CN100349801C - Surface-treated calcium carbonate, method for production thereof and resin composition comprising said calcium carbonate - Google Patents
Surface-treated calcium carbonate, method for production thereof and resin composition comprising said calcium carbonate Download PDFInfo
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Abstract
A surface-treated calcium carbonate, characterized in that it comprises calcium carbonate surface-treated with an organic agent for surface treatment, and has respective specific ranges of values for a BET specific surface area (Sw), a weight reduction by heat per unit specific surface area (As), an average pore diameter (Dxp) at which an increase in mercury penetration takes a maximum value in a specific range of pore diameter distribution by the mercury porosimetry, and an amount of the average pore diameter [a maximum value of the increase in mercury penetration (Dyp)/ an average pore diameter (Dxp)] and a method for producing the calcium carbonate which comprises adding a complex-forming material to a calcium hydroxide slurry, followed by blowing a carbon dioxide gas, to synthesize calcium carbonate, adjusting a calcium carbonate concentration, followed by aging, and treating the surface of the product with an organic agent for surface treatment. The surface-treated calcium carbonate is useful especially for a resin and can be used for producing a resin composition having improved adhesion to an article to be attached and forming a tough coating film.
Description
Technical field
The present invention relates to handle lime carbonate, its preparation method that forms and be mixed with the resin combination that this lime carbonate forms through the organic system surface treatment agent.More particularly, relate to through the organic system surface treatment agent and handle lime carbonate, its preparation method that forms and the resin combination that forms feature to mix this lime carbonate, described surface treated lime carbonate for example is being used for seal gum, when tackiness agent is the gel-type resin of representative, is provided to have viscosity, also have the resin combination that excellent seam is followed the trail of property (joint conformability) the thixotropy effect time; In the time of for example in being mixed into coating, printing ink, plastisol, provide not only have high gloss and high thixotropic, sag prevention, also can obtain the resin combination that high strength is filmed.
Background technology
Lime carbonate is widely used as the filler or the pigment of plastics, coating, printing ink, seal gum, tackiness agent, paper, rubber etc.For example, with regard to seal gum, be widely used in waterproof, sealing etc. in fields such as building, automobile, earth materials, also a lot of in the situation of vertical component construction, require certainly constructing not sagging of setting up period, need possess high viscosity, high thixotropic.
For solving above-mentioned problem, present inventors have proposed preparation method's (Japanese kokai publication hei 10-72215 number) of precipitated chalk, in recent years, and along with the further increase of demand, to the also further raising of requirement of physical properties.
For example, individual dwelling house aspect sharply increases the demand of wallboard, consider that the wallboard drying makes moist repeatedly and the activity of parts, can use the seal gum of low modulus, but it is flexible that wallboard will be produced by the influence of temperature, humidity, thereby require the seal gum butt seam to have tracking.For giving these features, all use colloidal calcium carbonate all the time, can reduce the modulus after the curing, improve in a way by the tracking of bur, meticulous adjusting viscosity, but for further regulate viscosity by reduction modulus, trace interpolation for, there is the limit in existing colloidal calcium carbonate, thereby wishes to develop finer polymolecularity material.
Coating, printing ink are from begin to use colloidal calcium carbonate a long time ago always.In recent years, need set 10 years duration of security such as assurance, so need the more excellent coating of weather resistance to coating.And, exist lime carbonate to reduce this problem always, thereby wish to reduce the combined amount of existing colloidal calcium carbonate and keep ink characteristics with the different transparencys of printing ink that cause of specific refractory power between the printing ink vehicle for printing ink.
In addition,,, used wollastonite, needle-like calcium carbonate for the weld line strength that prevents injection moulding machine is low for plastics, but the both be tens of micron to 200 microns, particle diameter is bigger, thereby causes the problem that shock strength is low.The intensity that existing colloidal calcium carbonate is difficult to suppress welded bonds is low, shock strength is low.
And, in plastisol,, use vinyl chloride-based resin in a large number particularly as body of a motor car usefulness, in recent years, based on the consideration of environment aspect, studying with acrylic resin is that material is as its surrogate.Particularly in acrylic resin system, not only from weight reduction, but also consider and the price difference of vinyl chloride resin system, inquiring into and be made into film, this need add the weighting agent that can give high viscosity on a small quantity, but existing colloidal calcium carbonate can not satisfy these requirements.
The present invention is in view of above-mentioned practical situation, provide through the organic system surface treatment agent and handle lime carbonate, its preparation method form and be mixed with this lime carbonate and the resin combination that forms, described surface treated lime carbonate for example is being used for seal gum, when tackiness agent is the gel-type resin of representative, except that having viscosity, thixotropic effect, follow the trail of property but also have seam; When in for example coating, printing ink, plastisol, using, have high gloss, excellent sag prevention, high coating strength; When in plastics for example, using, can prevent that the intensity of welded bonds face is low, also can obtain to have the resin combination of good impact strength, and can come weight reduction by the addition that reduces in resin.
Present inventors are for solving above-mentioned problem, further investigate, found that: after adding special material and carrying out carbonation reaction, the material that carries out obtaining after the slaking under specific concentrations is the precipitated chalk with specific fine property and good dispersion, by organic system surface treatment agent this lime carbonate is carried out surface treatment, can improve by the cohesive force of bur, improve formed intensity of filming self with specified quantitative, thereby address the above problem a little, finished the present invention.
Summary of the invention
That is, the content of a first aspect of the present invention is a surface treatment lime carbonate, it is characterized in that: satisfy following formula (a) and (b), (c) and (d) through the surface-treated lime carbonate of organic system surface treatment agent.
(a)20≤Sw≤200 (m
2/g)
(b)1.0≤As≤7.5 (mg/m
2)
(c)0.003≤Dxp≤0.03(μm)
(d)50≤Dyp/Dxp≤180
Wherein
Sw: by the BET specific surface area (m of determination of nitrogen adsorption
2/ g)
As: the hot decrement (mg/m of the per unit specific surface area of calculating by following formula
2) (every 1g is through the hot decrement mg/g of 200 ℃ of-500 ℃ of surface-treated lime carbonate)/Sw
Dxp: in the mercury penetration method, during micropore in the scope of range of micropores 0.001-0.1 μ m distributed, mercury was pressed into increment (accumulation (Plot calculates) the average micro-pore diameter of micropore volume increment/log) average micro-pore diameter (μ m) during for maximum value (Dyp)
Dyp: mercury is pressed into the maximum value (mg/l) of increment
Dyp/Dxp: average micropore mass runoff
The content of a second aspect of the present invention is a surface treatment lime carbonate, it is characterized in that: satisfy following formula (a) and (b), (e) and (f) through the surface-treated lime carbonate of organic system surface treatment agent.
(a)20≤Sw≤200 (m
2/g)
(b)1.0≤As≤7.5 (mg/m
2)
(e)0.03≤Dxs≤1 (μm)
(f) Dys≤30 (% weight)
Wherein
Sw: by the BET specific surface area (m of determination of nitrogen adsorption
2/ g)
As: the hot decrement (mg/m of the per unit specific surface area of calculating by following formula
2) (every 1g is through the hot decrement mg/g of 200 ℃ of-500 ℃ of surface-treated lime carbonate)/Sw
Dxs: (Shimadzu Seisakusho Ltd. makes laser-diffractometer: SALD-2000) in the size-grade distribution of Ce Dinging, start at the median size (μ m) of weight accumulative total 50% from big particle side
Dys: in the above-mentioned size-grade distribution, surpass the weight accumulative total (% weight) of the particle diameter of 3 μ m
The content of a third aspect of the present invention is a surface treatment lime carbonate, it is characterized in that: by constituting with the surface-treated lime carbonate of organic system surface treatment agent, satisfy following formula (a)-(f).
(a)20≤Sw≤200 (m
2/g)
(b)1.0≤As≤7.5 (mg/m
2)
(c)0.003≤Dxp≤0.03(μm)
(d)50≤Dyp/Dxp≤180
(e)0.03≤Dxs≤1 (μm)
(f) Dys≤30 (% weight)
Wherein
Sw: by the BET specific surface area (m of determination of nitrogen adsorption
2/ g)
As: the hot decrement (mg/m of the per unit specific surface area of calculating by following formula
2) (every 1g is through the hot decrement mg/g of 200 ℃ of-500 ℃ of surface-treated lime carbonate)/Sw
Dxp: in the mercury penetration method, during the micropore in the scope of range of micropores 0.001-0.1 μ m distributes, the average micro-pore diameter (μ m) when mercury is pressed into increment (the average micro-pore diameter of accumulation micropore volume increment/log) for maximum value (Dyp)
Dyp: mercury is pressed into the maximum value (mg/l) of increment
Dyp/Dxp: average micropore mass runoff
Dxs: (Shimadzu Seisakusho Ltd. makes laser-diffractometer: SALD-2000) in the size-grade distribution of Ce Dinging, start at the median size (μ m) of weight accumulative total 50% from big particle side
Dys: in the above-mentioned size-grade distribution, the content of weight accumulative total (% weight) a fourth aspect of the present invention that surpasses the particle diameter of 3 μ m is the preparation method of surface treatment lime carbonate, it is characterized in that: the material of 0.5-15% weight and metallic ion coordination formation complex compound is added in the calcium hydroxide slurry, carry out carbonation reaction by being blown into carbon dioxide, synthetic calcium carbonate, with this lime carbonate concentration adjustment to 2.4-13.0% weight, slaking is carried out surface treatment with the lime carbonate of gained with the organic system surface treatment agent.
The content of a fifth aspect of the present invention is a resin combination, it is characterized in that: above-mentioned surface treated lime carbonate is mixed into resin and forms.
The best mode that carries out an invention
Below detailed content of the present invention is specifically described.
(a) formula is by the BET specific surface area of the surface treated lime carbonate of the present invention of determination of nitrogen adsorption, requires to be 20-200m
2/ g.This specific surface area is less than 20m
2During/g, be difficult to have the object of the invention place-high viscosity.And above 200m
2During/g, though preferred because of the primary particle pettiness, stability is variation in time, and problem also takes place in dispersed aspect.Thereby, preferred 30-150m
2/ g, more preferably 40-120m
2/ g.
In addition, as the device that is used to measure the BET specific surface area, use the NOVA2000 type of Yuasa Ionics company.
(b) formula is the required organic system surface treatment dosage of per unit specific surface area of surface treated lime carbonate of the present invention, and requiring the organic system surface treatment amount As of per unit specific surface area is 1.0-7.5mg/m
2In existing lime carbonate, there are a lot of very thin lime carbonate of primary particle that satisfy (a) formula to sell on the market, but the primary particles aggregate of these lime carbonate forms secondary particle, the further each other aggegation of secondary particle forms three grades of particles, thereby the surface treatment treatment capacity of covering lime carbonate is less than 1.0mg/m
2Be sufficient treatment capacity, but lime carbonate of the present invention compares with existing lime carbonate, three grades of particles form things seldom, and secondary particle forms the dispersed high of thing, thereby is difficult to abundant covering surfaces.So when promptly carrying out drying, powdered under the insufficient situation of treatment capacity, being untreated forms three grades of aggegations between the face, thereby can not give full play to the effect of this surface treated lime carbonate.And above 7.5mg/m
2The time, because surface treatment agent is too much, cause that surface treatment agent is free in resinous principle or plasticizer component, become and ooze the reason of moving phenomenon, surface irregularity phenomenon.Therefore, preferred 1.5-5.0mg/m
2, more preferably 2.0-4.0mg/m
2
Following the trying to achieve of hot decrement of per unit specific surface area: with the TG-8110 type of リ ガ Network society manufacturing, get on the test portion dish (platinum system) that the surface treated lime carbonate of about 100mg places diameter 10mm, heat-up rate with 15 ℃/minute, hot decrement till measuring 200-500 ℃, obtain the hot reduction rate (mg/g) of the surface treated lime carbonate of every 1g, remove this value with BET specific surface area value.
(c) formula and (d) formula become the index of the dispersion state of knowing surface treated lime carbonate of the present invention.
(c) formula is in the micropore distribution in the 0.001-0.1 mu m range of measuring with mercury penetration method (porosimeter), and the average micro-pore diameter (Dxp) when mercury is pressed into increment and is maximum value (Dyp) is represented the fineness in the gap between surface treated calcium carbonate granule.Therefore, it is not a particulate fineness shown in (nitrogen) gas adsorption method of expression (a) formula, but the mean distance in the gap of expression between primary granule requires the m into 0.003-0.03 μ.When on average micropore diameter is less than 0.003 μ m, because primary particle or secondary particle are too thin, the problem that stability changes in time appears.And surpass 0.03 μ m, and then primary particle is too big, and the secondary particle that perhaps exists the strong aggegation of primary particle to form in a large number forms thing, can not get the high viscosity physical properties at the object of the invention place.Thereby, preferred 0.005-0.025 μ m, more preferably 0.006-0.020 μ m.
In addition, mercury is pressed into increment and is meant the micropore volume increment, with calculating formula (the average micro-pore diameter of accumulation micropore volume increment/log) expression (unit: ml/g).Certainly, because micro-pore diameter is more little, micropore volume is just more little, depends on micro-pore diameter so maximum mercury is pressed into increment (Dyp).
(d) formula is represented the number of the average micro-pore diameter of (c) formula, is the index of indication as the high viscosity of the object of the invention.As previously mentioned, micropore diameter is more little, and micropore volume is just more little, therefore, by maximum mercury is pressed into increment (Dyp) and (c) the average micro-pore diameter (Dxp) of formula add together, just can derive micropore mass runoff (number) required for the present invention, the numerical value of Dyp/Dxp is high more, and then viscosity is high more.So requiring average micropore mass runoff of the present invention (Dyp/Dxp) is 50-180.Dyp/Dxp can't obtain the high viscosity as the object of the invention less than 50 o'clock.And surpass 180, and then average micropore mass runoff is extremely too small, and the stability of primary particle or secondary particle will go wrong in time.Therefore, preferred 60-150, more preferably 70-130.
When surface treated lime carbonate of the present invention was outside (c) formula, (d) formula scope, the gloss of coating composition that this lime carbonate occurs for example having mixed is low, and the breaking tenacity of sealant composition was low etc.
Used pressure mercury device (porosimeter) and main condition determination are as follows among the present invention.
＜determinator 〉
Shimadzu Seisakusho Ltd.'s 9520 types
＜main condition determination 〉
Mercury purity=99.99 (%)
Mercury surface tension=480 (dyns/cm)
Mercury contact angle=135 ℃
Cell constant of conductometric vessel=10.79 (μ l/pF)
Test portion weight: the about 0.10g of each weighing measures
Surface treated lime carbonate of the present invention can be the material that satisfies following formula (e)-(f), more preferably when satisfying above-mentioned formula (a)-(d), satisfies the material of following formula (e)-(f).
(e)0.03≤Dxs≤1 (μm)
(f) Dys≤30 (% weight)
Wherein,
Dxs: (Shimadzu Seisakusho Ltd. makes laser-diffractometer: SALD-2000) in the size-grade distribution of Ce Dinging, start at the median size (μ m) of weight accumulative total 50% from big particle side
Dys: in the above-mentioned size-grade distribution, (e) formula, (f) formula are to know the index of the dispersion state in the resin combination for example to surpass the weight accumulative total (% weight) of particle diameter of 3 μ m.Therefore, being included above-mentioned formula as Consideration is preferred scheme.
In addition, the following mensuration of size-grade distribution: the following mixing material of weighing (I) and (II) to be equipped with the 140ml mayonnaise the bottle in, be stirred to visual dispersion with the stainless steel spoon, dilute with mixing material (III), on ultrasonic disperser, carry out pre-dispersed then, as test portion, (Shimadzu Seisakusho Ltd. makes: SALD-2000) measure by laser diffraction formula size-grade distribution meter with the gained material.
(I) neutral detergent (dilute with water 5 times after material) 2.0g
(II) lime carbonate test portion 0.4g
(III) water 40g
After especially preferably having carried out above-mentioned blended adjustment as pre-treatment, carry out ultrasonic dispersing under certain condition as pre-dispersed employing, used ultrasonic disperser is with US-300T (Japanese smart mechanism do society of institute make) in the embodiment of the invention, carries out pre-dispersed under the certain condition of 100 μ A-60 seconds.Neutral detergent is not particularly limited, can uses the commodity of selling on the common market, what use among the present invention is マ マ レ モ Application (registered trademark Lion corporate system).
In the above-mentioned particle size distribution method, median size of the present invention (Dxs) is during less than 0.03 μ m, occurs the situation that the stability of primary particle or secondary particle reduces in time sometimes.And surpass 1 μ m, then as mentioned above, three grades of particles form thing and increase easily, the dispersed variation easily in the resin combination.Therefore, more preferably 0.05-0.8 μ m, further preferred 0.08-0.5 μ m.
Surpass 30% weight if surpass the weight accumulative total (Dys) of the median size of 3 μ m, the dispersion state in the then not talkative resin combination is fully, is difficult to obtain required high viscosity physical property.Therefore, more preferably below 25% weight, most preferably below 20% weight.
When surface treated lime carbonate of the present invention when in above-mentioned (e) formula and (f) scope of formula is outer, the gloss of coating composition that has then for example mixed this lime carbonate is low, easy generation problem such as the breaking tenacity of sealant composition.
Surface treated lime carbonate of the present invention more preferably satisfies following formula (g)-(j).Their separate provision the preferable range of above-mentioned formula (c), (d), (e), (f).
(g)0.005≤Dxp≤0.025 (μm)
(h)60≤Dyp/Dxp≤150
(i)0.05≤Dxs≤0.8 (μm)
(j) Dys≤25 (% weight)
Surface treated lime carbonate of the present invention more preferably satisfies following formula (k).
(k)0.1≤Sw·Dxp≤1.5
(k) formula is the product of BET specific surface area value (Sw) and the average fine pore (Dxp) of expression secondary particle fineness of the primary particle fineness of the lime carbonate of expression after surface treatment.Primary particle and secondary particle limit in formula (a)-(j) respectively, but preferably are not separately to limit separately, but both take into account and limit as (k) formula, and this is easy to obtain required viscosity rerum natura.(k) SwDxp of formula is less than 0.1 o'clock, the situation that the stability of elementary or secondary particle reduces in time can occur.And surpass at 1.5 o'clock, then as mentioned above, three grades of particles form thing and increase easily.Therefore, more preferably 0.3-1.2, further preferred 0.5-1.0.
Further preferred surface treated lime carbonate of the present invention satisfies following formula (l).
(l)0.03≤Is≤3 (μmol/m
2)
Wherein,
Is: alkali metal content { metal content of every 1g lime carbonate (μ mol/g) }/Sw (m of the per unit specific surface area of calculating by following formula
2/ g)
(l) formula is represented the alkali metal content in the surface treated lime carbonate, usually preferred 0.03-3 μ mol/m
2Scope.In the alkali metal compound, especially sodium compound is because the thermopositive reaction height is easy to the moisture reaction outer with system, so surpass 3 μ mol/m if exist in the lime carbonate
2The sodium compound of amount then particularly can take place disperse the bad problem that waits aspect the storage stability in the sealing material purposes.If make alkali metal content reach 0.03 μ mol/m
2Level or less than 0.03 μ mol/m
2, then need 1) and make surface treatment amount few; Perhaps 2) after surface treatment, carry out the over-drastic washing; Perhaps 3) use as surface treatment agent with acid such as lipid acid or resinous acids.1) situation it is bad that above-mentioned rerum natura takes place easily situation, 2) is owing to need a large amount of water, and cost will improve.And 3) situation also owing to need the temperature more than fusing point carry out surface treatment, not only cost increases easily, and the selectivity of surface treatment agent also limited, so more preferably 0.15-2 μ mol/m
2, further preferred 0.3-1.5 μ mol/m
2
As preferred scheme, in the calcium carbonate slurry before carrying out surface treatment, preferably the characteristic of this slurry satisfies following (m) formula.
(m)0.03≤Dx≤0.40
Wherein,
Dx: by centrifugal size-grade distribution meter (Shimadzu Seisakusho Ltd.'s system: SA-CP4) in the size-grade distribution of Ce Dinging, start at 50% o'clock particle diameter (μ m) of weight accumulative total from big particle diameter side
(m) formula is represented the median size of the secondary particle of surface treated lime carbonate of the present invention before surface treatment, is the size-grade distribution index that has adopted clear and definite numerical value.The of the present invention surface treated lime carbonate that satisfies (m) formula can demonstrate the object of the invention place-high viscosity really and give effect.Therefore, Dx was less than 0.03 o'clock, and the stability in time of lime carbonate primary particle, dispersiveness be the generation problem easily.And when surpassing 0.40 μ m, because three grades of particles form the increasing proportion of things as mentioned above, thereby in the lime carbonate after surface treatment, be difficult to obtain the object of the invention place-high viscosity and give effect.So, more preferably 0.07-0.35 μ m, further preferred 0.10-0.30 μ m.
Primary particle shape to lime carbonate is not particularly limited, and can adopt sphere, fusiform, needle-like, bulk, chain (chain) etc., wherein chain not only give aspect the high viscosity preferred, and give aspect the mechanical strength of resin also preferred.
As the scheme that is more preferably, preferred surface treated lime carbonate of the present invention satisfies following formula.
(n)VIS2≥400(Pa·s)
(o)VIS20≥80(Pa·s)
(p)VIS2/VIS20≥5.0
Wherein,
VIS2: the 2rpm viscosity (Pas) that the mixing mashed prod of diisononyl phthalate (DINP) and surface treatment lime carbonate records by BH type viscometer
VIS20: the 20rpm viscosity (Pas) of above-mentioned mashed prod
(n)-(p) expression surface treated lime carbonate of the present invention resinous principle in viscous characteristics.DINP is as described below with the making method of mixing mashed prod of this lime carbonate.
Lime carbonate test portion 50 weight parts
DINP 30 weight parts
DINP 30 weight parts (appending)
DINP 30 weight parts (appending)
(1) the 30g DINP that packs in 1 liter of dixie cup takes by weighing 50g lime carbonate subsequently.Dixie cup is placed on the planetary whipping appts KK-502N (manufacturing of Network ラ ボ ウ society), mediated 60 seconds, manually stir with the stainless steel spoon then, continue 180 seconds with rotation 765rpm, revolution 765rpm.
(2) in cup, append 30g DINP, mediated 60 seconds, manually stir with the stainless steel spoon then, continue to mediate 180 seconds with rotation 765rpm, revolution 765rpm.
(3) in cup, append 30g DINP again, mediated 60 seconds, manually stir with the stainless steel spoon then, continue to mediate 180 seconds, make mashed prod with rotation 765rpm, revolution 765rpm.
To put cold 12 hours at 20 ℃ by the mashed prod that aforesaid method is made, use the viscosity of BH type viscometer determining 2rpm and 20rpm then.
Preferably the mashed prod viscosity of making by aforesaid method satisfies formula (n)-(p).
VIS2 is during less than 400Pas, and sag prevention etc. is little with the currently available products difference sometimes.VIS20 is difficult to obtain viscosity required for the present invention and gives effect during less than 80Pas.If VIS2/VIS20 less than 5.0, then is difficult to give high thixotropic.Therefore, more preferably VIS2 〉=500, VIS20 〉=90, VIS2/VIS20 〉=5.5, further preferred VIS2 〉=800, VIS20 〉=130, VIS2/VIS20 〉=6.
Preparation method to the lime carbonate of surface treated lime carbonate of the present invention before carrying out surface treatment is not particularly limited, but with put down in writing in the Japanese kokai publication hei 10-72215 communique for example as existing method in milk of lime, add the reagent that forms complex compound with calcium, make it carry out carbonation reaction, the preparation method who carries out slaking compares then, and for example the difference by slaking concentration, curing time etc. makes and has any different on the dispersing method this point.In the above-mentioned existing method, clearly height obtains dispersed microparticles by keeping the BET specific surface area after the slaking as far as possible, but for realizing problem of the present invention---give high viscosity and lightweight, then need further to carry out again the dispersive preparation method.
The preferred preparation condition of used lime carbonate is as described below among the present invention.
(reaction conditions)
1. lime milk concentration: 3.5-10.2% weight
2. complex compound forms material: 0.5-15% weight
3. flow of carbon dioxide gas amount: 300-3000L/hr
4. gas concentration: 10-50%
(slaking condition)
5. lime carbonate concentration: 2.4-13.0% weight
6. curing time: 24-240 hour
(surface treatment)
7. surface treatment amount: 3.5-50% weight
Preferred preparation method to the used lime carbonate of the present invention is specifically described below.
(reaction conditions)
1. the preferred 3.5-10.2% weight of lime milk concentration.Lime milk concentration was less than 3.5% o'clock, and not only productive rate is low, and cost uprises, even and concentration further diluted, also can't improve dispersiveness.And if surpass 10.2% weight, then be easy to take place the aggegation of primary particle diameter after the reaction, even carry out slaking, it is bigger that the median size of secondary particle also will become, and is difficult to obtain required viscosity rerum natura.Therefore, more preferably 5.0-9.0% weight, further preferred 6.0-8.0% weight.
2. complex compound forms the preferred 0.5-15% weight of addition of material.Addition is during less than 0.5% weight, be difficult to obtain target particulate of the present invention, if and surpass 15% weight, then because reacted primary particle is too thin, secondary particle particle diameter after the slaking does not satisfy the scope as (f) formula of preferred dispersion state sometimes, and the result is difficult to obtain required high viscosity and gives effect.For the interpolation time, can be before carbonation reaction or carbonation reaction midway, also can be before reaction and the reaction all add midway.
Forming material as complex compound, can be hydroxycarboxylic acid and an alkali metal salt, alkaline earth salt and ammonium salts such as citric acid, oxalic acid, oxysuccinic acid; Multi-hydroxy carboxy acid such as glyconic acid, tartrate and an alkali metal salt thereof, alkaline earth salt and ammonium salt; Amino polycarboxylic acid and an alkali metal salt, alkaline earth salt and ammonium salts such as imino-acetic acid, ethylenediamine tetraacetic acid (EDTA), nitrilotriacetic acid(NTA); Tripyrophosphoric acid such as hexa metaphosphoric acid, tripolyphosphate and an alkali metal salt thereof, alkaline earth salt and ammonium salt; Ketones such as methyl ethyl diketone, methyl acetoacetate, acetoacetic acid allyl ester; Sulfuric acid and an alkali metal salt thereof, alkaline earth salt and ammonium salt etc., these complex compounds form material and can use separately, also can two or more be used in combination.Wherein, the associativity height of hydroxycarboxylic acid and calcium particularly can preferably use citric acid.
3. flow of carbon dioxide gas amount is generally every 1Kg calcium hydroxide 300-3000L/hr.During less than 300L/hr, it is big that reacted primary particle becomes easily, when surpassing 3000L/hr, and the industrial production cost up, not preferred.
4. the preferred 10-50% of oxygen concentration.Gas concentration was less than 10% o'clock, and it is big that reacted primary particle becomes easily, surpasses at 50% o'clock, and the industrial production cost up is not preferred.
(slaking condition)
5. the preferred 2.4-13.0% weight of lime carbonate concentration.During less than 2.4% weight, commercial productivity is low, and when surpassing 13.0% weight, improving dispersiveness by slaking, under the situation that the structural viscosity of system rises, to the even stirring of the system difficulty that becomes, the median size of secondary particle does not satisfy the scope of (f) formula sometimes.The result is difficult to obtain required high viscosity and gives effect.Therefore, more preferably 4.0-11.0% weight, further preferred 5.0-9.0% weight.
As mentioned above, be used to improve dispersed important indicator because slaking concentration becomes easily, so the particle of pettiness, then the effect that concentration is diluted in preferable range is effective more.
About the curing time 6., if slaking is proceeded to the degree that satisfies as (f) formula of dispersed index preferable range, the high viscosity that then is easy to obtain the object of the invention place is given effect, thereby preferred.Therefore and since about above-mentioned preparation condition the curing time, thereby the curing time is not particularly limited, but is preferably 24-240 hour usually.The curing time less than 24 hours situation under, be difficult to obtain required dispersed particle, surpass 240 hours, then industrial cost increases.Therefore, more preferably 30-200 hour, further preferred 40-180 hour.
Preparation condition beyond above-mentioned can equally with existing common method carry out.For example, the synthesis temperature condition is generally 5-30 ℃ of scope, and the curing temperature condition is generally 30-70 ℃ of scope.Agitation condition during slaking be so long as can get final product all whipping forces that evenly stirs of liquid system, but if existing stirring capacity, need then to have no alternative but the concentration of reduction system, and this increases cost easily.About productive rate, this considers on the one hand from dispersiveness is improved certainly, and preferred stirring capacity is higher than existing stirring capacity.In addition, Mixing Machine uses splash bar, turbine, water screw, quick runner etc. usually.
(surface treatment)
About surface treatment amount 7., owing to change with the specific surface area of lime carbonate raw material, thereby so long as get final product in the scope of the As of formula (b), there is no particular limitation as to it, is generally 3.5-50% weight.Surface treatment amount is during less than 3.5% weight, can not fully cover the surface of the lime carbonate of fine, polymolecularity of the present invention sometimes.Consequently dry, when making powder, being untreated forms the secondary aggegation between the face, thereby is difficult to give full play to the effect of this surface treated lime carbonate.And if surpass 50% weight, then because surface treatment agent is too much, free in resinous principle or plasticizer component will take place, become easily and ooze the reason of moving phenomenon, surface irregularity phenomenon.Therefore, more preferably 5-40% weight, further preferred 7-35% weight.Surface treatment method is not particularly limited, and can be any way of wet type or dry type.
Among the present invention used organic system surface treatment agent can with following acid separately or two or more be used in combination: with sad, lauric acid, myristic acid, palmitinic acid, stearic acid, the acid of ア ラ ギ Application is the saturated fatty acid of representative, with oleic acid, elaidic acid, linolic acid, ricinoleic acid is the unsaturated fatty acids of representative, with the naphthenic acid is the alicyclic carboxylic acid of representative, with sylvic acid, pimaric acid, the acid of パ ラ ス ト リ Application, neoabietic acid is the resinous acid of representative and with their nilox resin, staybelite, dimerization colophonium, three polymerized rosins are the modified rosin of representative, with the alkyl benzene sulphonate (ABS) is the sulfonic acid class of representative and their an alkali metal salt, alkaline earth salt, ammonium salt, amine salt, and the following anionic that exemplifies, cationic, nonionic surface active agent.Particularly an alkali metal salt of an alkali metal salt of lipid acid, resinous acid is being preferred aspect the absorption reaction of lime carbonate.
The example of aniorfic surfactant has alkyl oxide sulfuric acid such as Voranol EP 2001 sulfuric acid; alkyl oxide phosphoric acid such as Voranol EP 2001 phosphoric acid; alkyl aryl ether sulfuric acid such as polyoxyethylene alkyl phenyl ether sulfuric acid; alkylaryl ether phosphoric acids such as polyoxyethylene alkyl phenyl ether phosphoric acid; alkyl sulfuric esters such as polyoxy alkyl sulfuric ester; alkyl phosphates such as polyoxy alkyl phosphate; alkyl aryl sulfates such as polyoxy alkyl phenyl sulfuric ester; alkyl aryl phosphate esters such as polyoxy alkyl phenyl phosphoric acid ester; alkylamide sulfates such as the sulfuric ester of fatty acid alkyl alcohol amide; alkylsulphonic acids such as polyxyethylated sulfonic acid; alkyl benzene sulphonate (ABS); alkyl naphthalene sulfonic acid; sulfo-succinic acid; sulfosuccinic esters such as dialkyl sulfosuccinate succinate; alpha-olefin sulfonic acid; N-acyl group sulfonic acid and/or their an alkali metal salt; alkaline earth salt; amine salt; aniorfic surfactant such as ammonium salt; α; the β unsaturated monocarboxylic acid; α; the β unsaturated dicarboxylic acid; alkyl methacrylate; (methyl) propenyl ether with alkoxyl group; (methyl) acrylate with cyclohexyl; α; the unsaturated hydroxy ester of β monoene key; polyalkylene glycol list (methyl) acrylate; vinyl ester; ethene base system aromatics; unsaturated nitrile; the unsaturated dicarboxylic acid ester; vinyl ether; conjugated diolefine; chain alkene; cyclic olefin; the anionic macromolecule dispersing agents such as multipolymer that form by monomer that contains sulfo group etc., and they pass through basic metal; alkaline-earth metal; the salt that forms etc. that partially or completely neutralizes such as ammonium.
The example of cationic surfactant has: stearylamine acetate, aliphatic amine salt such as stearyl amine hydrochloride, lauryl trimethyl ammonium chloride, aliphatic quaternary ammonium salts such as stearyl trimethyl ammonium chloride, aromatics quaternary ammonium salts such as alkyl benzyl dimethyl ammonium chloride, cationic surfactants such as heterocyclic quaternary ammonium material, has amino (primary amine groups), imino-(secondary amine), tertiary amine groups, quaternary ammonium group, the cationic high-molecular of diazanyl isopolarity group is a dispersion agent, can with the monomer of monomer copolymerization α for example with these polar groups, the β unsaturated monocarboxylic acid, α, the β unsaturated dicarboxylic acid, alkyl methacrylate, (methyl) propenyl ether with alkoxyl group, (methyl) acrylate with cyclohexyl, α, the unsaturated hydroxy ester of β monoene key, polyalkylene glycol list (methyl) acrylate, vinyl ester, ethene base system aromatics, unsaturated nitrile, the unsaturated dicarboxylic acid ester, vinyl ether, conjugated diolefine, chain alkene, cyclic olefin, with contain the multipolymer that monomer such as sulfomonomer forms, and they pass through basic metal, alkaline-earth metal, the salt that forms etc. that partially or completely neutralizes such as ammonium.
Examples of nonionic surfactants has trimethyl-glycine, aminocarboxylic acid, imidazolidine derivatives such as polyoxyethylene and derivative thereof, carboxybetaine, sultaine.
After the surface treatment, preferably filter contained foreign ions such as alkalimetal ion in the washing slurry, above-mentioned to satisfy (l) formula.In addition, the specific conductivity of filtrate is not particularly limited, is generally below the 10mS/cm, more preferably below the 1mS/cm, further below the preferred 300 μ S/cm.
Method for washing is not particularly limited, can washes, concentrate with thickener, Oliver filter, rotary filter, automatic pressure filter (Larox company) etc.
As mentioned above, surface treated lime carbonate of the present invention is specially adapted to resin, for example be mixed into molding resin, coating resin, resin for printing ink, seal gum with resin, tackiness agent with in the various resins such as resin, make have excellent specific property, the resin combination of rerum natura.
Molding resin is not particularly limited, its example has: with polyolefin-based resins such as ABS resin, fluoro-resin, polyethylene terephthalate, polycarbonate, polyethylene, polypropylene, ethylene/propene copolymer, ethene or propylene and other monomeric multipolymer, polystyrene resin, acrylic resin, metha crylic resin, vinyl chloride-based resin, vinylidene chloride is that resin, polyamide-based resin, polyethers are that resin, polyvinyl acetate resin, polyvinyl alcohol resin etc. are the thermoplastic resin of representative; With resol, urea resin, melamine resin, Resins, epoxy, urethane resin, polyimide resin etc. is the thermosetting resin of representative, and these resinous principles can use separately, also can two or more be used in combination.
Mixture ratio to surface treated lime carbonate of the present invention and these resins is not particularly limited, as long as according to the suitably decision of required rerum natura, usually preferably with respect to 100 parts by weight resin, surface treated lime carbonate is the 1-100 weight part.Certainly add various additives such as stablizer as required.
Coating resin is not particularly limited, and its example has: with Synolac, acrylic resin, polyvinyl acetate resin, urethane resin, silicone resin, fluoro-resin, styrene resin, melamine resin, Resins, epoxy etc. is that the solvent of representative is a coating resin; Water-borne coatings has Synolac, acrylic resin, latex resin, polyvinyl acetate resin, urethane resin, silicone resin, fluoro-resin, styrene resin, melamine resin, Resins, epoxy etc. to be the common coating of representative emulsion resin; With Synolac, polyimide resin, vinylbenzene/vinyl carbinol resin, amino-alkyd resin, polybutadiene etc. is the common aqueous coating soluble resin of representative; The coating dispersion type resin that emulsion resin and water soluble resin fusion form; With the dispersion type resin of cross-linking type water soluble resin as emulsifying agent; The acrylic acid or the like water-sol etc.These resinous principles can use separately, also can two or more be used in combination.
Mixture ratio to surface treated lime carbonate of the present invention and these resins is not particularly limited, as long as according to the suitably decision of required rerum natura, usually preferably with respect to 100 parts by weight resin, surface treated lime carbonate is the 1-100 weight part.Certainly add various additives such as softening agent, dispersion agent as required.
Plastisol has vinylchlorid colloidal sol, acrylic acid sol, water soluble propene's acid-sol, urethane colloidal sol etc. with the example of resin, and these resinous principles can use separately, also can two or more be used in combination.
Mixture ratio to surface treated lime carbonate of the present invention and these resins is not particularly limited, as long as according to the suitably decision of required rerum natura, usually preferably with respect to 100 parts by weight resin, surface treated lime carbonate is the 1-100 weight part.Certainly add various additives such as stablizer as required.
Resin for printing ink is not particularly limited, rosin modified phenolic resin, urea resin, melamine resin, ketone resin, polyvinyl chloride (PVC) RESINS, polyvinyl chloride-acetate ethylene copolymer, butyral resin, the styrene-maleic acid resin, Chlorinated Polypropylene III, acrylic resin, coumarone-indene resin, petroleum resin, vibrin, Synolac, polyamide resin, Resins, epoxy, urethane resin, soluble cotton, ethyl cellulose, the ethyl hydroxylated cellulose, thermoprene, chlorinated rubber etc., these resinous principles can use separately, also can two or more be used in combination.
Mixture ratio to surface treated lime carbonate of the present invention and these resins is not particularly limited, as long as according to the suitably decision of required rerum natura, usually preferably with respect to 100 parts by weight resin, surface treated lime carbonate is the 1-100 weight part.Certainly add various additives such as stablizer, siccative as required.
Seal gum is not particularly limited with resin, its example has urethane resin, thio resin, silicone resin, modified organic silicone resin, polyisobutene resin, Resins, epoxy, vibrin etc., these resinous principles can use separately, also can two or more be used in combination.
Mixture ratio to surface treated lime carbonate of the present invention and these resins is not particularly limited, as long as according to the suitably decision of required rerum natura, usually preferably with respect to 100 parts by weight resin, surface treated lime carbonate is the 1-100 weight part.Certainly add various additives such as tinting material, stablizer as required.
Tackiness agent is not particularly limited with resin, its example has: urea resin, resol, Resins, epoxy, silicone resin, acrylic resin, urethane resin, vibrin etc., these resins can use separately, also can two or more be used in combination.
Mixture ratio to surface treated lime carbonate of the present invention and these resins is not particularly limited, as long as according to the suitably decision of required rerum natura, usually preferably with respect to 100 parts by weight resin, surface treated lime carbonate is the 1-100 weight part.Certainly add various additives such as stablizer, softening agent as required.
In the resin combination of the present invention except surface treated lime carbonate of the present invention, in order to regulate viscosity and other physical property, can also add colloidal calcium carbonate, water-ground limestone, colloidal silica, talcum, kaolin, zeolite, resin circle (balloon), bulking agents such as glass collar, dioctyl phthalate (DOP), softening agent such as dibutyl phthalate, toluene, oil series solvents such as dimethylbenzene, acetone, ketones such as butanone, ether-ether equal solvents such as cellosolve acetate, perhaps silicone oil, fatty acid ester modified silicon oil etc., and other various additives as required, tinting material etc., these reagent can add a kind of, also can two or more combinations add.
Resin combination of the present invention has excellent viscosity, thixotropy and seam and follows the trail of property for being under the situation of curable resin composition of representative with seal gum, tackiness agent for example.Under the situation for for example coating, resin for printing ink composition, have excellent sag prevention, high gloss, high transparent, high coating strength.And then, under the situation for for example molding resin composition, can prevent that the intensity of welded bonds face from reducing, have excellent intensity.
Provide embodiment and comparative example below, the present invention will be described in more detail, but the present invention only otherwise exceed its scope, is not limited to these examples.
In the following record, unless otherwise indicated, otherwise % is meant % weight, and part is meant weight part.
Embodiment 1
With the citric acid that forms material as complex compound being that 1.7% amount is added in the milk of lime of 10 ℃ of temperature, concentration 8% with respect to calcium hydroxide, importing every 1kg calcium hydroxide in this slurry is 20% carbon dioxide of 1700L/hr, makes calcium carbonate slurry.Then this calcium carbonate slurry is adjusted to concentration 10%, the temperature 45-50 ℃ of stirring slaking of carrying out 50 hours.Median size after the slaking (Dx)=0.20 μ m.Add 10% sodium stearate of heat of solution in warm water in this calcium carbonate slurry, making it is 15% with respect to the lime carbonate solids component, by stirring, make this surface treatment agent fully be adsorbed in the lime carbonate surface, dehydration, drying are made powder then, synthetic BET specific surface area (Sw)=48m
2The lime carbonate of/g through organic system surface treatment agent surface treatment formation.In addition, this surface treated lime carbonate is at hot reduction rate (Tg)=118mg/g of 200 ℃-500 ℃.Average micropore diameter (Dxp)=0.016 μ m, average micropore mass runoff (Dyp/Dxp)=79.Each physics value of the surface treated lime carbonate of gained is listed in the table 1.
Embodiment 2
Except that calcium carbonate slurry concentration is become 7%, by preparation method similarly to Example 1, the synthetic lime carbonate that forms through the surface treatment of organic system surface treatment agent.Each physics value of the surface treated lime carbonate of gained is listed in the table 1.
Embodiment 3
Except that becoming the curing time 120 hours, by preparation method similarly to Example 2, the synthetic lime carbonate that forms through the surface treatment of organic system surface treatment agent.Each physics value of gained surface treatment lime carbonate is listed in the table 1.
Embodiment 4
After the surface treatment, (Larox company) washes calcium carbonate filter cake, dewater with pressure filter, makes the specific conductivity of filtrate reach 300 μ S/cm, in addition, by preparation method similarly to Example 1, the synthetic lime carbonate that forms through the surface treatment of organic system surface treatment agent.Each physics value of gained surface treatment lime carbonate is listed in the table 1.
Embodiment 5
Except that surface treatment amount is become 25%, by preparation method similarly to Example 1, the synthetic lime carbonate that forms through the surface treatment of organic system surface treatment agent.Each physics value of gained surface treatment lime carbonate is listed in the table 1.
Embodiment 6
With the citric acid that forms material as complex compound being that 10% amount is added in the milk of lime of 10 ℃ of temperature, concentration 5% with respect to calcium hydroxide, importing every 1kg calcium hydroxide in this slurry is 20% carbon dioxide of 1700L/hr, makes calcium carbonate slurry.Then this calcium carbonate slurry is adjusted to concentration 30%, the temperature 45-50 ℃ of stirring slaking of carrying out 150 hours.Median size after the slaking (Dx)=0.38 μ m.Add 10% sodium stearate of heat of solution in warm water in this calcium carbonate slurry, making it is 35% with respect to the lime carbonate solids component, by stirring, make this surface treatment agent fully be adsorbed in the lime carbonate surface, dehydration, drying are made powder then, synthetic BET specific surface area (Sw)=125m
2The lime carbonate of/g through organic system surface treatment agent surface treatment formation.In addition, this surface treatment lime carbonate is at hot reduction rate (Tg)=296mg/g of 200 ℃-500 ℃.Average micropore diameter (Dxp)=0.005 μ m, average micropore mass runoff (Dyp/Dxp)=148.Each physics value of the surface treated lime carbonate of gained is listed in the table 1.
Embodiment 7
Interpolation is as the trisodium citrate of complex compound formation material, and making it is 3% with respect to calcium hydroxide, passes through preparation method similarly to Example 1 in addition, the synthetic lime carbonate that forms through the surface treatment of organic system surface treatment agent.Each physics value of gained surface treatment lime carbonate is listed in the table 1.
Embodiment 8
Except that the organic system surface treatment agent is become the lauric acid, by preparation method similarly to Example 1, the synthetic lime carbonate that forms through the surface treatment of organic system surface treatment agent.Each physics value of the surface treated lime carbonate of gained is listed in the table 1.
Embodiment 9
Except that the organic system surface treatment agent is become the sodium laurate, by preparation method similarly to Example 1, the synthetic lime carbonate that forms through the surface treatment of organic system surface treatment agent.Each physics value of the surface treated lime carbonate of gained is listed in the table 2.
Embodiment 10
Except that the organic system surface treatment agent is become the Sodium pentadecanecarboxylate, by preparation method similarly to Example 1, the synthetic lime carbonate that forms through the surface treatment of organic system surface treatment agent.Each physics value of the surface treated lime carbonate of gained is listed in the table 2.
Embodiment 11
Except that the organic system surface treatment agent is become sodium stearate: resinous acid potassium=3: 2, by preparation method similarly to Example 1, the synthetic lime carbonate that forms through the surface treatment of organic system surface treatment agent.Each physics value of the surface treated lime carbonate of gained is listed in the table 2.
Embodiment 12
Except that the organic system surface treatment agent is become the resinous acid potassium, by preparation method similarly to Example 1, the synthetic lime carbonate that forms through the surface treatment of organic system surface treatment agent.Each physics value of the surface treated lime carbonate of gained is listed in the table 2.
Embodiment 13
Except that the organic system surface treatment agent is become sodium stearate: sodium alkyl benzene sulfonate=3: 1, by preparation method similarly to Example 1, the synthetic lime carbonate that forms through the surface treatment of organic system surface treatment agent.Each physics value of the surface treated lime carbonate of gained is listed in the table 2.
Comparative example 1
Except that the addition with the organic system surface treatment agent becomes 5%, by preparation method similarly to Example 1, the synthetic lime carbonate that forms through the surface treatment of organic system surface treatment agent.Each physics value of the surface treated lime carbonate of gained is listed in the table 2.
Comparative example 2
With the citric acid that forms material as complex compound being that 18% amount is added in the milk of lime of 10 ℃ of temperature, concentration 4% with respect to calcium hydroxide, importing every 1kg calcium hydroxide in this slurry is 20% carbon dioxide of 17000L/hr, makes calcium carbonate slurry.Then this calcium carbonate slurry is adjusted to concentration 2%, the temperature 45-50 ℃ of stirring slaking of carrying out 200 hours.Median size after the slaking (Dx)=2.3 μ m.Add 10% sodium stearate of heat of solution in warm water in this calcium carbonate slurry, making it is 45% with respect to the lime carbonate solids component, by stirring, make this surface treatment agent fully be adsorbed in the lime carbonate surface, dehydration, drying are made powder then, synthetic BET specific surface area (Sw)=175m
2The lime carbonate of/g through organic system surface treatment agent surface treatment formation.In addition, this surface treated lime carbonate is at hot reduction rate (Tg)=402mg/g of 200 ℃-500 ℃.Average micropore diameter (Dxp)=0.003 μ m, average micropore mass runoff (Dyp/Dxp)=47.Each physics value of the surface treated lime carbonate of gained is listed in the table 2.
Comparative example 3
As described in the embodiment 1 of Japanese kokai publication hei 10-72215 communique, with the trisodium citrate that forms material as complex compound being that 3% amount is added in the milk of lime of 10 ℃ of temperature, concentration 11.8% with respect to calcium hydroxide, importing every 1kg calcium hydroxide in this slurry is 20% carbon dioxide of 1700L/hr, makes calcium carbonate slurry.This calcium carbonate slurry is not carried out the concentration adjustment then, directly with 14.9% lime carbonate concentration the temperature 45-50 ℃ of stirring slaking of carrying out 50 hours.Median size after the slaking (Dx)=0.50 μ m.Add 10% sodium stearate of heat of solution in warm water in this calcium carbonate slurry, making it is 15% with respect to the lime carbonate solids component, stirs by brute force, make this surface treatment agent fully be adsorbed in the lime carbonate surface, dehydration, drying are made powder then, synthetic BET specific surface area (Sw)=42m
2The lime carbonate of/g through organic system surface treatment agent surface treatment formation.In addition, this surface treated lime carbonate is at hot reduction rate (Tg)=101mg/g of 200 ℃-500 ℃.Average micropore diameter (Dxp)=0.018 μ m, average micropore mass runoff (Dyp/Dxp)=27.Each physics value of the surface treated lime carbonate of gained is listed in the table 2.
Comparative example 4
With the citric acid that forms material as complex compound being that 0.2% amount is added in the milk of lime of 10 ℃ of temperature, concentration 11.8% with respect to calcium hydroxide, importing every 1kg calcium hydroxide in this slurry is 20% carbon dioxide of 1700L/hr, makes lime carbonate.This calcium carbonate slurry is not carried out the concentration adjustment then, directly with 14.9% lime carbonate concentration the temperature 45-50 ℃ of stirring slaking of carrying out 50 hours.Median size after the slaking (Dx)=0.49 μ m.Add 10% sodium stearate of heat of solution in warm water in this calcium carbonate slurry, making it is 5% with respect to the lime carbonate solids component, stirs by brute force, make this surface treatment agent fully be adsorbed in the lime carbonate surface, dehydration, drying are made powder then, synthetic BET specific surface area (Sw)=17m
2The lime carbonate of/g through organic system surface treatment agent surface treatment formation.In addition, this surface treated lime carbonate is at hot reduction rate (Tg)=42mg/g of 200 ℃-500 ℃.
Average micropore diameter (Dxp)=0.042 μ m, average micropore mass runoff (Dyp/Dxp)=38.Each physics value of the surface treated lime carbonate of gained is listed in the table 2.
Comparative example 5
Except that the organic system surface treatment agent is become the resinous acid potassium, by the preparation method same, the synthetic lime carbonate that forms through the surface treatment of organic system surface treatment agent with comparative example 3.Each physics value of the surface treated lime carbonate of gained is listed in the table 2.
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | |
| (a)Sw(m 2/g) (b)As(mg/m 2) (c)Dxp(μm) (d)Dyp/Dxp | 48 2.5 0.016 79 | 51 2.4 0.016 86 | 53 2.4 0.015 99 | 48 2.4 0.015 91 | 43 5.0 0.012 53 | 125 2.4 0.005 148 | 44 2.8 0.016 71 | 49 2.3 0.016 80 |
| (e)Dxs(μm) (f)Dys(％) | 0.25 12 | 0.15 5 | 0.11 0 | 0.23 9 | 0.53 24 | 0.83 23 | 0.87 28 | 0.25 9 |
| (k)Sw·Dxp | 0.77 | 0.82 | 0.80 | 0.72 | 0.52 | 0.63 | 0.70 | 0.78 |
| (l)Is(μmol/m 2) | 1.68 | 1.61 | 1.60 | 0.36 | 4.21 | 1.61 | 3.39 | 2.57 |
| (m)Dx(μm) | 0.20 | 0.11 | 0.08 | 0.23 | 0.23 | 0.38 | 0.42 | 0.20 |
| (n)VIS2(Pa·s) (o)VIS20(Pa·s) (p)VIS2/VIS20 | 1150 170 6.8 | 1350 195 6.9 | 1480 210 7.0 | 970 155 6.3 | 1430 295 4.8 | 1620 245 6.6 | 555 115 4.8 | 1200 175 6.9 |
| 1. lime milk concentration (%) | 8.0 | 8.0 | 8.0 | 8.0 | 8.0 | 5.0 | 8.0 | 8.0 |
| 2. complex compound forms substrate concentration (%) | 1.7 | 1.7 | 1.7 | 1.7 | 1.7 | 10 | 3.0 | 1.7 |
| Complex compound forms material | Citric acid | Citric acid | Citric acid | Citric acid | Citric acid | Citric acid | Trisodium citrate | Citric acid |
| 3. the carbon dioxide gas scale of construction (L/hr) | 1700 | 1700 | 1700 | 1700 | 1700 | 1700 | 1700 | 1700 |
| 4. gas concentration (%) | 20 | 20 | 20 | 20 | 20 | 20 | 20 | 20 |
| 5. lime carbonate concentration (%) | 10 | 7.0 | 7.0 | 10 | 10 | 3.0 | 10 | 10 |
| 6. curing time (hr) | 50 | 50 | 120 | 50 | 50 | 150 | 50 | 50 |
| 7. surface treatment amount (%) | 15 | 15 | 15 | 15 | 25 | 35 | 15 | 15 |
| Surface treatment agent | Sodium stearate | Sodium stearate | Sodium stearate | Sodium stearate | Sodium stearate | Sodium stearate | Sodium stearate | Lauric acid |
| The specific conductivity of filtrate (μ S/cm) | 2000 | 2000 | 2000 | 300 | 3600 | 2200 | 1900 | 200 |
Table 2
| Embodiment 9 | Embodiment 10 | Embodiment 11 | Embodiment 12 | Embodiment 13 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | |
| (a)Sw(m 2/g) (b)As(mg/m 2) (c)Dxp(μm) (d)Dyp/Dxp | 50 2.5 0.016 110 | 47 2.5 0.016 80 | 47 2.4 0.016 77 | 47 2.3 0.016 69 | 46 2.3 0.016 75 | 51 0.8 0.031 27 | 175 2.3 0.003 47 | 42 2.4 0.018 27 | 17 2.5 0.042 38 | 44 3.0 0.018 26 |
| (e)Dxs(μm) (f)Dys(％) | 0.25 7 | 0.31 13 | 0.29 15 | 0.36 18 | 0.3 18 | 0.76 35 | 8.6 68 | 1.3 44 | 0.56 22 | 1.7 58 |
| (k)Sw·Dxp | 0.80 | 0.75 | 0.75 | 0.75 | 0.74 | 1.58 | 0.53 | 0.76 | 0.71 | 0.79 |
| (l)Is(μmol/m 2) | 2.57 | 1.97 | 2.09 | 1.94 | 1.85 | 0.61 | 1.64 | 2.84 | 2.45 | 2.80 |
| (m)Dx(μm) | 0.20 | 0.20 | 0.20 | 0.20 | 0.20 | 0.58 | 2.3 | 0.50 | 0.49 | 0.50 |
| (n)VIS2(Pa·s) (o)VIS20(Pa·s) (p)VIS2/VIS20 | 1250 175 7.1 | 985 155 6.4 | 985 155 6.4 | 890 150 5.9 | 975 155 6.3 | 390 75 5.2 | 95 15 6.3 | 325 80 4.1 | 245 70 3.5 | 275 70 3.9 |
| 1. lime milk concentration (%) | 8.0 | 8.0 | 8.0 | 8.0 | 8.0 | 8.0 | 4.0 | 11.8 | 11.8 | 11.8 |
| 2. complex compound forms material concentration (%) | 1.7 | 1.7 | 1.7 | 1.7 | 1.7 | 1.7 | 18 | 3.0 | 0.2 | 3.0 |
| Complex compound forms material | Citric acid | Citric acid | Citric acid | Citric acid | Citric acid | Citric acid | Citric acid | Trisodium citrate | Citric acid | Trisodium citrate |
| 3. the carbon dioxide gas scale of construction | 1700 | 1700 | 1700 | 1700 | 1700 | 1700 | 1700 | 1700 | 1700 | 1700 |
| 4. gas concentration (%) | 20 | 20 | 20 | 20 | 20 | 20 | 20 | 20 | 20 | 20 |
| 5. lime carbonate concentration (%) | 10 | 10 | 10 | 10 | 10 | 10 | 2.0 | 14.9 | 14.9 | 14.9 |
| 6. curing time (hr) | 50 | 50 | 50 | 50 | 50 | 50 | 200 | 50 | 50 | 50 |
| 7. surface treatment amount (%) | 15 | 15 | 15 | 15 | 15 | 5 | 45 | 15 | 5 | 13 |
| Surface treatment agent | Sodium laurate | Sodium pentadecanecarboxylate | Sodium stearate: resinous acid potassium=3: 2 | Resinous acid potassium | Sodium stearate: DBS-Na=3: 1 | Sodium stearate | Sodium stearate | Sodium stearate | Sodium stearate | Resinous acid potassium |
| The specific conductivity of filtrate (μ S/sm) | 800 | 2000 | 2200 | 2200 | 2200 | 800 | 3800 | 2000 | 1400 | 2100 |
Embodiment 14-20, comparative example 6-9
With the surface treated lime carbonate of synthetic among the foregoing description 1-7, the comparative example 1-4, prepare molding resin composition according to following proportioning.The evaluation result of gained molding resin composition is listed in the table 3.
(proportioning)
15 parts in surface treated lime carbonate
85 parts of acrylic resins
Above-mentioned two kinds of compositions are carried out dry blending in Henschel mixer (カ ワ society system) after, (the system NEXT T-60 of society of Kobe Steel) goes up and granulates at extrusion shaping machine, make the dumb-bell shape sheet by injection moulding machine then, test its tensile strength, crooked elastic rate, shock strength.Just, for the test film of the intensity of measuring the welded bonds face, be to inject from two cast gates, form the welded bonds interface in the center.The test film of other physical property measurement is to inject from a cast gate.
Measure, estimate the various characteristics of gained test film by following method.
(tensile strength, flexural strength, shock strength)
Tensile strength is measured by the plastic tensile test method of JIS K7113, flexural strength is measured by the bend test method of the rigid plastics of JIS K7203, and shock strength is measured by the Charpy impact test method of the rigid plastics of JIS K7111.
(anti-scratch test)
With anti-scratch trier (the smart mechanism of Japan is done society of institute and made) plastic plate that is shaped to 30mm * 80mm, thickness 1mm is carried out anti-scratch test, according to its state of following benchmark evaluation.
◎: fabulous (not having cut fully)
Zero: good (almost not having cut)
△: common (some cuts are arranged)
*: bad (a lot of cuts are arranged)
Table 3
| Used surface treated lime carbonate | Tensile strength (the N/mm of common part 2) | Tensile strength (the N/mm at welded bonds interface 2) | Flexural strength (the N/mm of common part 2) | Flexural strength (the N/mm at welded bonds interface 2) | Shock strength (Ncm/cm 2) | Anti-scratch test | |
| Embodiment 14 embodiment 15 embodiment 16 embodiment 17 embodiment 18 embodiment 19 embodiment 20 | Embodiment 1 embodiment 2 embodiment 3 embodiment 4 embodiment 5 embodiment 6 embodiment 7 | 34 36 37 34 29 41 30 | 32 33 33 32 30 35 29 | 47 49 50 46 44 54 42 | 36 37 38 35 32 41 33 | 43 45 45 43 36 49 38 | ○ ◎ ◎ ○ △～○ ○ ○ |
| Comparative example 6 comparative examples 7 comparative examples 8 comparative examples 9 | Comparative example 1 comparative example 2 comparative examples 3 comparative examples 4 | 19 13 16 21 | 17 11 15 19 | 34 22 29 24 | 24 15 21 19 | 27 19 25 23 | × × × × |
As can be known from the results of Table 3, be mixed with molding resin composition that surface treated lime carbonate of the present invention forms not only tensile strength, flexural strength, shock strength excellence, and prevent from also to show aspect the reduction of welded bonds face intensity good, hence one can see that its with also good by the adhesive power of bur.And the comparable present decrement about 5% of the addition of lime carbonate, also be effective as can be known aspect lightweight.
Embodiment 21-27, comparative example 10-13
With the surface treated lime carbonate of synthetic among the foregoing description 1-7, the comparative example 1-4, prepare coating resin composition according to following proportioning.
(proportioning)
50 parts in surface treated lime carbonate
Water-ground limestone (the system Super-SSS of Marno Calcium Co., Ltd.)
41 parts
Synolac
(the big system Beccozol P-470-70 of Japanese ink (イ Application キ) chemical industry Co., Ltd.)
250 parts
120 parts of titanium dioxide (the system TIPAQUE R-820 of the former industry of stone society)
70 parts of petroleum solvents (mineral spirit)
14 parts in siccative
1.5 parts of antis
350 parts of granulated glass spherees
With said mixture with the SG shredder be dispersed to through grindometer be measured as 20 microns or below, take out granulated glass sphere, make coating resin composition, measure, estimate various characteristics by following method.The result is as shown in table 4.
(gloss after gloss, the waterproof test, gloss retention)
Each coating resin composition is coated on the one side of sheet glass with 100 microns spreaders, dry 24 hours at normal temperatures, measures 60 ° of gloss with village's following formula glossmeter then.Afterwards sheet glass be impregnated in the water, measure the gloss retention after 3 days.
(flow)
Regulate each coating resin composition with the petroleum solvent dilution, make its KU value reach 78, coat complete black mensuration, immediately coated face is vertically erected after the coating with on the paper with 250,200,150,100 microns spreader, placed at normal temperatures 24 hours, according to its sagging state of following benchmark evaluation.
Zero: good (not having sagging fully)
: common (some saggings are arranged)
*: bad (generation sagging)
(scratch test of filming)
Each coating resin composition is coated on the one side of sheet glass with 1000 microns spreaders, after dry at normal temperatures 1 week, carried out scratch test with scratch tester (the smart mechanism of Japan is made society of institute system), according to its state of following benchmark evaluation.
◎: fabulous (not having cut fully)
Zero: good (almost not having cut)
△: common (some cuts are arranged)
*: bad (a lot of cuts are arranged)
Table 4
| Used surface treated lime carbonate | 60 ° of initial stage gloss | 60 ° of gloss after the waterproof test | Gloss retention % | Flow | The anti-scratch test of filming | ||||
| 250μm | 200μm | 150μm | 100μm | ||||||
| Embodiment 21 embodiment 22 embodiment 23 embodiment 24 embodiment 25 embodiment 26 embodiment 27 | Embodiment 1 embodiment 2 embodiment 3 embodiment 4 embodiment 5 embodiment 6 embodiment 7 | 90.5 92.5 93.0 90.0 87.5 93.5 88.5 | 87.0 89.0 90.0 87.0 85.5 85.5 84.5 | 96 96 97 95 98 91 95 | △ △ ○ △ ○ ○ △ | ○ ○ ○ ○ ○ ○ △ | ○ ○ ○ ○ ○ ○ ○ | ○ ○ ○ ○ ○ ○ ○ | ○ ○ ◎ ○ ○ ◎ ○ |
| Comparative example 10 comparative examples 11 comparative examples 12 comparative examples 13 | Comparative example 1 comparative example 2 comparative examples 3 comparative examples 4 | 85.5 88.0 84.5 78.5 | 74.5 68.5 75.5 73.5 | 87 78 89 94 | × △ × × | × △ × × | × ○ △ × | △ ○ △ × | × △ △ × |
As can be known from the results of Table 4, be mixed with the coating resin composition that surface treated lime carbonate of the present invention forms and have excellent sag prevention, thereby have high thixotropy, and the gloss retention excellence after the waterproof test, hence one can see that, and it has high-durability and firm coating strength.
Embodiment 28-34, comparative example 14-17
With the surface treated lime carbonate of synthetic among the foregoing description 1-7, the comparative example 1-4, the plastisol resin combination that forms is regulated in preparation according to following proportioning.
(proportioning)
300 parts in surface treated lime carbonate
Acrylic resin Zeon Acrylic Resin F345 (the industrial society of new first salt PVC system)
250 parts
120 parts of end-blocking (Block ロ Star Network) curable urethane resin agent (the military field of Mitsui chemistry society system)
500 parts of DINP
80 parts in turps
6 parts of polyurethane curing agents (the military field of Mitsui chemistry society system)
With each mixture in the omnipotent stirrer of 5L (Dulton manufacturing) under normal temperature kneading make the acrylic acid sol resin combination to there not being particle, by following method evaluation of measuring various characteristics.The result is as shown in table 5.
(viscosity, thixotropy)
Based on the 2rpm of the acrylic acid sol of said ratio adjusting, the viscosity of 20rpm, represent thixotropy with BH type viscometer determining with 2rpm/20rpm viscosity.
(chip resistance (chipping) property)
To electroplate filming on the spray coating plate and after solidifying and become 60 ° of angles to fix smearing under the above-mentioned drying conditions to be plated on level, and make spraying towards last, the length that aligned perpendicular is stood on this coated surface is the lower end of the pipe of 2m, according to JIS nut (nut) shatter test method, the M-4 nut is fallen, represent crumpling resistance to the accumulating weight that exposes the nut till the basal surface so that spraying face is destroyed.
Table 5
| Acrylic acid sol viscosity | Crumpling resistance (kg) | ||||
| 2rpm (Pa·s) | 20rpm (Pa·s) | Thixotropy 2rpm/20rpm | |||
| Embodiment 28 | Embodiment 1 | 650 | 95 | 6.8 | 82 |
| Embodiment 29 | Embodiment 2 | 680 | 105 | 6.5 | 86 |
| Embodiment 30 | Embodiment 3 | 770 | 115 | 6.7 | 90 |
| Embodiment 31 | Embodiment 4 | 620 | 90 | 6.9 | 88 |
| Embodiment 32 | Embodiment 5 | 550 | 105 | 5.2 | 68 |
| Embodiment 33 | Embodiment 6 | 920 | 145 | 6.3 | 76 |
| Embodiment 34 | Embodiment 7 | 540 | 85 | 6.4 | 72 |
| Comparative example 14 | Comparative example 1 | 330 | 60 | 5.5 | 48 |
| Comparative example 15 | Comparative example 2 | 180 | 40 | 4.5 | 34 |
| Comparative example 16 | Comparative example 3 | 280 | 55 | 5.1 | 42 |
| Comparative example 17 | Comparative example 4 | 140 | 35 | 4.0 | 32 |
As shown in Table 5, be mixed with surface treated lime carbonate of the present invention and the plastisol resin combination that forms, obtaining obvious improvement aspect viscosity, the intensity (crumpling resistance).
Embodiment 35-46, comparative example 18-21
With the surface treated lime carbonate of synthetic among the foregoing description 1-11 and 13, the comparative example 1-4, regulate according to following proportioning, estimate the various characteristics of gained curable resin composition.The result is shown in table 6,7.
(proportioning)
(base material)
400 parts in surface treated lime carbonate
500 parts of resins (MS polymkeric substance S810 clock deep pool chemistry system)
345 parts of DOP
400 parts of water-ground limestones (ball tail calcium system Super S)
5 parts of aminosilanes
(solidifying agent)
20 parts of colloidal calcium carbonates (ball tail calcium system Calfine 200M)
6 parts of stannous octoates
1 part of lauryl amine
11 parts of DOP
28 parts of water-ground limestones (ball tail calcium system Super SSS)
Each mixture is fully mediated to there not being particle in the omnipotent stirrer of 5L (Dulton manufacturing), made base material and solidifying agent, by following method evaluation of measuring various characteristics.The result is as shown in table 6.
(viscosity, thixotropy)
Based on the 1rpm of the base material of the curable resin composition of said ratio adjusting, the viscosity of 10rpm, represent thixotropy with BS type viscometer determining with 1rpm viscosity/10rpm viscosity.
(storage stability test)
Above-mentioned curable resin composition in thermostat, was left standstill for 2 weeks in 20 ℃, measure base material viscosity then.
(H type tensile strength and elongation test)
With base material: solidifying agent=10: 1 carries out abundant froth breaking to be mixed, and prepares H type resin combination according to JIS A57576.11 tensile stress and elongation test then and estimates.
(adhesion test)
In above-mentioned H type tensile strength test, according to following benchmark evaluation binding property.
Zero: good (generating material destruction)
△: common (interface peel takes place a little, but also generating material destroying)
*: bad (generation interface peel)
(carrying out tension test of H type and adhesion test after the test of tracking property)
In the above-mentioned H type tensile strength test, cured article was fixed for 1 week to have extended 50% state, H type tensile strength (unrelieved stress) is measured in operation equally then, and by estimating binding property, estimates the tracking of sealing material butt seam.
Table 6
| Used surface treated lime carbonate | The base material viscosity of firm preparation | Base material viscosity after 20 ℃ * 2 weeks | |||||
| 1rpm (Pa·s) | 10rpm (Pa·s) | Thixotropy 1rpm/10rpm | 1rpm (Pa·s) | 10rpm (Pa·s) | Thixotropy 1rpm/10rpm | ||
| Embodiment 35 embodiment 36 embodiment 37 embodiment 38 embodiment 39 embodiment 40 embodiment 41 embodiment 42 embodiment 43 embodiment 44 embodiment 45 embodiment 46 | Embodiment 1 embodiment 2 embodiment 3 embodiment 4 embodiment 5 embodiment 6 embodiment 7 embodiment 8 embodiment 9 embodiment 10 embodiment 11 embodiment 13 | 4400 4550 4650 4300 4600 6490 3950 4100 4500 3900 4050 4150 | 640 650 660 630 780 980 670 590 630 610 620 620 | 6.9 7.0 7.0 6.8 5.9 6.6 5.9 6.9 7.1 6.4 6.5 6.7 | 5160 5430 5580 4450 7850 7850 5150 4250 5450 5120 4890 4520 | 760 780 820 650 1350 1180 950 630 770 830 770 710 | 6.8 7.0 6.8 6.8 5.8 6.7 5.4 6.7 7.1 6.2 6.4 6.4 |
| Comparative example 18 comparative examples 19 comparative examples 20 comparative examples 21 | Comparative example 1 comparative example 2 comparative examples 3 comparative examples 4 | 1570 1950 2780 820 | 325 385 530 170 | 4.8 5.1 5.2 4.8 | 2040 2450 3890 1000 | 390 510 740 225 | 5.2 4.8 5.3 4.4 |
Table 7
| Used surface treated lime carbonate | The initial stage rerum natura | Rerum natura after the test of tracking property | |||||
| Extend 50% o'clock tensile strength (N/mm 2) | Tensile strength (N/mm during fracture 2) | Elongation (%) | Binding property | Tensile strength (N/mm during fracture 2) | Binding property | ||
| Embodiment 35 embodiment 36 embodiment 37 embodiment 38 embodiment 39 embodiment 40 embodiment 41 embodiment 42 embodiment 43 embodiment 44 embodiment 45 embodiment 46 | Embodiment 1 embodiment 2 embodiment 3 embodiment 4 embodiment 5 embodiment 6 embodiment 7 embodiment 8 embodiment 9 embodiment 10 embodiment 11 embodiment 13 | 0.23 0.21 0.19 0.23 0.28 0.17 0.25 0.24 0.22 0.25 0.23 0.23 | 1.05 0.15 1.20 1.00 0.80 1.30 0.95 0.95 1.10 0.90 1.00 1.00 | 890 920 930 910 720 980 870 900 900 850 880 880 | ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ | 0.90 1.05 1.10 0.95 0.75 1.25 0.80 0.80 0.90 0.85 0.85 0.85 | △ △ △ △ △ △ △ △ △ △ ○ △ |
| Comparative example 18 comparative examples 19 comparative examples 20 comparative examples 21 | Comparative example 1 comparative example 2 comparative examples 3 comparative examples 4 | 0.48 0.33 0.28 0.13 | 0.55 0.60 0.75 0.85 | 430 780 640 550 | × △ △ × | 0.38 0.45 0.62 0.55 | × × × × |
By the result of table 6 and table 7 as can be known, be mixed with surface treated lime carbonate of the present invention and form with seal gum, tackiness agent be the curable resin composition of representative the breaking tenacity height, with the bounding force excellence of adherend, in the test of tracking property, also can keep such effect.
By embodiment 4 and 8 as can be known, by washing the alkali metal content that reduces in the lime carbonate with water, make the storage stability excellence of lime carbonate.
Embodiment 47, comparative example 22
With the surface treated lime carbonate of synthetic in the foregoing description 12, the comparative example 5, preparation is based on the ink resin composition of following proportioning.The evaluation result of gained ink resin composition is as shown in table 8.
(proportioning)
25 parts in surface treated lime carbonate
35 parts of rosin modified phenolic resins
20 parts of Toenol 1140s
17 parts in refining light oil
3 parts in siccative
With three roller kneaders (aboveground making is made) said mixture is dispersed to hondrometer and is determined as below 5 microns, make the ink resin composition.
(viscosity, thixotropy)
With 1rpm, the 10rpm viscosity of BS type viscometer determining, represent thixotropy with 1rpm viscosity/10rpm viscosity based on the ink resin composition of said ratio adjusting.
(transparency)
To coat with 25 microns spreader on the one side of sheet glass based on the ink resin composition that said ratio is regulated, and dry 24 hours at normal temperatures, use photo-electro-spectrophotometer (society of Shimadzu Seisakusho Ltd. system) to measure 550 μ m transmittances then.
(gloss)
With above-mentioned the same dope inkwood oil/fat composition, dry 24 hours at normal temperatures, measure 60 ° of gloss with village's following formula glossmeter then.
(rub resistance test)
Each resin combination is coated complete black mensuration with on the one side of paper with 25 microns spreaders, dry 24 hours at normal temperatures, then according to the test of the rub resistance of JISK5701, estimate according to following benchmark with S type wear testing machine (Sutherland ' s Rub Tester).
Zero: good (not having wearing and tearing)
△: common (abrasion are arranged slightly)
*: bad (a large amount of abrasion)
(binding property)
After above-mentioned the same coating, drying, adhesive plaster (Celltape (registered trademark)) [Nichiban corporate system T405A-18] is pasted on film surface, it is peeled off rapidly, according to the state of peeling off of following benchmark evaluation printing ink.
◎: fabulous (not peeling off fully)
Zero: good (peeling off hardly)
△: common (peeling off a little)
*: bad (peeling off in a large number)
(scrath resistance)
After above-mentioned same coating, drying, carry out anti-scratch test with anti-scratch trier (the smart mechanism of Japan is made society of institute system), according to its state of following benchmark evaluation.
◎: fabulous (not having cut fully)
Zero: good (almost not having cut)
△: common (some cuts are arranged)
*: bad (a lot of cuts are arranged)
Table 8
| Viscosity | The transparency | 60 ° of gloss | Wearability | Binding property | Scrath resistance | ||||
| 1rpm (Pa·s) | 10rpm (Pa·s) | Thixotropy 1rpm/10rpm | |||||||
| Embodiment 47 | Embodiment 12 | 1380 | 410 | 3.4 | 88.5 | 87.0 | ○ | ◎ | ○ |
| Comparative example 22 | Comparative example 5 | 560 | 230 | 2.4 | 72.0 | 73.5 | × | △ | × |
As shown in Table 8, be mixed with surface treated lime carbonate of the present invention and the ink resin composition that forms not only to give aspect the effect performance in viscosity, thixotropy excellent, and gloss, the transparency are also high.And wearability, anti-scratch trace are good, are also showing excellence aspect the high coating strength, and be also excellent with the bounding force of adherend.Its result compares than prior art, can reduce the addition of lime carbonate, and is effective to stablizing ink characteristics.
Industrial applicability
As mentioned above, of the present invention through organic system surface conditioning agent surface treatment calcium carbonate that form, that have the specified particle size characteristic, can be used as especially the resin purposes, when being mixed in the resin, the bonding force of this resin combination and adherend can be improved, and tough filming can be formed.
Surface treated calcium carbonate of the present invention for example when being used for molding resin composition, can prevent the strength decreased of melt run face, and, when the resin combination that will have an excellent impact strength for example is used for coating, printing ink; When the resin combination that will have high glaze and excellent resist sagging, high coating strength is used for that for example plastisol is used resin combination; When the resin combination that will have excellent viscosity, thixotropy and a crumpling resistance for example is used for gel-type resin take fluid sealant, adhesive as representative, can provide have excellent viscosity, thixotropy and seam follow the trail of the resin combination of property.
Claims (16)
1. surface treated lime carbonate is characterized in that: constitutes by having carried out surface-treated lime carbonate, satisfies following formula (a) and (b), (c), (d) and (l) through the organic system surface treatment agent,
(a)20≤Sw≤200m
2/g
(b)1.0≤As≤7.5mg/m
2
(c)0.003≤Dxp≤0.03μm
(d)50≤Dyp/Dxp≤180
(1)0.03≤Is≤3μmol/m
2
Wherein
Sw: by the BET specific surface area of determination of nitrogen adsorption, m
2/ g
As: the hot decrement of the per unit specific surface area of calculating by following formula, mg/m
2
Every 1g is through the hot decrement mg/g/SwDxp of 200 ℃ of-500 ℃ of surface-treated lime carbonate: in the mercury penetration method, during the micropore in range of micropores 0.001-0.1 mu m range distributes, use
The mercury that the average micro-pore diameter of accumulation micropore volume increment/log is calculated is pressed into increment for maximum
Average micro-pore diameter during value Dyp, μ m
Dyp: mercury is pressed into the maximum value of increment, mg/l
Dyp/Dxp: average micropore mass runoff
Is: the alkali metal content of the per unit specific surface area of calculating by following formula
The metal content μ mol//Swm of every 1g lime carbonate
2/ g.
2. the surface treated lime carbonate of claim 1 is characterized in that: further satisfy following formula (e)-(f),
(e)0.03≤Dxs≤1μm
(f) Dys≤30% weight
Wherein
Dxs: in the size-grade distribution that the laser-diffractometer SALD-2000 that makes with society of Shimadzu Seisakusho Ltd. measures, start at the median size of weight accumulative total 50%, μ m from big particle side
Dys: in the above-mentioned size-grade distribution, surpass the weight accumulative total of the particle diameter of 3 μ m, % weight.
3. claim 1 or 2 surface treated lime carbonate have wherein carried out surface-treated lime carbonate through the organic system surface treatment agent and have further satisfied following formula (g)-(j),
(g)0.005≤Dxp≤0.025μm
(h)60≤Dyp/Dxp≤150
(i)0.05≤Dxs≤0.8μm
(j) Dys≤25% weight.
4. claim 1 or 2 surface treated lime carbonate have wherein carried out surface-treated lime carbonate through the organic system surface treatment agent and have satisfied following formula (k),
(k)0.1≤Sw·Dxp≤1.5。
5. claim 1 or 2 surface treated lime carbonate, wherein the calcium carbonate slurry before the organic system surface treatment agent carries out surface treatment, after the slaking satisfies following formula (m),
(m)0.03≤Dx≤0.40μm
Wherein,
Dx: in the size-grade distribution that the centrifugal size-grade distribution meter SA-CP4 by society of Shimadzu Seisakusho Ltd. system measures, start at 50% o'clock particle diameter of weight accumulative total, μ m from big particle diameter side.
6. claim 1 or 2 surface treated lime carbonate, wherein the organic system surface treatment agent is at least a material that is selected from saturated fatty acid, unsaturated fatty acids, resinous acid, sulfonic acid, these sour an alkali metal salts, alkaline earth salt, ammonium salt, amine salt, cationic surfactant, aniorfic surfactant and nonionic surface active agent.
7. the preparation method of claim 1 or 2 surface treated lime carbonate, it is characterized in that: the material of 0.5-15% weight and metallic ion coordination formation complex compound is added in the calcium hydroxide slurry, carry out carbonation reaction by being blown into carbon dioxide, synthetic calcium carbonate, with this lime carbonate concentration adjustment to 2.4-13.0% weight, slaking is carried out surface treatment with the lime carbonate of gained with the organic system surface treatment agent.
8. resin combination is characterized in that: the surface treated lime carbonate of claim 1 is mixed into resin and forms.
9. resin combination is characterized in that: the surface treated lime carbonate of claim 2 is mixed into resin and forms.
10. claim 8 or 9 resin combination, wherein resin is a molding resin.
11. the resin combination of claim 8 or 9, wherein resin is a coating resin.
12. the resin combination of claim 8 or 9, wherein resin is the plastisol resin.
13. the resin combination of claim 8 or 9, wherein resin is a resin for printing ink.
14. the resin combination of claim 8 or 9, wherein resin is the seal gum resin.
15. the resin combination of claim 8 or 9, wherein resin is the tackiness agent resin.
16. the resin combination of claim 8 or 9, wherein the combined amount of surface treated lime carbonate is the 1-100 weight part with respect to 100 parts by weight resin.
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| WO2010008607A1 (en) * | 2008-07-18 | 2010-01-21 | Armstrong World Industries, Inc. | Aldehyde reducing compositions |
| US9221970B2 (en) * | 2008-12-19 | 2015-12-29 | 3M Innovative Properties Company | Nanocalcite composites |
| CN101671494B (en) * | 2009-09-19 | 2013-03-20 | 张家界恒亮新材料科技有限公司 | Surface modified calcium carbonate and preparation method thereof |
| ES2763961T3 (en) * | 2010-02-15 | 2020-06-01 | Shiraishi Kogyo Kaisha Ltd | Surface treated calcium carbonate and paste-like resin composition containing the same |
| US9422419B2 (en) * | 2012-05-08 | 2016-08-23 | Maruo Calcium Co., Ltd. | Surface-treated calcium carbonate filler, and curable resin composition containing the filler |
| CN103897434B (en) * | 2014-04-19 | 2016-03-30 | 芮城新泰纳米材料有限公司 | The preparation method that plastic master batch is Nano calcium carbonate dedicated |
| CN107429079B (en) * | 2015-03-23 | 2019-08-23 | 丸尾钙株式会社 | Curable resin composition surface treatment pearl filler and the curable resin composition containing the filler |
| CN105111501B (en) * | 2015-07-30 | 2018-05-01 | 杭州明鑫钙业有限公司 | A kind of thermoplasticity calcium carbonate toughness reinforcing particle and preparation method thereof |
| CN105062118B (en) * | 2015-08-04 | 2017-07-14 | 南京林业大学 | A kind of micropore antimicrobial sheet material based on discarded pharmaceutical pack plastics and preparation method thereof |
| CN108359274A (en) * | 2018-02-07 | 2018-08-03 | 广西大学 | Rosin derivative chelates calcium modified Nano or lightweight CaCO3Powder preparation method |
| CN116023802A (en) * | 2022-12-27 | 2023-04-28 | 池州市贵兴非矿新材料有限公司 | Modified heavy calcium carbonate with low oil absorption value |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1072215A (en) * | 1996-08-29 | 1998-03-17 | Maruo Calcium Co Ltd | Production of fine particulate calcium carbonate |
| JPH11268912A (en) * | 1998-03-24 | 1999-10-05 | Maruo Calcium Co Ltd | Inorganic dispersing agent, stabilizer for suspension polymerization, polymeric particle, unsaturated polyester resin composition, and toner composition |
| CN1305956A (en) * | 2000-01-18 | 2001-08-01 | 北京化工大学 | Process for preparing calcium carbonate deposit by continuous method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1072215A (en) * | 1996-08-29 | 1998-03-17 | Maruo Calcium Co Ltd | Production of fine particulate calcium carbonate |
| JPH11268912A (en) * | 1998-03-24 | 1999-10-05 | Maruo Calcium Co Ltd | Inorganic dispersing agent, stabilizer for suspension polymerization, polymeric particle, unsaturated polyester resin composition, and toner composition |
| CN1305956A (en) * | 2000-01-18 | 2001-08-01 | 北京化工大学 | Process for preparing calcium carbonate deposit by continuous method |
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