CN1668710A - Modified calcium carbonate, polymer composition containing the same and process for producing them - Google Patents

Modified calcium carbonate, polymer composition containing the same and process for producing them Download PDF

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Publication number
CN1668710A
CN1668710A CNA038172356A CN03817235A CN1668710A CN 1668710 A CN1668710 A CN 1668710A CN A038172356 A CNA038172356 A CN A038172356A CN 03817235 A CN03817235 A CN 03817235A CN 1668710 A CN1668710 A CN 1668710A
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layer
calcium carbonate
acid
silicon dioxide
resinate
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CN1290935C (en
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筒井昌一
石田博嗣
细井和幸
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Shiraishi Central Laboratories Co Ltd
Shiraishi Kogyo Kaisha Ltd
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Shiraishi Central Laboratories Co Ltd
Shiraishi Kogyo Kaisha Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/02—Compounds of alkaline earth metals or magnesium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/18—Carbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/02—Ingredients treated with inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/02—Compounds of alkaline earth metals or magnesium
    • C09C1/021—Calcium carbonates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/02—Compounds of alkaline earth metals or magnesium
    • C09C1/021—Calcium carbonates
    • C09C1/022—Treatment with inorganic compounds
    • C09C1/024—Coating
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area

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  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Inorganic Chemistry (AREA)
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  • Pigments, Carbon Blacks, Or Wood Stains (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)

Abstract

A modified calcium carbonate comprising calcium carbonate as a raw material and, superimposed on the surface thereof, (i) a silica layer, (ii) an organic acid layer constituted of at least one member selected from the group consisting of fatty acids, fatty acid salts, fatty acid esters, resin acids, resin acid salts and resin acid esters and (iii) a layer of silane coupling agent; and a polymer composition comprising the modified calcium carbonate.

Description

Modified calcium carbonate and contain the polymer composition and the manufacture method thereof of modified calcium carbonate
Technical field
The present invention relates to effectively to be used as polymkeric substance such as rubber, plastics reinforcing filler modified calcium carbonate and contain the polymer composition and the manufacture method thereof of this modified calcium carbonate.
Background technology
At present, white carbon black (for example wet silicon dioxide) needing to be widely used as the reinforcing filler of the polymer product of high strength, high rigidity.But because wet silicon dioxide is acid filler, so when directly cooperating with polymkeric substance, it is slow to vulcanize, for this reason, the agent of needs interpolation polyoxyethylene glycol isoreactivity.And wet silicon dioxide also has shortcoming aspect rerum natura, and in the time of for example in being matched with rubber, tensile-permanent set is poor.And wet silicon dioxide can make the viscosity of unvulcanized rubber increase aspect processibility, goes wrong at aspects such as roll-type crimp tendency.
Because the lime carbonate as polymeric extenders, toughener etc. is weakly alkaline, so in being engaged in polymkeric substance the time, need not to add promoting agent.And compare with wet silicon dioxide, lime carbonate can be brought up the polymkeric substance of tensile-permanent set excellence.But, when with lime carbonate when the polymkeric substance reinforcing filler, can not give mechanical characteristics such as the tensile stress worked as with the polymer phase that cooperates wet silicon dioxide, tensile strength, tear strength, wearability.
In addition, the problem of the lime carbonate after the material that mercaptan or amine etc. has a reactive functional group carries out surface treatment is: although the tensile stress when hardness and low elongation is big, but compare with wet silicon dioxide, rerum naturas such as tensile strength, tear strength, wearability are relatively poor.
For solving the problem of this base polymer with reinforcing filler, people attempt having adopted (i) that filler particles anisotropy (high length-diameter ratio) is changed, (ii) use fine filler particles, (iii) utilize for example to coat silane coupling agent etc. and reactive functional group is imported schemes such as filler particles surface.
According to (i) give filler anisotropic scheme owing to hindered the flowability of polymkeric substance, so obtained mechanical properties such as high rigidity, high-modulus.According to the scheme of (ii) use subparticle, owing to strengthened interaction between filler-polymkeric substance or the interaction between filler-filler, so improved tensile elongation, tensile strength.And, between filler-polymkeric substance, imported chemical bond, so improved tensile-permanent set and wearability etc. according to the scheme of (iii) importing reactive functional group.
But; under the situation of lime carbonate; owing to there is the situation that is difficult to obtain anisotropy, particularly diaxial orientation; so scheme (i) is not too suitable; and, attempt to improve the rerum natura when being matched with in the polymkeric substance according to the fine filler particles of use (ii) or importing reactive functional group (iii) scheme to the filler particles surface.
This class example can be enumerated No. 910471 grade of Japanese Patent and have the method on the mass treatment lime carbonate surface of OH base with silica hydrosol etc., or No. the 2745033rd, Japanese Patent etc. had not only had the COOH base but also had the method etc. of the polymer treatment of OH base.
But when using silica hydrosol to handle submicron order lime carbonate, when drying, silica hydrosol can make lime carbonate condense curing by force, produces big particle, causes flocculated particle to be difficult to separate.And when use has the polymer treatment of COOH base and the basic two kinds of groups of OH, might cover the OH base fully as the alkyl chain of skeleton, and can not fully combine with silane coupling agent.
Summary of the invention
Main purpose of the present invention is to provide a kind of modified calcium carbonate, makes when this modified calcium carbonate is matched with in the polymkeric substance, can obtain demonstrating the polymer product of the mechanical characteristic suitable with white carbon black, and can give play to excellent forming polymer processibility.
The inventor finds: reaching (iii) by the organic acid layer that with (i) silicon dioxide layer, (ii) be selected from least a formation in lipid acid, soap, fatty acid ester, resinous acid, resinate and the resinate, silane coupling agent layer is attached to raw material lime carbonate surface, significantly improved the rerum natura that cooperates the polymer product of lime carbonate, after the further investigation, finished the present invention in view of the above.
That is, the present invention relates to following modified calcium carbonate, the polymer composition that contains this modified calcium carbonate, their manufacture method, the formed body that can obtain by the moulding of this polymer composition.
(1) a kind of modified calcium carbonate, it is characterized in that, on the surface of lime carbonate, possess (i) silicon dioxide layer, (ii) be selected from the organic acid layer and the (iii) silane coupling agent layer of at least a formation of lipid acid, soap, fatty acid ester, resinous acid, resinate and resinate.
(2) as (1) described modified calcium carbonate, wherein, the BET specific surface area of lime carbonate is 5～120m 2/ g.
(3) as (1) described modified calcium carbonate, wherein, the BET specific surface area of modified calcium carbonate is 4～110m 2/ g.
(4) as (1) described modified calcium carbonate, it is characterized in that, is 100 weight parts with lime carbonate, and then the silicon dioxide layer adhesion amount is 0.5～15 weight part, and organic acid layer adhesion amount is 0.5～20 weight part, and the silane coupling agent layer adhesion amount is 0.05～10 weight part.
(5) the modified calcium carbonate manufacture method of (1) described modified calcium carbonate particularly is characterized in that, comprising:
1. by silica hydrosol is added in the calcium carbonate slurry, form the operation of (i) silicon dioxide layer on the lime carbonate surface;
2. add in the calcium carbonate slurry with this silicon dioxide layer being selected from least a of lipid acid, soap, fatty acid ester, resinous acid, resinate and resinate, form the (ii) operation of organic acid layer;
3. to having gained (i) silicon dioxide layer and the (ii) operation that dehydrates of the calcium carbonate slurry of organic acid layer;
4. with silane coupling agent to have gained (i) silicon dioxide layer and (ii) the calcium carbonate granule of organic acid layer carry out surface treatment, form the (iii) operation of silane coupling agent layer.
(6) contain following (a) and polymer composition (b), wherein,
(a) for possessing (i) silicon dioxide layer on the lime carbonate surface, (ii) reaching the (iii) modified calcium carbonate of silane coupling agent layer by at least a organic acid layer that forms that is selected from lipid acid, soap, fatty acid ester, resinous acid, resinate and the resinate; (b) be polymkeric substance.
(7) as (6) described polymer composition, wherein, lime carbonate BET specific surface area is 5～120m 2/ g.
(8) as (6) described polymer composition, wherein, the BET specific surface area of modified calcium carbonate is 4～110m 2/ g.
(9) as (6) described polymer composition, it is characterized in that, be 100 weight parts with lime carbonate, and the silicon dioxide layer adhesion amount is 0.5～15 weight part, the adhesion amount of organic acid layer is 0.5～20 weight part, and the adhesion amount of silane coupling agent layer is 0.05～10 weight part.
(10) as (6) described polymer composition, it is characterized in that, is 100 weight parts with polymkeric substance, and modified calcium carbonate content is 5～150 weight parts.
(11) as the manufacture method of (6) described polymer composition, it is characterized in that, also comprise: to the lime carbonate surface have (i) silicon dioxide layer, (ii) be selected from lipid acid, soap, fatty acid ester, resinous acid, resinate and resinate at least a formation the organic acid layer and (iii) the modified calcium carbonate of silane coupling agent layer be added into polymkeric substance, blended operation then.
(12) as the manufacture method of (6) described polymer composition, it is characterized in that, also comprise: the modified calcium carbonate of organic acid layer that will have (i) silicon dioxide layer, (ii) is selected from least a formation of lipid acid, soap, fatty acid ester, resinous acid, resinate and resinate is added into polymkeric substance, then silane coupling agent is added into polymkeric substance, decomposite operation.
(13) as the manufacture method of (6) described polymer composition, it is characterized in that, also comprise: silane coupling agent is added into polymkeric substance, and the modified calcium carbonate of organic acid layer that will have (i) silicon dioxide layer then, (ii) is selected from least a formation of lipid acid, soap, fatty acid ester, resinous acid, resinate and resinate is added into decomposite operation behind the polymkeric substance.
(14) formed body that gets by (6) described polymer composition moulding.
Below, specify the present invention.
In the present invention, " layer " is to cover lime carbonate or handle lime carbonate all or the structure of local surfaces, remove this and be not particularly limited, needn't cover all surface continuously, handle lime carbonate be have silicon dioxide layer, one or both the modified calcium carbonate in organic acid layer or the silane coupling agent layer.
The contriver infers, the surface layer structure of modified calcium carbonate of the present invention comprises (1) part, (2) part, and (3) state of the partially mixed existence that exists of part, (4) silicon dioxide layer, organic acid layer, the silane coupling agent layer independent (individual layer) of lamination silicon dioxide layer, organic acid layer successively of lamination silicon dioxide layer, silane coupling agent layer successively of lamination silicon dioxide layer, organic acid layer, silane coupling agent layer successively.
Bed thickness is not particularly limited, and each layer thickness can suitably be adjusted according to the expection rerum natura.
Raw material lime carbonate
In the present invention, the kind of raw material lime carbonate is not had special restriction, can use known water-ground limestone, synthetic (settleability) lime carbonate etc.
Water-ground limestone can get by using known dry type such as roller crusher, high speed rotating pulverizer (pulverizer is cut off in impact), ball mill, upset (tumbler) pulverizer, planetary ball mill, aeropulverizer or case of wet attrition method to pulverize modulation.
Synthetic (settleability) lime carbonate can obtain by milk of lime-carbon dioxide reaction method, calcium chloride-SODA ASH LIGHT 99.2 reaction method, milk of lime-known methods such as SODA ASH LIGHT 99.2 reaction method.Example as milk of lime-carbon dioxide reaction method, can be by with oil such as coke or heavy oil or light oil being burning limestone mines such as fuel, natural-gas, LPG, generate unslaked lime, water and reaction by this unslaked lime, generate calcium hydroxide slurry, bubble with the combustion by-products carbonic acid gas again,, generate lime carbonate with this slurry reaction.Condition during by the setting carbon dioxide reaction, the sub-micron particulate that can obtain expecting.In addition, also be suitable for adopting the zinc salts such as zinc hydroxide that hydrolysis is formed to add in the calcium hydroxide slurry, meanwhile bubble also and slurry reaction, make the method (No. 401044, Japanese Patent) of the lime carbonate finer than above-mentioned lime carbonate by carbonic acid gas.
BET specific surface area to raw material lime carbonate among the present invention is not particularly limited, and is generally 5～120m 2/ g, preferable range is 20～110m 2/ g, more preferably scope is 50～100m 2/ g.
BET specific surface area available gas absorption method is tried to achieve by the nitrogen adsorptive capacity that detects lime carbonate.
When the BET of raw material lime carbonate specific surface area was excessive, needing increased at least a organic acid consumption that is selected from lipid acid, soap, fatty acid ester, resinous acid, resinate and resinate, and cost benefit is poor.Because of lipid acid, soap, fatty acid ester, resinous acid, resinate and resinate also play the effect of tenderizer, so can be detrimental to reinforced effects to polymkeric substance.
And when the BET of raw material lime carbonate specific surface area is too small, might reduce the effect that reaches by subparticle, reduce reinforced effects to polymkeric substance.
The particle diameter of raw material lime carbonate can suitably be selected, to obtain desired result.And usually, when observing with scanning electron microscope, raw material lime carbonate particulate primary granule directly is preferably 0.01～0.5 μ m, more preferably 0.02～0.4 μ m.
Silicon dioxide layer
In the present invention, silicon dioxide layer is the layer that gets with the silica hydrosol processing.
The used silica hydrosol of the present invention can adopt the colloidal sol that is made by known method.For example, can use acid decomposition and silica hydrosol.Also can use by with mineral acids such as hydrochloric acid, sulfuric acid, Tai-Ace S 150, or organic acids such as acetate, vinylformic acid, or acidic substance such as carbonic acid gas etc. add in the sodium silicate solution and the amorphous silica water-sol that generates.The silica hydrosol that utilizes dialysis method to generate that also can use water glass to see through semi-permeable membranes and generate.In addition, also can adopt the silica hydrosol that generates by the ion exchange method that makes spent ion exchange resin.
The method of utilizing silica hydrosol that lime carbonate is handled can be enumerated, for example, the sodium silicate aqueous solution with proper concn adds in the calcium carbonate slurry acidic substance such as stirring while dropping inorganic acid or organic acid to, generate the active silica water-sol, handle the method on lime carbonate surface.
When using in advance synthetic silica hydrosol, silica hydrosol can be added in the calcium carbonate slurry, stir by brute force and handle.
It is 0.5～20% that calcium carbonate slurry can use solid content, is preferably the slurry about 1～15%.The concentration of sodium silicate aqueous solution is used about 1～40% the aqueous solution.The ratio of the solid content of sodium silicate silicate and calcium carbonate slurry is 11.3%～200%.
Silicon-dioxide in the silica hydrosol is roughly quantitatively attached on the lime carbonate.
The lime carbonate adhesion amount of the silica hydrosol that the present invention is used is not particularly limited, with raw material lime carbonate is 100 weight parts, the silica volume that is got by the silica hydrosol adhesion amount of lime carbonate is generally 0.5～15 weight part, be preferably 1～12 weight part, more preferably 2～10 weight parts.
The adhesion amount of silica hydrosol can be according to suitably adjusting as the BET specific surface area etc. of the lime carbonate that adheres to object.
By attached to the silica hydrosol on the lime carbonate silicon-dioxide adhesion amount when very few, can reduce with silane coupling agent combining required reaction area, so might can not show the rubber rerum natura of expection.And when adhesion amount was too much, except that attached to the lime carbonate surface, the remaining silica water-sol existed in solution, so silica hydrosol solidifies the strong aggegation of lime carbonate when drying, the difficult big particle of pulverizing increases.The pearl filler that contains this class big particle might cause reductions such as the tensile break strength of polymkeric substance, counter-bending cracking.
The organic acid layer
In the present invention, the organic acid layer is meant the layer that gets with at least a processing that is selected from lipid acid, soap, fatty acid ester, resinous acid, resinate and resinate.
The used lipid acid of the present invention can be enumerated carbonatoms 6～24, particularly 10～20 saturated or unsaturated fatty acids.
Saturated or the unsaturated fatty acids of carbonatoms 6～24 can be enumerated stearic acid, palmitinic acid, lauric acid, mountain Yu acid, oleic acid, sinapinic acid, linolic acid etc.Be preferably stearic acid, palmitinic acid, lauric acid, oleic acid especially.They also can two kinds and above mixing use.
Soap can be enumerated an alkali metal salts such as the sodium salt, sylvite of above-mentioned carbonatoms about 6～24, particularly 10～20 saturated or unsaturated fatty acids.
And fatty acid ester can be enumerated the ester that the saturated fatty alcohol of alcohol, the particularly carbonatoms 10～18 of above-mentioned carbonatoms about 6～24, particularly 10～20 saturated or unsaturated fatty acids and carbonatoms 6～18 generates etc.
Can enumerate following method with the method that lipid acid, soap and/or fatty acid ester are handled.
At first, in the basic metal aqueous solution such as the NaOH aqueous solution, the KOH aqueous solution, limit heating lipid acid limit saponification (generating metal-salts such as Na salt, K salt) is the solution shape.
The water-soluble liquid measure of basic metal is removed this and is not had special restriction so long as the fatty acid saponification aequum gets final product.The concentration of the basic metal aqueous solution is about 1～40%, is preferably about 1～20%.
The calcium carbonate water suspension liquid that will form silicon dioxide layer then is preheated to 30～50 ℃, and above-mentioned solution shape fatty acid soaps is added in this suspension liquid, mixes, and forms the organic acid layer of fatty acids and/or soap.The ratio that adds fatty acid soaps to lime carbonate water-based suspension liquid is about 10～70%, is preferably about 10～50%.
When directly using soap such as lipid acid Na, the aqueous solution after the modulation preheating is earlier handled with method same as above.
And, also can use lipid acid to handle without saponification.For example, keep at the lime carbonate that forms silicon dioxide layer can being heated to more than the fusing point of lipid acid under the situation of pulverulence, stir simultaneously,,, form the organic acid layer of fatty acids through mixing to wherein adding lipid acid.
The used Resin Acid of the present invention can be enumerated rosin acids or its polymkeric substance, nilox resin, staybelite, polymerized rosin, abietate (for example an alkali metal salt, alkaline earth salt) or rosin esters (for example pentalyn, ester gum, staybelite pentaerythritol ester) etc. such as sylvic acid, dehydroabietic acid, dihydro sylvic acid.Wherein, be preferably sylvic acid and dehydroabietic acid.
The method of handling with resinous acid, resinate and/or resinate can adopt and use the same mode of lipid acid, soap and/or fatty acid ester.Particularly, can be in the basic metal aqueous solution such as the NaOH aqueous solution, the KOH aqueous solution, the limit heating edge is the solution shape with resinous acid saponification (generating metal-salts such as Na salt, K salt).
The water-soluble liquid measure of basic metal is removed this and is not had special restriction so long as resinous acid saponification aequum gets final product.The concentration of the basic metal aqueous solution is about 1～40%, is preferably about 1～20%.
The calcium carbonate water suspension liquid that will form silicon dioxide layer then is preheated to 30～50 ℃, and above-mentioned solution shape resin acid soaps is added in this suspension liquid, mixes, and forms the organic acid layer of resinous acid and/or resinate.The ratio that adds resin acid soaps to lime carbonate water-based suspension liquid is about 10～70%, is preferably about 10～50%.
When directly using soap such as resinous acid Na, the resin acid soaps aqueous solution after the modulation preheating is earlier handled with method same as above.
And, also can use resinous acid to handle without saponification.For example, keep at the lime carbonate that forms silicon dioxide layer can being heated to more than the fusing point of resinous acid under the situation of pulverulence, stir simultaneously,,, form the organic acid layer of resinous acid through mixing to wherein adding resinous acid.
To organic acid layer consumption, at least a adhesion amount that promptly is selected from lipid acid, soap, fatty acid ester, resinous acid, resinate and resinate is not particularly limited, with raw material lime carbonate is 100 weight parts, be generally about 0.5～20 weight part, be preferably about 1～15 weight part, more preferably about 2～12 weight parts.
Silane coupling agent layer
Silane coupling agent layer of the present invention is the layer that gets with the silane coupling agent processing.
The used silane coupling agent of the present invention can be enumerated for example vinyl trichloro silane, vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three (beta-methoxy-oxyethyl group) silane, β-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, γ-(2-aminoethyl) aminopropyl trimethoxysilane, γ-glycidyl propyl trimethoxy silicane, γ-glycidyl oxypropyl trimethyl diethoxy silane, γ-glycidyl propyl-triethoxysilicane, γ-metacryloxy propyl group methyl dimethoxysilane, γ-metacryloxy propyl trimethoxy silicane, γ-metacryloxy propyl group methyldiethoxysilane, γ-metacryloxy propyl-triethoxysilicane, N-β (aminoethyl) γ-aminopropyl methyl dimethoxysilane, N-β (aminoethyl) γ-An Bingjisanjiayangjiguiwan, N-β (aminoethyl) γ-An Bingjisanyiyangjiguiwan, the 3-aminopropyl trimethoxysilane, the 3-aminopropyl triethoxysilane, N-phenyl-γ-An Bingjisanjiayangjiguiwan, γ-r-chloropropyl trimethoxyl silane, γ-Qiu Jibingjisanjiayangjiguiwan, two-(the 3-[triethoxysilyl]-propyl group)-four sulfanes (TESPT), two-(the 3-[triethoxysilyl]-propyl group)-disulphanes etc.
Especially preferably use γ-(2-aminoethyl) aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, N-β (aminoethyl) γ-An Bingjisanjiayangjiguiwan, γ-Qiu Jibingjisanjiayangjiguiwan, two-(3-[triethoxysilyl]-propyl group)-four sulfanes, two-(3-[triethoxysilyl]-propyl group)-disulphanes.
The present invention is not particularly limited the method for using silane coupling agent to handle lime carbonate, can suitably use known various surface treatment methods at present.
When the lime carbonate with silicon dioxide layer and organic acid layer is dried powder, for example applicablely stir this calcium carbonate powders limit at the mixing tank inner edge and drip silane coupling agent, or use atomizer to spray, make silane coupling agent attached to the lip-deep method of lime carbonate etc.At this moment, as required, after surface treatment, also can carry out heat drying.
And when under the suspension liquid state, obtaining having the lime carbonate of silicon dioxide layer and organic acid layer, can be by the soluble silane coupling agent be dropped into this suspension liquid, make silane coupling agent be adsorbed on the lime carbonate surface and carry out surface treatment, filtration treatment thing and dry can make with the modified calcium carbonate after the silane coupling agent processing then.Form the lime carbonate of silicon dioxide layer and organic acid layer on the surface or be under the situation of suspension liquid through the lime carbonate of coupling agent treatment on this basis, handle evenly, also can use stirrer or wet grinding machines such as ball mill, sand mill for making.
Adhesion amount to the silane coupling agent that constitutes silane coupling agent layer is not particularly limited, and the raw material lime carbonate with respect to 100 weight parts is generally about 0.05～10 weight part, is preferably about 0.07～5 weight part, more preferably about 0.1～3 weight part.Above-mentioned adhesion amount can be by adhering to object as silane coupling agent the BET specific surface area etc. of lime carbonate suitably adjust.
Modified calcium carbonate
Modified calcium carbonate of the present invention be with (i) silicon dioxide layer, (ii) by at least a organic acid layer that constitutes that is selected from lipid acid, soap, fatty acid ester, resinous acid, resinate and resinate and (iii) silane coupling agent layer attached to forming on the raw material lime carbonate surface.
The concrete available following method manufacturing of modified calcium carbonate of the present invention.
For example, comprise the method for following operation: add silica hydrosol in the calcium carbonate slurry to (1), forms the operation of silicon dioxide layer on the lime carbonate surface; (2) add in the calcium carbonate slurry that possesses above-mentioned silicon dioxide layer being selected from least a of lipid acid, soap, fatty acid ester, resinous acid, resinate and resinate, form the operation of organic acid layer; (3) form above-mentioned silicon dioxide layer and organic acid layer calcium carbonate slurry dehydrate operation; (4) with silane coupling agent the gained calcium carbonate granule is carried out surface treatment, form the operation of silane coupling agent layer.
Utilize this method, just obtain being characterized as raw material lime carbonate particle surface and have (i) silicon dioxide layer, (ii) the organic acid layer and the (iii) modified calcium carbonate of the present invention of silane coupling agent layer.
The BET specific surface area of the modified calcium carbonate of this courage is not particularly limited, and is generally 4～110m 2About/g, preferable range is 15～100m 2About/g, more preferably scope is 40～90m 2About/g.
BET specific surface area gas adsorption method is tried to achieve by the nitrogen adsorption amount that detects lime carbonate.
When the BET of modified calcium carbonate specific surface area is excessive, might impair reinforced effects to polymkeric substance.And when the BET of modified calcium carbonate specific surface area is too small, by may reducing the effect that obtains by subparticle, reduce with reinforced effects after polymkeric substance cooperates.
And the particle diameter of modified calcium carbonate of the present invention can suitably be set according to desired result.Usually, when observing with scanning electron microscope, modified calcium carbonate particulate primary granule size is preferably 0.01～0.6 μ m, more preferably 0.02～0.5 μ m.
Polymer composition
Polymer composition of the present invention adds in the polymkeric substance such as rubber or plastics by the modified calcium carbonate with the invention described above and obtains.
The modified calcium carbonate addition of polymer composition is not particularly limited, and is 100 weight parts with polymkeric substance, is generally 5～150 weight parts, is preferably 30～120 weight parts, more preferably 50～110 weight parts.
When with respect to polymkeric substance, when the modified calcium carbonate use level is too much, can hinder the flowability of polymkeric substance, so do not select for use.Particularly when polymkeric substance was rubber, rubber is mobile to disappear poor in processability.The shortcoming that also has hardness to become too high.And when use level is very few, fail to improve the elasticity of flexure coefficient or the shock strength of polymkeric substance, so do not select for use.Particularly when polymkeric substance was rubber, the silane coupled dosage that reacts with rubber was few, can not demonstrate the rerum natura of expection.
Polymkeric substance in the polymer composition of the present invention for example can use natural rubber, synthetic rubber, synthetic resins, thermoplastic elastomer etc.
Natural rubber is meant the rubber-like polymer substance that is obtained by natural phant, so long as have cis-1 in the chemical structure, 4-polyisoprene structure gets final product, and shape, tone etc. is not particularly limited.
Synthetic rubber can be enumerated for example synthetic polyisoprene, benzene fourth rubber, divinyl rubber, chloroprene rubber, paracril, isoprene-isobutylene rubber, halogenated butyl rubber, ethylene-propylene rubber(EPR), urethanes, silicon rubber, viton, chlorosulfonated polyethylene, epichloro hydrin rubber, polysulfide rubber etc.
Synthetic resins both can use thermoplastic resin, also can use thermosetting resin.
Thermoplastic resin can be enumerated for example new LDPE (film grade), medium-density polyethylene, high density polyethylene(HDPE), straight-chain low density polyethylene, ultra-low density polyethylene, vinyl-vinyl acetate copolymer (EVA), ethylene-ethyl acrylate copolymer (EEA), ethylene-propylene copolymer, alfon, ethylene-propylene rubber, polybutene, isoprene-isobutylene rubber, high impact polystyrene (HIPS), polystyrene (PS), ABS, vinyl chloride-based resin, methacrylic resin, methyl methacrylate (MMA)-styrol copolymer, nylon 6, nylon 66, NYLON610, nylon 12, polyamide resins such as nylon 46, polycarbonate, polyformaldehyde resin, polybutylene terephthalate (PBT), polyethylene terephthalate polyester such as (PET), polyphenylene oxide, polyphenylene sulfides, polyether-ether-ketone, polyallyl ether ketone, polyamidoimide, polyimide, polyetherimide, polysulfones, polyethersulfone, fluoro-resin, urethane, ionic polymer, polyvinylidene chloride, polyvinyl chloride, poly-Dicyclopentadiene (DCPD), methylpentene resin, the plain resin of polyacrylonitrile fibre etc.
Thermosetting resin can be enumerated for example resol, bisphenol A type epoxy resin, cresols-phenol aldehyde type epoxy resin, phenolic aldehyde-phenol aldehyde type epoxy resin, bisphenol-type epoxy resin, naphthalene-ring containing Resins, epoxy, allyl group phenolic aldehyde-phenol aldehyde type epoxy resin, alicyclic epoxy resin, Resins, epoxy such as hetero ring type Resins, epoxy and halogenide thereof, urethane (injection molded article is used), furane resin, unsaturated polyester, melmac, urea resin, allylic resin (DAP), polyimide, silicone resin (comprising ambient cure) etc.
Thermoplastic elastomer can be used polystyrene thermoplastic elastomer, polypropylene-based thermoplastic elastomer, polydiene based thermoplastic elastomerics, chlorine based thermoplastic elastomerics, engineering plastics based elastomers etc.
The polymer composition that contains modified calcium carbonate of the present invention can be obtained by following method, and for example (1) will have (i) silicon dioxide layer, (ii) be selected from the organic acid layer and the (iii) manufacture method that cooperates with above-mentioned polymkeric substance of the modified calcium carbonate of the present invention of silane coupling agent layer of at least a formation of lipid acid, soap, fatty acid ester, resinous acid, resinate and resinate; Or, the manufacture method that partially modified lime carbonate before (2) will have (i) silicon dioxide layer and (ii) be selected from the handling with silane coupling agent of organic acid layer of at least a formation of lipid acid, soap, fatty acid ester, resinous acid, resinate and resinate and silane coupling agent cooperate with other polymkeric substance.
(2) method specifically can enumerate by will have (i) silicon dioxide layer and (ii) the partially modified lime carbonate of organic acid layer add in the polymkeric substance, again silane coupling agent is added in the polymkeric substance, blended manufacture method then, or silane coupling agent added in the polymkeric substance, will have then (i) silicon dioxide layer and (ii) the partially modified lime carbonate of organic acid layer add blended manufacture method in the polymkeric substance to.
As mentioned above, in the time will having (i) silicon dioxide layer and (ii) the partially modified lime carbonate of organic acid layer and silane coupling agent add in the polymkeric substance respectively, after adding respectively, through mixing, silane coupling agent is adsorbed on have (i) silicon dioxide layer and the (ii) partially modified lime carbonate surface of organic acid layer, formation has (i) silicon dioxide layer, (ii) the organic acid layer reaches (iii) three layers of modified calcium carbonate of silane coupling agent layer, makes the polymer composition that adds this modified calcium carbonate.
In the time will having (i) silicon dioxide layer and (ii) the modified calcium carbonate of organic acid layer and silane coupling agent add in the polymkeric substance respectively, with raw material lime carbonate is 100 weight parts, be used to form have (i) silicon dioxide layer, (ii) the organic acid layer and (iii) the use level of the silane coupling agent of the modified calcium carbonate of silane coupling agent layer be about 0.05～10 weight part, be preferably about 0.07～5 weight part, more preferably 0.1～3 weight part.
In the polymer composition of the present invention, also can add known Synergist S-421 95 as required.For example also can use other fillers such as silicon-dioxide, clay, aluminium hydroxide simultaneously.And, as required, also can add additives such as machine oil, antioxidant, antiaging agent, promoting agent, stearic acid, zinc oxide, wax, vulcanizing agents such as sulphur, vulcanization aid etc.
Polymkeric substance of the present invention can by polymkeric substance, modified calcium carbonate and the above-mentioned Synergist S-421 95 that adds as required is mixing, heat, extrude, sulfuration etc. makes.
Mixing condition is not had special restriction, can suitably select rotating speed, punching press etc., melting temperature, the mixing time of volume, the turner of input kneading device, each condition such as kind of kneading device according to purpose.Above-mentioned kneading device does not have special restriction, can use closed or open in any, for example known kneading device specifically can use Banbury (registered trademark), Intermix (registered trademark), kneading machine, roller etc.
Heating condition is not particularly limited, can selects each condition such as suitable Heating temperature, heat-up time, heating unit according to purpose.Heating unit can be enumerated for example roller machine etc.
Extrusion condition does not have special restriction, can select suitable to find time according to purpose, each condition such as extruded velocity, extrusion device, extrusion temperature.Extrusion device can be enumerated and for example be used to forcing machine of extruding rubber composition for tire etc.
Formed body
Formed body of the present invention can utilize in the known various forming method any to make the polymer composition moulding that contains modified calcium carbonate of the present invention and get.
If rubber item, the used forming method of the present invention with regard to available rolling processing, extrude processing, coin etc., if resin, with regard to available injection molding, compressed moulding, transfer formation, extrusion moulding, blow molding, rolling processing etc.
For example, if resin, polymer composition of the present invention just can obtain film or sheet-like formed body by rolling processing or extrusion moulding.And be suitable under the temperature of used polymer composition, this film or laminar formed body are implemented thermoforming, just can obtain thermally molded article each.And after obtaining particle, utilize extrusion moulding of gained particle or blow molding for example melt extruding above-mentioned polymer composition and granulation, just can obtain injection molded article or hollow molded body respectively.
And if rubber, after above-mentioned moulding, can be by metal pattern molding sulfuration, plate sulfuration, directly-methods such as indirect steam sulfuration, ratio-frequency heating endless vulcanization obtain the sulfidization molding body.Do not have special restriction to carrying out sulfurized device, method, condition etc., can suitably select according to purpose.
Because formed body of the present invention contains modified calcium carbonate of the present invention, so each excellent such as mechanical property, wear resistance, permanent extension can be used for tire, roller, sole, hose, flexible pipe etc.
Embodiment
Below, by specific embodiment and comparative example explanation the present invention, but the present invention is not limited to these embodiment.
In addition, in following embodiment and comparative example, silica hydrosol use with acidic substance add to sodium silicate solution (Japan and the pure medicine system of light, 193-08185) in and the water-sol of generation.
Lipid acid uses the fatty acid mixt (with the pure medicine system of light, oleic acid (159-00246), stearic acid (199-10995), palmitinic acid (165-00102)) that contains oleic acid, stearic acid, palmitinic acid etc.
Resinous acid uses sylvic acid (with the pure medicine system of light, 017-00011).
Silane coupling agent uses the 3-aminopropyl triethoxysilane, and (CHISSO (strain) makes, S-330).
In following embodiment and comparative example, if no special instructions, " % " expression " weight % ".
Embodiment 1
One side fully stirs BET specific surface area 80m 2The synthetic calcium carbonate slurry of/g (solid content 8%), one side is heated to 40 ℃.With the synthetic calcium carbonate in this slurry is 100 weight parts, at room temperature, adds 3% sodium silicate aqueous solution, and making silicon-dioxide is 7 weight parts, in the importing and 3.5% diluted hydrochloric acid aqueous solution of water glass aequum, generates silicon dioxide layer on the lime carbonate surface.
Then, add 5 weight parts pass through add sodium hydroxide and 90 ℃ of following heated and stirred and the saponified fatty acid mixt, form sodium soap, dewater with pressure filter then, use compartment dryer, dry under 80 ℃ condition, use micropulverizer (thin river Micron system, ultramicro-grinder) pulverizes the dry thing of gained, make calcium carbonate powders with silicon dioxide layer and organic acid layer.
Stir this calcium carbonate powders with stirrer, and being that the consumption of 1.1 weight parts sprays the 3-aminopropyl triethoxysilane (CHISSO (strain) system S-330), stirs after 10 minutes with respect to 100 weight part raw material lime carbonate, 100 ℃ of following heat dryings 60 minutes, make modified calcium carbonate of the present invention.
The adhesion amount of silicon dioxide layer, organic acid layer and the silane coupling agent layer of the per 100 weight part raw material lime carbonate in the gained modified calcium carbonate is as shown in table 1.
Use two rollers of 8 inches, under 40～50 ℃ condition, will utilize aforesaid method and modified calcium carbonate with the consumption of 100 parts by weight of rubber, 100 weight parts, be coupled to synthetic rubber (divinyl rubber (SBR), 1502) in, make polymer composition of the present invention.
Embodiment 2
Remove and use BET specific surface area 40m 2The synthetic calcium carbonate slurry of/g is counted 3% sodium silicate aqueous solution of 5 weight parts with silicon-dioxide, and outside the 2.5 weight part mixed fatty acids, other and embodiment 1 the same the operation obtain modified calcium carbonate of the present invention.
The adhesion amount of silicon dioxide layer, organic acid layer and the silane coupling agent layer of the per 100 weight part raw material lime carbonate in the gained modified calcium carbonate is as shown in table 1.
The same with embodiment 1, with the consumption of the above-mentioned gained modified calcium carbonate of 100 weight part synthetic rubber (styrene-butadiene rubber(SBR) (SBR), 1502) cooperation 100 weight parts, make polymer composition.
Embodiment 3
One side fully stirs BET specific surface area 80m 2The synthetic calcium carbonate slurry of/g (solid content 8%), one side is heated to 40 ℃.With the synthetic calcium carbonate in this slurry is 100 weight parts, at room temperature, adds 3% sodium silicate aqueous solution, and making silicon-dioxide is 7 weight parts, in the importing and 3.5% diluted hydrochloric acid aqueous solution of water glass aequum, generates silicon dioxide layer on the lime carbonate surface.After adding to fatty acid mixt 5 weight parts in the calcium carbonate slurry that gained possesses silicon dioxide layer, equally with embodiment 1 dewater, dry, pulverize, make calcium carbonate powders with silicon dioxide layer and organic acid layer.
According to method similarly to Example 1, with respect to 100 parts by weight of rubber, will utilize aforesaid method and the lime carbonate with silicon dioxide layer and organic acid layer be coupled in the synthetic rubber (SBR 1502).
Then being that the consumption of 1.1 weight parts is directly with 3-aminopropyl diethoxy silane (CHISSO (strain) system with respect to 100 weight part raw material lime carbonate, S-330) add back mixing in the polymkeric substance to, make the polymer composition of the present invention that contains modified calcium carbonate of the present invention.
Silicon dioxide layer, organic acid layer and the silane coupling agent layer adhesion amount of the per 100 weight part raw material lime carbonate in the gained modified calcium carbonate are as shown in table 1.
Embodiment 4
Carry out operation similarly to Example 1 except that replacing the lipid acid, obtain modified calcium carbonate and polymer composition with resinous acid.
Silicon dioxide layer, organic acid layer and the silane coupling agent layer adhesion amount of the per 100 weight part raw material lime carbonate in the gained modified calcium carbonate are as shown in table 1.
Comparative example 1
Except adding the latter to BET specific surface area 80m with the ratio of 100 weight part lime carbonate, 5 weight part fatty acid mixts 2The synthetic calcium carbonate slurry of/g (solid content 8%) at home and abroad, other dewaters similarly to Example 1, dry, pulverize, modulation possesses the partially modified lime carbonate of organic acid layer.
The same with embodiment 1, cooperate the above-mentioned consumption of 100 weight parts with 100 parts by weight of rubber with partially modified lime carbonate of organic acid layer, the latter is cooperated with synthetic rubber (SBR 1502), form polymer composition.
Comparative example 2
One side fully stirs BET specific surface area 80m 2The synthetic calcium carbonate slurry of/g (solid content 8%), one side is heated to 40 ℃.With the synthetic calcium carbonate in this slurry is 100 weight parts, at room temperature, adds 3% sodium silicate aqueous solution, and making silicon-dioxide is 7 weight parts, in the importing and 3.5% diluted hydrochloric acid aqueous solution of water glass aequum, generates silicon dioxide layer on the lime carbonate surface.
The same with embodiment 1, cooperate the above-mentioned ratio of 100 weight parts to cooperate with 100 parts by weight of rubber with synthetic rubber (SBR 1502) with partially modified lime carbonate of silicon dioxide layer, form polymer composition.
Comparative example 3
The fatty acid treatment lime carbonate that comparative example 1 is made is stirred with stirrer in the limit, add 3-aminopropyl triethoxysilane (CHISSO (strain) system with the amount of 100 weight part raw material lime carbonate, 1.1 weight parts on one side, S-330), stir after 10 minutes, 100 ℃ of following heat dryings 60 minutes, modulation possessed the partially modified lime carbonate of organic acid layer and silane coupling agent layer.
The same with embodiment 1, the partially modified lime carbonate that will have above-mentioned fatty-acid layer and a silane coupling agent layer is added into synthetic rubber (SBR 1502) with the ratio of 100 parts by weight of rubber, 100 weight parts, makes polymer composition.
Comparative example 4
Being that the consumption of 1.1 weight parts is with 3-aminopropyl triethoxysilane (CHISSO (strain) system with respect to 100 weight part raw material lime carbonate, S-330) add in the lime carbonate of making in the comparative example 2 with silicon dioxide layer, stir after 10 minutes, 100 ℃ of following heat dryings 60 minutes, modulation had the partially modified lime carbonate of silicon dioxide layer and silane coupling agent layer.
The same with embodiment 1, cooperate the above-mentioned consumption of 100 weight parts with 100 parts by weight of rubber with partially modified lime carbonate of silicon dioxide layer and silane coupling agent layer, the latter is cooperated with synthetic rubber (SBR 1502), make polymer composition.
Comparative example 5
Remove to BET specific surface area 4m 2Add outside 3% sodium silicate aqueous solution with the ratio of 100 weight part synthetic calcium carbonates, 2 weight part silicon-dioxide in the synthetic calcium carbonate slurry of/g, other operation is the same with comparative example 2, forms silicon dioxide layer on the lime carbonate surface.Stir this lime carbonate with agitator on one side, the ratio that is 0.3 weight part with used lime carbonate 100 weight parts of raw material is added the 3-aminopropyl triethoxysilane on one side, stir after 10 minutes, 100 ℃ of following heat dryings 60 minutes, modulation had the partially modified lime carbonate of silicon dioxide layer and silane coupling agent layer.
The same with embodiment 1, cooperate the above-mentioned consumption of 100 weight parts with 100 parts by weight of rubber with partially modified lime carbonate of silicon dioxide layer and silane coupling agent layer, the latter is added in the synthetic rubber (SBR 1502), make polymer composition.
Comparative example 6
Filler uses untreated BET specific surface area 175m 2The wet silicon dioxide of/g (Japanese Silica industry system, ニ Star プ シ one Le VN3).
Ratio with 100 parts by weight of rubber (SBR 1502), 40 weight parts cooperates above-mentioned wet silicon dioxide, makes polymer composition.In polymer composition, changing with lime carbonate is the proportioning of filler of parent and the proportioning of wet silicon dioxide, to satisfy the hardness of vulcanized rubber.
Mixing with the polymer composition that two rollers are made 5 part by weight of zinc oxide, 1 weight part stearic acid, 1.2 weight part vulcanization aid DM (dibenzothiazyl disulfide), 0.2 weight part vulcanization aid TS (tetramethylthiuram monosulfide), 2 weight part sulphur and embodiment and comparative example, obtain preparation (sulfuration) rubber.Comparative example 6 is a wet silicon dioxide, and other then adds 5 weight part Diethylene Glycols.
The gained unvulcanized rubber is placed on the vibration disc type rheometer, calculate preferred curing time tc (90), it is crosslinked to pressurize in this time, obtains the press vulcanization sheet.
By following method, estimate each polymer composition and add the rerum natura of compressing tablet.
＜evaluation method 〉
1. tension test
According to the method for JIS K 6251 regulations, the following test subject under use Shore tension testing machine is measured 23 ℃.
300% modulus M 300: the tensile strength during 300% elongation;
500% modulus M 500: the tensile strength during 500% elongation;
Tensile strength T B: the load during fracture is divided by the quotient of test piece sectional area
Elongation E B: the elongation during fracture
2. hardness test
According to the method for JIS K 6253 regulation, the hardness Hs (Type A) under measuring 23 ℃.
3. tear strength
According to the method for JIS K 6252 regulations, use the Shore tension testing machine, measure down at 23 ℃.Arc (jagged) used in test piece.
4. wearability
According to the method for JIS K 6264 regulation, use the system Akron of Shimadzu Seisakusho Ltd. wear testing machine, under the condition of 15 ° of load 61b, angle, preparation friction 200 times, formally rub 1000 times the research wear volume.
5. counter-bending cracking
According to the method for JIS K 6260 regulations, the island makes made DEMATTIA flexing machine in the use, and the be full of cracks length when measuring bending changes to the number of bends (cycle index) of 10mm from 2mm.Used thickness of test piece 6.3mm, crooked back and forth movement per minute 300 times.The test piece clamp movement is apart from 57mm, and ultimate range is 75mm between anchor clamps.
6. elongation
According to the method for JIS K 6255 regulation, use Lupke formula elongation rate test device, the value under measuring 23 ℃.The cylindric print of test piece used thickness 12.5mm, diameter 29mm.
7. tensile-permanent set
Use No. 1 dumbbell plate, the setting graticule is 40mm.About 50% of elongation when extending fracture in above-mentioned 1 the tension test kept 30 minutes under this state.Remove external force after 30 minutes, left standstill again 30 minutes, measure the residual elongation of this moment.The result's residual elongation of percentage ratio mark with respect to former length (40mm).
8. roller processibility
Polymer composition twisting cohesion the complexity on roller of roller processibility during according to compounding rubber estimated.Twisting cohesion to used pair of roller is good more, the easy more mixing or easy more additive of sneaking into.The twisting cohesion degree of the polymer composition when evaluation is paid attention to sneak into filler according to following judgement criteria, is arranged in order easy twisting cohesion sample, divides 5 grades and estimates.
A: very good
B: good
C: good slightly
D: poor
E: non-constant
Evaluation result is as shown in table 1
Table 1
Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative example 5 Comparative example 6
Raw material lime carbonate BET specific surface area [m 2/g] ??80 ??40 ??80 ??80 ??80 ??80 ??80 ??100 ??4 ??-
Wet silicon dioxide [m 2/g] ??- ??- ??- ??- ??- ??- ??- ??- ??- ??175
Layer constitutes
Silicon-dioxide [weight part] ??7 ??5 ??7 ??7 ??- ??7 ??- ??7 ??2 ??-
Lipid acid [weight part] ??5 ??2.5 ??5 ??- ??5 ??- ??5 ??- ??- ??-
Resinous acid [weight part] ??- ??- ??- ??5 ??- ??- ??- ??- ??- ??-
Silane coupling agent [weight part] ??1.1 ??1.1 ??1.1 ??1.1 ??- ??- ??1.1 ??1.1 ??0.3 ??-
Mechanical characteristic
300% modulus [MPa] ??4.2 ??5.4 ??6.4 ??4.4 ??1.2 ??1.4 ??2.4 ??6.1 ??2.4 ??2.2
500% modulus [MPa] ??9.6 ??11.9 ??14.3 ??9.9 ??2.1 ??2.4 ??5.4 ??10.7 ??3.5 ??4.1
Tensile strength [MPa] ??17.7 ??15.7 ??16.8 ??18.0 ??10.0 ??9.7 ??14.6 ??11.9 ??5.8 ??17.2
Elongation [%] ??680 ??610 ??550 ??670 ??900 ??880 ??690 ??540 ??740 ??860
Hardness ??65 ??64 ??69 ??66 ??59 ??60 ??61 ??73 ??64 ??67
Tear strength [N/mm] ??37.4 ??32.8 ??36.4 ??41.9 ??18 ??20 ??23.6 ??50.1 ??17.1 ??41.5
Wearability [cc/1000 time] ??0.40 ??0.37 ??0.60 ??0.42 ??0.60 ??0.50 ??0.51 ??0.40 ??0.95 ??0.43
Counter-bending cracking [Kc2 → 10] ??1.0 ??1.0 ??1.5 ??1.2 ??1.5 ??1.2 ??1.5 ??3.3 ??＜1 ??3.4
Elongation [%] ??46 ??51 ??46 ??46 ??45 ??45 ??46 ??40 ??55 ??49
Tensile-permanent set [%] ??5.6 ??2.5 ??5.1 ??4.9 ??11.8 ??9.0 ??5.9 ??15.0 ??9.8 ??21.7
The roller processibility ??A ??B ??A ??A ??A ??E ??A ??E ??A ??E
Shown in table 1 result, the rerum natura such as tensile strength, hardness of being furnished with the polymer composition of the modified calcium carbonate of the present invention shown in the embodiment 1～4 have can be suitable with white carbon black mechanical characteristic.And also has excellent specific property aspect the shortcoming of white carbon blacks such as tensile-permanent set and roller processibility.
Otherwise the polymer composition that contains the lime carbonate that only has fatty-acid layer shown in the comparative example 1 fails to reach rerum naturas such as sufficient modulus, hardness, tensile strength.
The polymer composition that contains the lime carbonate that only has silicon dioxide layer shown in the comparative example 2 fails to reach mechanical characteristics such as sufficient modulus, hardness, tensile strength.And the twisting cohesion situation of pair roller is poor.
The polymer composition that contains the lime carbonate that only has fatty-acid layer and silane coupling agent layer shown in the comparative example 3 fails to reach mechanical characteristics such as sufficient modulus, hardness, tensile strength.
The polymer composition that contains the lime carbonate that only has silicon dioxide layer and silane coupling agent layer shown in the comparative example 4 fails to reach mechanical characteristics such as sufficient tensile-permanent set.And the twisting cohesion of pair roller is poor, and the roller processibility is also poor.
The polymer composition that contains the lime carbonate that only has silicon dioxide layer and silane coupling agent layer that BET specific surface area shown in the comparative example 5 is little fails to reach mechanical characteristics such as sufficient tensile strength, counter-bending cracking, wearability.
And the polymer composition of the white carbon black that is untreated containing shown in the comparative example 6 fails to reach mechanical characteristics such as sufficient modulus, tensile-permanent set.And the roller processibility is insufficient.
Industrial applicability
The surface of modified calcium carbonate of the present invention has (i) silicon dioxide layer, (ii) by at least a organic acid layer that constitutes that is selected from lipid acid, soap, fatty acid ester, resinous acid, resinate and resinate, and (iii) silane coupling agent layer.
Therefore, the polymkeric substance of being furnished with modified calcium carbonate of the present invention shows the mechanical characteristic of working as with the polymer phase that cooperates white carbon black, and simultaneously, tensile-permanent set and roller processibility are also very excellent.And the cohesion during owing to the lime carbonate drying is suppressed, so the coarse particles that is difficult to pulverize is few.
The polymer composition that has the modified calcium carbonate of the present invention of excellent specific property like this and contain this modified calcium carbonate can be effective to purposes such as tire, sole.

Claims (14)

1. modified calcium carbonate, it is characterized in that, on the surface of lime carbonate, possess (i) silicon dioxide layer, the organic acid layer that (ii) is selected from least a formation of lipid acid, soap, fatty acid ester, resinous acid, resinate and resinate reaches (iii) silane coupling agent layer.
2. modified calcium carbonate as claimed in claim 1 is characterized in that, the BET specific surface area of described lime carbonate is 5～120m 2/ g.
3. modified calcium carbonate as claimed in claim 1 is characterized in that, the BET specific surface area of modified calcium carbonate is 4～110m 2/ g.
4. modified calcium carbonate as claimed in claim 1 is characterized in that, is 100 weight parts with lime carbonate, and the silicon dioxide layer adhesion amount is 0.5～15 weight part, and organic acid layer adhesion amount is 0.5～20 weight part, and the silane coupling agent layer adhesion amount is 0.05～10 weight part.
5. the manufacture method of modified calcium carbonate is characterized in that, comprising:
(1) by silica hydrosol is added in the calcium carbonate slurry, forms the operation of (i) silicon dioxide layer on the lime carbonate surface;
(2) add in the calcium carbonate slurry that possesses described (i) silicon dioxide layer being selected from least a of lipid acid, soap, fatty acid ester, resinous acid, resinate and resinate, form the (ii) operation of organic acid layer;
(3) described to having (i) silicon dioxide layer and (ii) the calcium carbonate slurry of organic acid layer dewater and the exsiccant operation; And
(4) with silane coupling agent to have (i) silicon dioxide layer and (ii) the calcium carbonate granule of organic acid layer carry out surface treatment, form the (iii) operation of silane coupling agent layer.
6. a polymer composition is characterized in that, contains following (a) and (b), wherein,
(a) for possessing (i) silicon dioxide layer on the lime carbonate surface, (ii) being selected from the organic acid layer and the (iii) modified calcium carbonate of silane coupling agent layer of at least a formation of lipid acid, soap, fatty acid ester, resinous acid, resinate and resinate; (b) be polymkeric substance.
7. polymer composition as claimed in claim 6 is characterized in that, the BET specific surface area of described lime carbonate is 5～120m 2/ g.
8. polymer composition as claimed in claim 6 is characterized in that, the BET specific surface area of modified calcium carbonate is 4～110m 2/ g.
9. polymer composition as claimed in claim 6, it is characterized in that, be 100 weight parts with lime carbonate, and the silicon dioxide layer adhesion amount is 0.5～15 weight part, organic acid layer adhesion amount is 0.5～20 weight part, and the silane coupling agent layer adhesion amount is 0.05～10 weight part.
10. polymer composition as claimed in claim 6 is characterized in that, is 100 weight parts with polymkeric substance, and the content of modified calcium carbonate is 5～150 weight parts.
11. the manufacture method of polymer composition as claimed in claim 6 is characterized in that, also comprises:
To the lime carbonate surface have (i) silicon dioxide layer, (ii) be selected from lipid acid, soap, fatty acid ester, resinous acid, resinate and resinate at least a formation the organic acid layer and (iii) the modified calcium carbonate of silane coupling agent layer be added into polymkeric substance, blended operation then.
12. the manufacture method of polymer composition as claimed in claim 6 is characterized in that, also comprises:
The modified calcium carbonate of organic acid layer that will have (i) silicon dioxide layer, (ii) is selected from least a formation of lipid acid, soap, fatty acid ester, resinous acid, resinate and resinate is added into polymkeric substance, then silane coupling agent is added into polymkeric substance, decomposite operation.
13. the manufacture method of polymer composition as claimed in claim 6 is characterized in that, also comprises:
Silane coupling agent is added into polymkeric substance, will has (i) silicon dioxide layer again, (ii) the modified calcium carbonate by at least a organic acid layer that constitutes that is selected from lipid acid, soap, fatty acid ester, resinous acid, resinate and resinate is added into the decomposite operation of polymkeric substance.
14. the formed body that gets by the described polymer composition moulding of claim 6.
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CN100362058C (en) * 2005-12-20 2008-01-16 中国地质大学（武汉） Dry process mechanical force and chemical modification method of superfine calcium carbonate
CN102365236A (en) * 2009-03-27 2012-02-29 白石工业株式会社 Surface-treated calcium carbonate and paste resin composition containing same
CN101516985B (en) * 2006-09-28 2012-07-25 白石工业株式会社 Calcium carbonate treated with curing active ingredient
CN103509206A (en) * 2013-07-03 2014-01-15 青阳县恒源化工原料有限责任公司 Aging-resistant flame-retardant modified calcium carbonate used for auto tyres, and preparation method thereof
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