good is designated as zero being lower than 5 more than 2, bad being designated as more than 5 *.
＜embodiment 1 〉
(1) the polyacrylonitrile based polymer particles is synthetic
The aqueous solution of 7 parts of dissolve polyvinyl alcohols (Network ラ レ makes PVA217), 10 parts in sodium sulfate, 1 part in copper sulfate 5 hydrates in 831 parts of the deionized waters is added in the glass reactive tank.Then, being dissolved with as 135 parts of monomeric vinyl cyanide, 15 parts of vinylbenzene, as 135 parts of the monomeric vinyl cyanide of catalysis, 15 parts of vinylbenzene, as 2 of catalyzer, the solution that 2 '-azo two (2-methyl valeronitrile) is 1 part adds in the reactive tank, make solution temperature be raised to 50 ℃ while stirring, keep 5 hours these temperature, make the water dispersion of polyacrylonitrile based polymer particles of the present invention.
(2) taking-up of polyacrylonitrile based polymer particles
With the qualitative filter paper of No.5C the water dispersion of polyacrylonitrile based polymer particles is carried out solid-liquid separation.The filter cake that obtains is dispersed in a large amount of deionized waters,, removes unreacted monomer or dispersion agent by adopting the solid-liquid separation of method same as described above repeatedly.Be dried to constant with 70 ℃ hot air dryer then, the standard sieve classification with 70 orders (210 microns of sieve apertures) obtains polyacrylonitrile based polymer particles of the present invention.
＜embodiment 2 〉
(1) the polyacrylonitrile based polymer particles is synthetic
The aqueous solution of 3 parts of Natvosols of dissolving, 20 parts of sodium polyacrylates, 10 parts in sodium sulfate, 1 part in copper sulfate 5 hydrates in 815 parts of the deionized waters is added in the glass reactive tank.Then, being dissolved with as 120 parts of monomeric vinyl cyanide, 24 parts of methyl methacrylates, 6 parts of ethylene glycol dimethacrylates, being added in the reactive tank as the solution of 1 part of the lauroyl peroxide of catalyzer, warming while stirring to 50 ℃, keep 5 hours these temperature, make the water dispersion of polyacrylonitrile based polymer particles of the present invention.
(2) taking-up of polyacrylonitrile based polymer particles
Carry out similarly to Example 1.
＜embodiment 3 〉
(1) the polyacrylonitrile based polymer particles is synthetic
The aqueous solution of 3 parts of Natvosols of dissolving, 10 parts of sodium polyacrylates, 10 parts in sodium sulfate, 1 part in copper sulfate 5 hydrates in 825 parts of the deionized waters is added in the reactive tank.Then, being dissolved with as 135 parts of monomeric vinyl cyanide, 10.5 parts of vinylbenzene, 4.5 parts of divinylbenzenes, adding in the reactive tank as the solution of 1 part of the lauroyl peroxide of catalyzer, make solution temperature be raised to 50 ℃ while stirring, keep 5 hours these temperature, make the water dispersion of polyacrylonitrile based polymer particles of the present invention.
(2) taking-up of polyacrylonitrile based polymer particles
Carry out similarly to Example 1.
＜embodiment 4 〉
(1) the polyacrylonitrile based polymer particles is synthetic
Except 4.5 parts of 10.5 parts of 135 parts of vinyl cyanide, the vinylbenzene, the Vinylstyrenes that replace embodiment 3 with 7.5 parts of 142.5 parts of vinyl cyanide, vinylbenzene, other adopt method similarly to Example 3 to synthesize.
(2) taking-up of polyacrylonitrile based polymer particles
Carry out similarly to Example 1.
＜embodiment 5 〉
(1) the polyacrylonitrile based polymer particles is synthetic
600 parts of deionized waters are added in the glass reactive tank, make temperature be raised to 60 ℃ while stirring.Under agitation 200 parts of vinyl cyanide, 100 parts of 0.5% sodium persulfate aqueous solutions, 100 parts of whiles of 0.5% aqueous solution of sodium bisulfite were added continuously in this reactive tank with 2 hours concurrently then, keep temperature again 2 hours when adding end, make the water dispersion of polyacrylonitrile based polymer particles of the present invention.
(2) taking-up of polyacrylonitrile based polymer particles
Carry out similarly to Example 1.
＜embodiment 6 〉
(1) the polyacrylonitrile based polymer particles is synthetic
Except 200 parts of the vinyl cyanide that replace embodiment 5 with 6 parts of 170 parts of vinyl cyanide, 24 parts of vinyl acetate between to for plastics, glycidyl methacrylate, other synthesize with method similarly to Example 5.
(2) taking-up of polyacrylonitrile based polymer particles
Carry out similarly to Example 1.
＜embodiment 7 〉
(1) the polyacrylonitrile based polymer particles is synthetic
The aqueous solution of 3 parts of Natvosols of dissolving, 10 parts of sodium polyacrylates, 10 parts in sodium sulfate, 1 part in copper sulfate 5 hydrates in 825 parts of the deionized waters is added in the polyethylene container made.Then dissolving as 142.5 parts of monomeric vinyl cyanide, 7.5 parts of vinylbenzene, add in this container as the solution of 1 part of the lauroyl peroxide of catalyzer, with vibrating disk (cold chemical industry system: the VD-H100-08 type) made solution circulated 30 minutes, become monomer suspension.Then this suspension is moved on in the glass reactive tank, make liquid temp be raised to 50 ℃ while stirring, kept this temperature 5 hours, make the water dispersion of polyacrylonitrile based polymer particles of the present invention.
(2) taking-up of polyacrylonitrile based polymer particles
Carry out similarly to Example 1.
＜embodiment 8 〉
(1) the polyacrylonitrile based polymer particles is synthetic
Carry out similarly to Example 5.
(2) taking-up of polyacrylonitrile based polymer particles
Make dry particles similarly to Example 1.This particulate use again jet mill (セ イ シ Application enterprise system STJ-200 type) pulverize, with the standard sieve classification of 400 orders (37 microns of sieve apertures), make polyacrylonitrile based polymer particles of the present invention.
＜comparative example 1 〉
(1) the polyacrylonitrile based polymer particles is synthetic
Except 135 parts of vinyl cyanide replacing embodiment 1 with 45 parts of 105 parts of vinyl cyanide, methyl methacrylate, vinylbenzene 15 especially, it is synthetic that other adopt similarly to Example 1 method attempting, the result has to one condensation product.
＜comparative example 2 〉
(1) polymethylmethacrylate based polymer particulate is synthetic
Except 15 parts of 135 parts of the vinyl cyanide, the vinylbenzene that replace embodiment 1 with 15 parts of 135 parts of methyl methacrylates, ethylene glycol dimethacrylate, other synthesize with method similarly to Example 1.
(2) taking-up of polymethylmethacrylate based polymer particulate
Carry out similarly to Example 1.
＜comparative example 3 〉
(1) the polyacrylonitrile based polymer particles is synthetic
Except 200 parts of the vinyl cyanide that replace embodiment 5 with 60 parts of 140 parts of vinyl cyanide, methyl acrylate, other adopt method similarly to Example 5 to synthesize.
(2) taking-up of polyacrylonitrile based polymer particles
Carry out similarly to Example 1.
＜comparative example 4 〉
(1) the polyacrylonitrile based polymer particles is synthetic
The aqueous solution of 10 parts of dissolve polyvinyl alcohols (Network ラ レ makes PVA217), 10 parts in sodium sulfate, 1 part in copper sulfate 5 hydrates in 778 parts of the deionized waters is added in the glass reactive tank, then dissolving as 160 parts of monomeric vinyl cyanide, 40 parts of methyl methacrylates, as 2 of catalyzer, the solution that 2 '-azo two (2-methyl valeronitrile) is 2 parts adds in the reactive tank, make liquid temperature rise to 50 ℃ while stirring, keep temperature 5 hours, and made the water dispersion of polyacrylonitrile based polymer particles.
(2) taking-up of polyacrylonitrile based polymer particles
Carry out similarly to Example 1.
＜comparative example 5 〉
(1) the polyacrylonitrile based polymer particles is synthetic
Carry out similarly to Example 5.
(2) taking-up of polyacrylonitrile based polymer particles
Make dry particles similarly to Example 1.This particulate uses vertical mill (mill heavy industry system SH-75 type is broadcast on the Ishikawa island) to pulverize again, and the standard sieve classification with 400 orders (37 microns of sieve apertures) makes the polyacrylonitrile based polymer particles.
＜comparative example 6 〉
Buying commercially available silicon dioxide microparticle (the シ リ シ ア of Fuji chemistry system サ イ ロ イ De 74) estimates spherical degree etc.
To the above-mentioned various particulates of making, estimate median size, spherical degree, particle internal pore rate, swelling capacity, extinction, coating weatherability.Result's conclusion is shown in table 1, table 2.Because the silicon dioxide microparticle of comparative example 6 is not dispersed in the water, only estimate spherical degree, swelling capacity, extinction, coating weatherability in addition, be shown in table 2 in the lump.
Table 1
| No. | Median size (μ m) | Spherical degree (-) | Particle internal pore rate (-) | Swelling capacity (volume %) | Glossiness (-) | Coating weatherability (Δ E) | Remarks | |||
| Virahol | Pimelinketone | solvesso 150 | Dimethylbenzene | |||||||
| Embodiment 1 | 56 | 70 | 0.158 | 1 | 2 | 9 | 5 | 11 ○ | 3.2 ○ | |
| Embodiment 2 | 61 | 85 | 0.345 | 1 | 0 | 8 | 3 | 13 ○ | 1.9 ○ | |
| Embodiment 3 | 25 | 75 | 0.182 | 0 | 0 | 5 | 3 | 10 ○ | 2.1 ○ | |
| Embodiment 4 | 190 | 40 | 0.204 | 0 | 0 | 4 | 4 | 19 ○ | 3.3 ○ | |
| Embodiment 5 | 36 | 76 | 0.140 | 0 | 1 | 3 | 2 | 9 ◎ | 1.1 ◎ | |
| Embodiment 6 | 103 | 61 | 0.276 | 1 | 2 | 8 | 5 | 18 ○ | 4.2 ○ | |
| Embodiment 7 | 5 | 52 | 0.198 | 1 | 1 | 2 | 4 | 8 ◎ | 1.8 ◎ | |
| Embodiment 8 | 9 | 38 | 0.162 | 0 | 1 | 4 | 1 | 5 ◎ | 1.2 ◎ | Embodiment 4 grinding and processing things |
Table 2
| No | Median size (μ m) | Spherical degree (-) | Particle internal pore rate (-) | Swelling capacity (volume %) | Glossiness (-) | Coating weatherability (Δ E) | Remarks | |||
| Virahol | Pimelinketone | Solvesso 150 | Dimethylbenzene | |||||||
| Comparative example 1 | ※2 | ※2 | ※2 | ※2 | ※2 | ※2 | ※2 | ※2 | ※2 | Can not obtain particle shape |
| Comparative example 2 | 95 | 96 | 0.009 | 8 | 10 | 1 | 42 | 27 × | 1.9 ◎ | |
| Comparative example 3 | 57 | 65 | 0.423 | 4 | 11 | 9 | 12 | 10 ○ | 3.4 ○ | |
| Comparative example 4 | 220 | 82 | 0.259 | 0 | 1 | 5 | 5 | 35 × | 2.9 ○ | |
| Comparative example 5 | 2 | 71 | 0.151 | 0 | 1 | 3 | 2 | 22 × | 1.7 ◎ | |
| Comparative example 6 | 3.5 ※1 | 53 | ※2 | 1 | 1 | 2 | 1 | 4 ◎ | 6.4 × | Commercially available silicon dioxide microparticle |
Up is measured value, and descending is evaluation result
※ 1: Directory Value, ※ 2: can not measure
Find out that by table 1, table 2 particulate of embodiments of the invention 1～8 can be given and bring into play filming of excellent function on extinction or coating weatherability, can conclude that especially coating weatherability is significantly better than the general inorganic particles (comparative example 6) that uses.
By contrast, median size is left the particulate of the comparative example 4,5 of recommended range, can not bring into play sufficient extinction, i.e. aesthetic property.In addition, do not contain the particulate (comparative example 2) of vinyl cyanide, though coating weatherability is good, the swelling capacity height can not obtain excellent coating composition.In addition, during the copolymerization ratio less than 80 weight % (comparative example 1,3) of vinyl cyanide, can not controlling polymers reaction, can not obtain particulate form, same reason particle internal pore rate is too low, the shortcoming that exists particle to be highly brittle can not reach the problem of invention.
Find out that by above explanation polyacrylonitrile based polymer particles of the present invention is to have as the aesthetic property of the desired height of coating composition additive and/or the particulate of weathering resistance characteristic.Therefore, no matter particulate of the present invention is added in the coating composition of water system, organic solvent system, powder system, all can be used for the covering with paint of various metal foils, resin board, timber etc.
Claims (5)
1. a polyacrylonitrile based polymer particles is characterized in that, contain more than the vinyl cyanide 80 weight %, and median size is 3～200 microns that spherical degree is 30～90, and particle internal pore rate is 0.1～0.4.
2. the described polyacrylonitrile based polymer particles of claim 1, it is characterized in that, be with the number of repeat unit that is selected from acrylate, methacrylic ester, vinylbenzene, vinyl acetate between to for plastic, glycidyl methacrylate, methacrylic acid 2-glycidyl ester, divinylbenzene, ethylene glycol be that the monomer copolymerization more than a kind of the polyethylene glycol dimethacrylate of 1-9 obtains.
3. claim 1 or 2 described polyacrylonitrile based polymer particles is characterized in that, the swelling capacity less than 10 volume % in oil system, fragrant family, pure series solvent.
4. a coating composition is characterized in that, with respect to the solids component in the coating composition, hybrid right requires each described polyacrylonitrile based polymer particles 1～60 weight % of 1～3.
5. film for one kind, it is to form after being coated with, being toasted by the described coating composition of claim 4, and aesthetic property and/or weathering resistance are improved.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002029323 | 2002-02-06 | ||
| JP2002029323A JP3978648B2 (en) | 2002-02-06 | 2002-02-06 | Polyacrylonitrile polymer fine particles |
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| CN1235927C true CN1235927C (en) | 2006-01-11 |
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| JP2009280751A (en) * | 2008-05-26 | 2009-12-03 | Nitto Denko Corp | Production method of porous polymer particle |
| WO2011078145A1 (en) | 2009-12-24 | 2011-06-30 | 東レ株式会社 | Carbon microparticle and process for production thereof |
| CN102108232B (en) * | 2009-12-25 | 2014-03-12 | 罗门哈斯公司 | Multiplayer coating system without titanium dioxide |
| JP6123156B2 (en) * | 2011-02-17 | 2017-05-10 | 日本エクスラン工業株式会社 | True spherical cross-linked polyacrylonitrile fine particles with large surface area |
| CN104559033B (en) * | 2014-12-31 | 2017-07-11 | 上海锦湖日丽塑料有限公司 | Low gloss heat-proof ABS resin composition and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5674157A (en) * | 1979-11-21 | 1981-06-19 | Nisshin Steel Co Ltd | Coating compound and metallic plate coated with it |
| JPS573867A (en) * | 1980-06-10 | 1982-01-09 | Nisshin Steel Co Ltd | Paint and metal plate coated with the same |
| JPS5819368A (en) * | 1981-07-29 | 1983-02-04 | Nisshin Steel Co Ltd | Coating with excellent weathering resistance |
| JPS61258810A (en) * | 1985-02-13 | 1986-11-17 | Mitsubishi Rayon Co Ltd | Acrylonitrile polymer fine powder and electrostatic recording medium |
| JPS6416812A (en) * | 1987-07-10 | 1989-01-20 | Japan Exlan Co Ltd | Polymer bead |
| JPH0260902A (en) * | 1988-08-25 | 1990-03-01 | Natoko Paint Kk | Production of spherical polymer particle |
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| CN1436800A (en) | 2003-08-20 |
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| KR100869996B1 (en) | 2008-11-24 |
| JP2003226720A (en) | 2003-08-12 |
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