CN1334848A - Surface-treated calcium carbonate filler, process for producing same, and resin composition contg. said filler - Google Patents
Surface-treated calcium carbonate filler, process for producing same, and resin composition contg. said filler Download PDFInfo
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- CN1334848A CN1334848A CN99816053A CN99816053A CN1334848A CN 1334848 A CN1334848 A CN 1334848A CN 99816053 A CN99816053 A CN 99816053A CN 99816053 A CN99816053 A CN 99816053A CN 1334848 A CN1334848 A CN 1334848A
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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
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
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- 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
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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
- C09C1/021—Calcium carbonates
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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
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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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
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
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- 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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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
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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
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K2200/02—Inorganic compounds
- C09K2200/0239—Oxides, hydroxides, carbonates
Abstract
A surface-treated calcium carbonate filler characterized in that the surface has been wet-treated with at least one member selected from the group consisting of saturated fatty acids, unsaturated fatty acids, alicyclic carboxylic acids, and resin acids. It is especially suitable for use as a filler for resins. When contained in a curable resin composition, the filler imparts not only excellent dry-state heat resistance but excellent thixotropic properties, excellent slump resistance, and satisfactory storage stability. When used in a plastic, the filler has excellent dispersibility and imparts excellent insulating properties, etc. When used in a coating material or ink, the filler imparts excellent water resistance, etc.
Description
Technical field
The method and the resin combination that contains this filler that the present invention relates to the surface-treated pearl filler and produce this filler.More particularly, the present invention relates to the surface-treated pearl filler, also relate to method of producing this filler and the resin combination that contains this filler in addition.Wherein said pearl filler is not only given the slump resistance and the good storage stability of excellent thixotropy, excellence when being applied to cured resin, and gives excellent thermotolerance when drying; When being applied to electronic material, give excellent insulating property; When being applied to paint and printing ink, give excellent gloss and water tolerance.
Background technology
Lime carbonate has been widely used as the filler or the pigment of paint, paper, rubber, plastics, sealing material.
In the middle of them, for example with regard to sealing material, lime carbonate is widely used as the purpose of waterproof and sealing in the field as building, automobile and flooring material.In these fields, moisture-curable one-pack type resin combination (hereinafter referred to as the single component resin combination) has lot of advantages when using, compare with the bi-component resin composition, do not need to be pre-mixed when using, so it does not need hybrid technology owing to two kinds of liquid; It can be shortened working hours etc.Because these advantages, production quantity increases sharply.In the application of described single component resin combination, especially as joint filler and sealing material the time, often be applied to vertical place, therefore do not wish that from applying it produces sagging up to solidifying nature.Therefore, though workability may influence a little in use, it should have high thixotropy and slump resistance.In order to give these performances, use colloidal silica, lime carbonate etc. so far always.Yet these are given thixotropic reagent and have a lot of shortcomings, and viscosity increases when for example storing, bonding interface foaming and be full of cracks when the curing of urethane resin.
For example, with regard to colloidal silica, as announcing by Japan's unexamined patent as described in (Kokoku) number 45-41110 and the 53-5899, a lot of applications have been produced so far and its superiority also gets the nod, but it comprises a lot of problems, as because the high-modulus after solidifying, to bonded object bad adaptability; Because quantity is the thixotropy height after a little while, thixotropy descends during the lapse of time, the trickle adjustment difficulty of viscosity; Weathering resistance difference and because the danger of silicosis is seen from work health viewpoint to be difficult to handle.
With regard to lime carbonate, will be called water-ground limestone as material and classification is obtained to the powder that obtains a class by the grinding stone lime stone usually, it is poor that it comprises thick particle and performance defectiveness such as thixotropy.Although described water-ground limestone carries out surface treatment with lipid acid or paraffin usually, but because it is to pass through dry process, be about to lime carbonate and surface treatment agent and stir under heating, the whole surface of lime carbonate is coating fully, has caused inevitable remaining uncoated water-wetted surface.Water adsorption is brought adverse influence to package stability on described water-wetted surface as a result.In addition, almost can not expect to give thixotropic effect.
On the other hand, with regard to precipitated chalk, the moisture-curing that in the single component resin combination, comprises in air, described curing reaction is from the surface of water adsorption at described lime carbonate.When it with common surface treatment agent (as an alkali metal salt of lipid acid and resinous acid), tensio-active agent (as alkyl benzene sulphonate (ABS) and their salt) when carrying out surface treatment, because strong hydrophilicity makes it tend to absorb moisture, polyreaction is by carrying out with the reaction of moisture.Under any one situation, it becomes the reason that sharply descends, foams and chap at package stability.For this reason, allow its seasoning during beginning, use then, but when carry out surface treatment with hydrophilic tensio-active agent, particularly low in dehydration rate, and also the influence of hydrophilic alkalimetal ion makes the package stability deterioration when inevitable.
With regard to the modified organic silicone resin that is used in sealing material, usually use an alkali metal salt to carry out surface-treated lime carbonate, but dehydration rate is low with lipid acid, it just can not use dewatering agent that therefore need not costliness.In Japanese unexamined patent publication (Kokai) number 2-38309, suggestion is carried out surface-treated lime carbonate with fatty acid ester, according to this technology, can solve the problem of front to a certain extent, in the sealing material field of typical single component resin combination, find effective direction.
Though ester bond is heat-staple hardly, the thermotolerance during therefore about drying also has problems.That is exactly in order to improve dehydration rate, for example, when being not less than under 130 ℃ the temperature long-time heating or at 150 ℃ of heating several hrs down, thermal ageing taking place, therefore destroys internal performance wherein.
In addition, in Japanese unexamined patent publication (Kokai) number 10-245221, suggestion is carried out surface-treated lime carbonate with the have compound and at least a carboxylic acid, sulfonic acid and their metal-salt of being selected from that are not less than 50 ℃ of fusing points of formula (1) representative.Yet when using this surface-treated lime carbonate, for example in one-pack type urethane, the seal gum variable color of acquisition is brown, therefore, wants albescent seal gum, must use expensive tinting material.In addition, owing to solidify slowly, when applying the back to curing, dirt deposition becomes problem on the seal gum surface.
A removes the residual group of isocyanate groups or removes the residual group that deaminizes from aminocompound from isocyanic ester (isocianate) compound in the formula, and n is 1 to 4 integer, and R is an alkyl, and wherein at least one R has the alkyl that is no less than 8 carbon atoms.
In addition, in resin combination such as plastics, paint and ink area, lime carbonate is used as filler or pigment.When in resin combination such as plastics, paint and printing ink, using lime carbonate, use two types of water-ground limestone and precipitated chalks.They carry out using after the surface treatment with an alkali metal salt of lipid acid, an alkali metal salt and the fatty acid ester of resinous acid usually.When an alkali metal salt that uses an alkali metal salt with lipid acid, resinous acid and fatty acid ester carry out surface-treated lime carbonate, for example in plastics, bad dispersibility often.In addition, use when the field that needs insulating property (as electric wire), can obtain actual available performance when its.But practical situation need the insulating property that improve more, for example with regard to capacitor film, if just the insulating property deficiency can not use.In addition, when it is used for paint and printing ink, can obtain actual available performance, but the fact is to expect more augmented performances such as water tolerance.
According to aforesaid situation, the invention provides the surface-treated pearl filler, and the method and the resin combination that comprises this filler of producing this filler.Described surface-treated pearl filler is not only given the slump resistance and the good storage stability of excellent thixotropy, excellence when being applied to curable resin composition, and gives excellent thermotolerance when drying; When being applied to plastics, give excellent dispersiveness and excellent insulativity; When being applied to paint and printing ink, give excellent gloss and excellent in water resistance.
The inventor has carried out a series of widely researchs, attempts solving aforesaid problem, finds that described special surface pearl filler of handling and the resin combination that comprises described surface-treated pearl filler reach predetermined purpose, have therefore finished the present invention.
Of the present invention open
In first aspect, the invention provides the surface-treated pearl filler, the surface of wherein said lime carbonate is with the surface treatment (claim 1) of wetting of at least a surface treatment agent that is selected from saturated fatty acid, unsaturated fatty acids, alicyclic carboxylic acid and resinous acid.
In second aspect, the invention provides the surface-treated pearl filler, the surface of wherein said lime carbonate is the surface treatment of wetting of the surface treatment agent with the metallic soap of the metallic soap of at least a metallic soap that is selected from saturated fatty acid, unsaturated fatty acids, alicyclic carboxylic acid's metallic soap and resinous acid, and alkali-metal content is no more than 1.0 * 10
-3Mol/100gCaCO
3(claim 2).
Embodiment preferred is the surface-treated pearl filler of claim 1 or 2, and the BET specific surface area of wherein said lime carbonate is 3 to 120m
2/ g (claim 3).
In the third aspect, the invention provides the method for the surface-treated pearl filler of production claim 1 or 3, said method comprising the steps of:
Add in the aqueous slurry calciferous at least a surface treatment agent that is selected from saturated fatty acid, unsaturated fatty acids, alicyclic carboxylic acid and resinous acid and
The mixture of heating gained is to the temperature that is not less than these sour fusing points, thus the described lime carbonate of surface treatment (claim 4).
In fourth aspect, the invention provides the method for the surface-treated pearl filler of production claim 2 or 3, said method comprising the steps of:
In aqueous slurry calciferous, add (A) at least a surface treatment agent that is selected from saturated fatty acid, unsaturated fatty acids, alicyclic carboxylic acid and resinous acid, (B) metal hydroxides or metal oxide, described metal hydroxides or metal oxide can by with (A) reaction produce the water-insoluble metallic soap and
With by (A) and (B) the described lime carbonate of metallic soap surface treatment (claim 5) of reaction (A) that obtain.
Aspect the 5th, the invention provides the method for the surface-treated pearl filler of production claim 2 or 3, said method comprising the steps of:
Be added at least a surface treatment agent that is selected from saturated fatty acid metallic soap, unsaturated fatty acids metallic soap, alicyclic carboxylic acid's metallic soap and resinous acid metallic soap in the organic solvent slurry in the aqueous slurry calciferous,
The dehydration and the slurry of dry gained and
The mixture of heating gained is to the temperature of the fusing point that is not less than adding metallic soap wherein, thus the described lime carbonate of surface treatment (claim 6).
Aspect the 6th, the invention provides the method for the surface-treated pearl filler of production claim 2 or 3, said method comprising the steps of:
The surface treatment agent that adds an alkali metal salt of an alkali metal salt, alicyclic carboxylic acid's an alkali metal salt of (C) at least a an alkali metal salt that is selected from saturated fatty acid, unsaturated fatty acids and resinous acid in the aqueous slurry calciferous,
With the described lime carbonate of described surface treatment agent surface treatment and
Wash the lime carbonate of described processing with water, be no more than 1.0 * 10 thereby control alkali-metal content
-3Mol/100gCaCO
3(claim 7).
Aspect the 7th, the invention provides the method for the surface-treated pearl filler of production claim 2 or 3, said method comprising the steps of:
The surface treatment agent that adds an alkali metal salt of an alkali metal salt, alicyclic carboxylic acid's an alkali metal salt of (C) at least a an alkali metal salt that is selected from saturated fatty acid, unsaturated fatty acids and resinous acid in the aqueous slurry calciferous,
With the described lime carbonate of described surface treatment agent surface treatment,
Adding can be by producing the metallic compound of metallic soap with described (C) an alkali metal salt reaction, thus carry out double decomposition generate (C) metallic soap and
Wash the lime carbonate of described processing with water, be no more than 1.0 * 10 thereby control alkali-metal content
-3Mol/100gCaCO
3(claim 8).
In eight aspect, the invention provides each the resin combination (claim 9) of surface-treated pearl filler that comprises with the claim 1 to 3 of resin alloy.
Embodiment preferred is the resin combination of claim 9, and wherein said resin is the resin (claim 10) that is applied to paint.
Embodiment preferred is the resin combination of claim 9, and wherein said resin is the resin (claim 11) that is applied to printing ink.
Embodiment preferred is the resin combination of claim 9, and wherein said resin is the resin (claim 12) that is applied to plastics.
Embodiment preferred is the resin combination of claim 9, and wherein said resin is the resin (claim 13) that is applied to seal gum.
Embodiment preferred is the resin combination of claim 9, and wherein said resin is cured resin (claim 14).
Embodiment preferred is the resin combination of claim 9, and wherein said resin is a moisture-curable resin (claim 15).
Aspect the 9th, the invention provides comprise with the claim 1 to 3 of resin alloy each surface-treated pearl filler and the compound that (D) is not less than 50 ℃ of fusing points with having of fatty acid ester and/or following formula (1) representative and at least aly be selected from the moisture-curable resin combination (16) that carboxylic acid, sulfonic acid and their metal-salt carry out surface-treated lime carbonate.
A removes the residual group of isocyanate groups or removes the residual group that deaminizes from aminocompound from isocyanate compound in the formula, and n is 1 to 4 integer, and R is an alkyl, and wherein at least one R has the alkyl that is no less than 8 carbon atoms.Implement best way of the present invention
Being applied to surface treatment agent of the present invention is that saturated fatty acid, unsaturated fatty acids, alicyclic carboxylic acid, resinous acid or their metallic soap are (in specification sheets of the present invention, metallic soap is meant the metal-salt except that basic metal), these materials use separately or two or more are used in combination.These surface treatment agents are not tensio-active agents, are hydrophobic therefore.Be coated on each corner and the crack on lime carbonate surface by wet processing methods.Therefore, when comparing with fatty acid ester, these surface treatment agents in various resin dispersiveness and thermally-stabilised be excellent, the thermostability that therefore adopts these surface treatment agents to carry out surface-treated lime carbonate also is high.Correspondingly, it can be at high temperature dry, for example, with regard to single-component modified polysiloxane seal gum, has and save the advantage of using expensive dewatering agent.In addition, it also is useful as the filler of fast setting seal gum with regulating set time.And, when surface-treated calcium carbonate applications of the present invention in as capacitor film the time, show excellent dispersiveness and insulativity, when being applied to as paint and printing ink, the demonstration excellent in water resistance.
The pearl filler of described surface active is by following method production.
First method is included in the aqueous slurry calciferous, add at least a surface treatment agent that is selected from saturated fatty acid, unsaturated fatty acids, alicyclic carboxylic acid and resinous acid, the mixture of heating gained is to the temperature that is not less than these sour fusing points, stir described mixture, then by usual method dehydration, dry and grinding.
Second method is included in the aqueous slurry calciferous, add (A) at least a surface treatment agent of saturated fatty acid, unsaturated fatty acids, alicyclic carboxylic acid and resinous acid and (B) metal hydroxides or metal oxide of being selected from, described metal hydroxides or metal oxide can be by producing metallic soap with (A) reaction, with by (A) and the described lime carbonate of metallic soap surface treatment that (B) reacts (A) of acquisition, follow by usual method dehydration, dry also grinding.The time that adds (B) can also can add with (A) before or after adding (A) simultaneously.
As by producing the metal hydroxides of metallic soap with at least a surface treatment agent reaction that is selected from saturated fatty acid, unsaturated fatty acids, alicyclic carboxylic acid and resinous acid, exemplary example such as hydrated barta, calcium hydroxide, magnesium hydroxide and strontium hydroxide, as by producing the metal oxide of metallic soap, exemplary example such as barium oxide, calcium oxide, magnesium oxide and strontium oxide with (A) reaction.These materials use separately or two or more are used in combination.
The third method is included in the aqueous slurry calciferous, the surface treatment agent that adds the metallic soap of metallic soap, alicyclic carboxylic acid's the metallic soap of at least a metallic soap that is selected from saturated fatty acid, unsaturated fatty acids and resinous acid, the mixture of vigorous stirring gained, thereby the described lime carbonate of surface treatment.These metallic soaps have strong repellency, and are incompatible with water, and the preferred thus form with the water-miscible organic solvent slurry adds.
As described water-miscible organic solvent, exemplary have alcohols such as methyl alcohol, ethanol and a propyl alcohol; Ketone such as butanone, 2 pentanone, these organic solvents use separately or two or more are used in combination.From obtaining the viewpoint of uniform coating, here the metallic soap of Shi Yonging should be expected thin as far as possible.And if described thermal treatment is carried out after dehydration and drying, temperature is not less than the fusing point of the metallic soap of use, and it becomes more perfect.
The 4th kind of method is included in the aqueous slurry calciferous, the surface treatment agent that adds an alkali metal salt of an alkali metal salt, alicyclic carboxylic acid's an alkali metal salt of (C) at least a an alkali metal salt that is selected from saturated fatty acid, unsaturated fatty acids and resinous acid, with the described lime carbonate of described surface treatment agent surface treatment, wash described lime carbonate with water, be no more than 1.0 * 10 thereby control alkali-metal content
-3Mol/100gCaCO
3In this method importantly when because alkali-metal wetting ability when causing problem about package stability, need replace the basic metal that is included in (C) with calcium, thereby form calcium soap, the calcium soap of unsaturated fatty acids, alicyclic carboxylic acid's calcium soap and the calcium soap of resinous acid of saturated fatty acid, the result, wash described basic ion freely with water, be no more than 1.0 * 10 thereby control alkali-metal content
-3Mol/100gCaCO
3
The 5th kind of method is included in the aqueous slurry calciferous, the surface treatment agent that adds an alkali metal salt of an alkali metal salt, alicyclic carboxylic acid's an alkali metal salt of (C) at least a an alkali metal salt that is selected from saturated fatty acid, unsaturated fatty acids and resinous acid, with the described lime carbonate of described surface treatment agent surface treatment, and add by producing the metallic compound of metallic soap, thereby carry out the metallic soap of double decomposition production (C) with an alkali metal salt reaction of (C).In this method,, must wash basic metal with water to being no more than 1.0 * 10 with same reason in the 4th kind of method
-3Mol/100gCaCO
3Level.If alkali-metal content surpasses 1.0 * 10
-3It is not enough that mol, described package stability will become.
As by producing the metallic compound of metallic soap, exemplary muriate such as aluminum chloride, calcium chloride, iron(ic) chloride, magnesium chloride, lead chloride and zinc chloride with (C) reaction; Vitriol such as sal epsom and Tai-Ace S 150, these metallic compounds use separately or two or more are used in combination.
Above-mentioned five kinds of methods can finish separately or two or more combinations are finished.
Although the saturated fatty acid, unsaturated fatty acids, alicyclic carboxylic acid and the resinous acid that use in the present invention are not specifically limited, preferably use those to have the material of carbon atom as much as possible.For example, when being used for gel-type resin, preferably use those to have the material that is no less than 8 carbon atoms, because except that package stability, thixotropy and slump resistance height also are gratifying.
For example, exemplary saturated fatty acid such as sad, lauric acid, tetradecanoic acid, palmitinic acid, stearic acid and eicosanoic acid; Unsaturated fatty acids such as oleic acid, elaidic acid, linolic acid and ricinolic acid; Alicyclic carboxylic acid such as naphthenic acid (naphtenic acid); Resinous acid such as abietic acid, pimaric acid, palustric acid and neoabietic acid.As these sour metallic soaps, the exemplary metallic soap that Ag, Al, Ba, Ca, Cu, Fe, Mg, Mn, Pb, Sn and Zn are arranged, these materials can use separately or two or more are used in combination.
The amount of described surface treatment agent is not specifically limited, but preferred per 100 parts of (weight) lime carbonate are with the surface treatment agent of 0.1 to 20.0 part (weight).If it is less than 0.1 part (weight), described surface-treated effect is often not enough, even and surpass 20.0 parts (weight), can not expect to obtain how significant effect, therefore uneconomic often.
With regard to described alkali-metal content, if be no more than 1.0 * 10
-3Mol/100gCaCO
3, can reach its intended purposes of the present invention, but when becoming still less, can more effectively reach its intended purposes of the present invention.Therefore, preferably be no more than 7.0 * 10
-4Mol/100gCaCO
3, more preferably no more than 5.0 * 10
-4Mol/100gCaCO
3
The lime carbonate of Shi Yonging is not specifically limited in the present invention, but selects according to the estimated performance of resin combination.For example, select arbitrarily by grinding according to described purpose as the Wingdale of material and the water-ground limestone that resulting powder particle size classification is on request obtained; Prepare unslaked lime by calcined limestone, prepare the aqueous slurry of white lime, the precipitated chalk that carbon dioxide is produced by described slurry with hydrate; Solution method lime carbonate by carbonate solution and calcium salt soln reaction acquisition.For example, for obtaining to be used for the high thixotropic and the excellent slump resistance of curable resin composition, the preferred use has 3 to 120m
2/ g, more preferably 5 to 100m
2The lime carbonate of the BET specific surface area of/g.If less than 3m
2/ g is difficult to give high viscosity, if surpass 120m
2/ g, the amount that need to increase described surface treatment agent is so that cover described hydrophilic surface, therefore cause expensive, so not preferred.More preferably use the precipitated chalk that can obtain higher BET specific surface area.And, when will be through the water-ground limestone of mechanical mill and classification during, be included in the few and surfactivity of the alkali-metal content here and hang down and make its dehydration rate excellence as described surface treatment pearl filler.For this reason, when being used in curable resin composition, it is favourable to package stability.
Surface-treated pearl filler of the present invention is excellent especially in dispersiveness, so it is applicable to various resins.For example, when in gel-type resin, using, provide excellent thixotropy, slump resistance and package stability as sealing material, tackiness agent, flooring material; When being used for paint and printing ink, provide gloss and water tolerance; When being used for plastics, provide excellent physical strength and thermostability.In addition, when being used for plastics film, provide excellent adhesion inhibiting properties and insulativity; Effective especially when being used for capacitor film.
Be not specifically limited with surface-treated pearl filler blended resin of the present invention, example is liquid resin such as urethane, polysulfide, polysiloxane, modified polyorganosiloxane and the polyisobutene that is used for sealing material; The liquid resin such as urea-formaldehyde resin, resol, Resins, epoxy, silicone resin and the acrylic resin that are used for tackiness agent; The liquid resin such as Resins, epoxy, urethane resin and the vibrin that are used for flooring material; Liquid resin that is used to paint such as resol, Synolac, unsaturated polyester resin, aminoresin, Resins, epoxy, polyvinyl resin, acrylic resin, urethane resin, silicone resin and fluoro-resin; Be used for printing ink as rosin, resol, Synolac, polyamide resin, urethane resin, Resins, epoxy, vibrin and acrylic resin; The thermosetting resin such as resol, urea-formaldehyde resin, melamine resin, unsaturated polyester resin, Resins, epoxy, urethane resin and the polyimide resin that are used for plastics; Thermoplastic resin such as polyvinyl chloride (PVC) RESINS, polyvinyl resin, acrylic resin, polystyrene resin, ABS resin, polyamide resin, polyacetal resin, polycarbonate resin, fluoro-resin and pet resin.These resins use separately or two or more are used in combination.
Depend on the purposes of the kind of resin and described resin combination with the amount of the surface-treated pearl filler of the present invention of described mixed with resin and change, but resin meter based on 100 parts (weight), be typically about 20 to about 200 parts (weight), preferably approximately 40 is to about 150 parts (weight).If be less than 20 parts (weight), can not give enough thixotropy, if surpass 200 parts (weight), viscosity becomes Tai Gao and makes the workability variation.
In order to regulate the purpose of other performance, resin combination of the present invention also can comprise other filler such as colloidal silica, talcum, kaolin, zeolite, resin balls and glass sphere; Softening agent such as dioctyl phthalate and phthalic acid dibutyl ester; Solvent such as aromatic hydrocarbons (as toluene and dimethylbenzene), aliphatic hydrocrbon (as hexane and butane); Oil solvent such as gasoline; Ether or ester such as ketone are as acetone, methylethylketone and cellosolve acetate; Additive such as silicone oil and fatty acid modified silicone oil, and other various additives and tinting material, separately or two or more combination.
When using surface treatment pearl filler of the present invention, for example in the moisture-curable resin combination,, can regulate the curing speed of described resin combination by being used in combination the filler that tradition is used.In described moisture-curable resin combination, with the compound and at least a carboxylic acid, sulfonic acid and their the metal-salt surface treatment lime carbonate of being selected from that is not less than 50 ℃ of fusing points that has of fatty acid ester and/or following formula (1) representative:
A removes the residual group of isocyanate groups or removes the residual group that deaminizes from aminocompound from isocyanate compound in the formula, and n is 1 to 4 integer, and R is an alkyl, and wherein at least one R has the alkyl that is no less than 8 carbon atoms.
The traditional surface-treated pearl filler that uses in described moisture-curable resin combination has the necessary package stability of described moisture-curable resin combination, but not talkative its set time is short, therefore must rely on the amount of regulating catalyzer.Yet, by being used in combination surface-treated pearl filler of the present invention, can improve the long shortcoming set time relevant with traditional surface-treated pearl filler with described traditional filler, shorten set time.
The ratio of surface-treated pearl filler of the present invention and described traditional filler is not specifically limited, and can determine to make described set time of satisfactory level arbitrarily.
Below will do more detailed explanation to the present invention, but the present invention is not limited to this by embodiment and comparative example.Embodiment 1
Contain and have 20m toward 10Kg
2(controlling concn is 160gCaCO to the aqueous slurry of the precipitated chalk of/gBET specific surface area
3/ kg water also is controlled at 75 ℃) the middle 80g stearic acid (fusing point is 70 ℃) that adds, implemented described surface coated in 1 hour thereby stir.Thereafter, with the mixture of gained dewater to solid content be 60% (weight), dry then and grind, thus obtain with stearic acid surface-treated calcium carbonate powders.Embodiment 2
Change into 50 ℃ except stearic acid changes lauric acid (fusing point is 44 ℃) and 75 ℃ into, other implements same method as mode same among the embodiment 1.Embodiment 3
Contain and have 20m toward 10Kg
2(controlling concn is 160gCaCO to the aqueous slurry of the precipitated chalk of/gBET specific surface area
3/ kg water, and be controlled at 75 ℃) at first add the 80g stearic acid in, add the calcium hydroxide slurry of 104.2g10% (weight) then, implemented described surface coated in 5 hours thereby stir.Thereafter, with the mixture of gained dewater to solid content be 60% (weight), dry then and grind, thus obtain with calcium stearate surface-treated calcium carbonate powders.Embodiment 4
Except the calcium hydroxide slurry of 104.2g10% (weight) changes into the 15.8g calcium oxide, other implements same method as mode same among the embodiment 3, thereby obtains with calcium stearate surface-treated calcium carbonate powders.Embodiment 5
Except described stearic acid changes lauric acid into, 75 ℃ of amounts that change 50 ℃ and calcium hydroxide slurry into are outside 104.2g changes 148g into, and other implements same method as mode same among the embodiment 3, thereby obtain with calcium laurate surface-treated calcium carbonate powders.Embodiment 6
Contain and have 20m toward 10Kg
2(controlling concn is 160gCaCO to the aqueous slurry of the precipitated chalk of/g BET specific surface area
3/ kg water, and be controlled at 75 ℃) add the methyl alcohol slurry that contains Magnesium Stearate (fusing point is 132 ℃) of 800g10% (weight) in, implemented described surface coated in 1 hour thereby stir.Subsequently, with the mixture of gained dewater to solid content be 60% (weight), dry then, grinds after one hour 140 ℃ of thermal treatments, thereby obtains usefulness Magnesium Stearate surface-treated calcium carbonate powders.Embodiment 7
Change into 160 ℃ except described Magnesium Stearate changes Magnesium monolaurate (fusing point is 150 ℃) and 140 ℃ into, other implements same method as mode same among the embodiment 5.Embodiment 8
Contain and have 20m toward 10Kg
2(controlling concn is 160gCaCO to the aqueous slurry of the precipitated chalk of/gBET specific surface area
3/ kg water, and be controlled at 75 ℃) add the hydrothermal solution that contains potassium stearate of 800g10% (weight) in, implemented described surface coated in one hour thereby stir.Subsequently, with the mixture of gained with 5 times of water agitation and dilutions and dewater to solid content be 60% (weight), dry then and grind, thus obtain with calcium stearate surface-treated calcium carbonate powders.By the amount of x-ray fluorescence analysis device (by the XFR-1500 of Shimadzu Corp. manufacturing) mensuration potassium, the result is 5.2 * 10
-4Mol/100gCaCO
3Embodiment 9
Except described diluting water changes into 2 times from 5 times, other implements same method as mode same among the embodiment 8.Be determined at the amount with the potassium in the calcium stearate surface-treated calcium carbonate powders that is obtained by x-ray fluorescence analysis device (by the XFR-1500 of Shimadzu Corp. manufacturing), the result is 8.5 * 10
-4Mol/100gCaCO
3Embodiment 10
Except the hydrothermal solution that contains potassium stearate of 800g10% (weight) changes into the hydrothermal solution that contains abietic acid potassium of 800g10% (weight), other implements same method as mode same among the embodiment 8.Be determined at the amount with the potassium in the abietic acid calcium surface-treated calcium carbonate powders that is obtained by x-ray fluorescence analysis device (by the XFR-1500 of Shimadzu Corp. manufacturing), the result is 5.0 * 10
-4Mol/100gCaCO
3Embodiment 11
Contain and have 20m toward 10Kg
2(controlling concn is 160gCaCO to the aqueous slurry of the precipitated chalk of/gBET specific surface area
3/ kg water) hydrothermal solution that contains potassium stearate that adds 800g10% (weight) in adds the magnesium chloride slurry of 236g10% (weight) then, implements described surface coated in 5 hours thereby stir.Subsequently, with the mixture of gained with 5 times of water agitation and dilutions and dewater to solid content be 60% (weight), dry then and grind, thus obtain with Magnesium Stearate surface-treated calcium carbonate powders.Be determined at potassic amount in the surface-treated lime carbonate of gained by x-ray fluorescence analysis device (XFR-1500 that is made by Shimadzu Corp.), the result is 4.1 * 10
-4Mol/100gCaCO
3Embodiment 12
Contain and have 2m
2(controlling concn is 200gCaCO to the aqueous slurry of the water-ground limestone of/gBET specific surface area
3/ kg water) by using the wet lapping machine to carry out wet lapping, obtain to contain to have 15m
2The aqueous slurry of the water-ground limestone of/gBET specific surface area.In the aqueous slurry of 10Kg gained, add the hydrothermal solution that contains potassium stearate of 800g10% (weight), thereby implement described surface coated.Thereafter, with the mixture of gained with 5 times of water agitation and dilutions and dewater to solid content be 60% (weight), dry then and grind, thus obtain with calcium stearate surface-treated calcium carbonate powders.Be determined at potassic amount in the surface-treated lime carbonate of gained by x-ray fluorescence analysis device (XFR-1500 that is made by Shimadzu Corp.), the result is 2.5 * 10
-4Mol/100gCaCO
3The comparative example 1
Contain (the SMV-20 type of making by Kawata Seisakusyo of precipitated chalk powder feed to the 20 liter super mixing tank of surface-treated precipitated chalk not with what 8Kg prepared in embodiment 1, agitating vane: S type and BL type twayblade) in, be heated to 90 ℃, add the 400g stearic acid then, under 2000rpm, mixed 30 minutes, implement described surface treatment by dry method, obtain thus with the dried surface-treated calcium carbonate powders of stearic acid.The comparative example 2
Change into 50 ℃ except 75 ℃, other implements same method as mode same among the embodiment 1.The comparative example 3
Except the calcium hydroxide slurry of 104.2g10% (weight) changes into the potassium hydroxide solution of 157.7g10% (weight), other implements same method as mode same among the embodiment 3.The comparative example 4
Except changing in 1 hour 120 ℃ of following thermal treatments 1 hour 140 ℃ of following thermal treatments, other implements same method as mode same among the embodiment 6.The comparative example 5
Except 5 times of water of no use carried out agitation and dilution (not dilution), other implemented same method as mode same among the embodiment 8.By x-ray fluorescence analysis device (XFR-1500 that makes by ShimadzuCorp.) be determined at gained with potassic amount in the calcium stearate surface-treated calcium carbonate powders, the result is 2.0 * 10
-3Mol/100gCaCO
3The comparative example 6
Except described stearic acid changes into the sodium stearate, other implements same method as mode same among the embodiment 1.(by the XFR-1500 of Shimadzu Corp. manufacturing) measures the amount with the contained sodium of calcium stearate surface-treated calcium carbonate powders by the x-ray fluorescence analysis device, and the result is 2.2 * 10
-3Mol/100gCaCO
3The comparative example 7
Except described stearic acid changes into the sodium laurate, other implements same method as mode same among the embodiment 1.(by the XFR-1500 of Shimadzu Corp. manufacturing) measures the amount with the contained sodium of calcium laurate surface-treated calcium carbonate powders by the x-ray fluorescence analysis device, and the result is 3.0 * 10
-3Mol/100gCaCO
3The comparative example 8
Except 5 times of water of no use carried out agitation and dilution (not dilution), other implemented same method as mode same among the embodiment 10.By x-ray fluorescence analysis device (XFR-1500 that makes by ShimadzuCorp.) be determined at gained with potassic amount in the calcium stearate surface-treated calcium carbonate powders, the result is 2.1 * 10
-3Mol/100gCaCO
3The comparative example 9
Except 5 times of water of no use carried out agitation and dilution (not dilution), other implemented same method as mode same among the embodiment 11.By x-ray fluorescence analysis device (XFR-1500 that makes by ShimadzuCorp.) be determined at gained with potassic amount in the Magnesium Stearate surface-treated calcium carbonate powders, the result is 1.9 * 10
-3Mol/100gCaCO
3The comparative example 10
Except described stearic acid changed stearyl glyceryl ester into, other implemented same method as mode same among the embodiment 1.The comparative example 11
Use in the sodium laurate surface-treated calcium carbonate powders toward 1Kg, the surface treatment agent that adds 50g formula (2) representative with 30 μ m mean diameters, by using Nautamixer to do surface treatment, wherein at room temperature carried out 15 minutes and under 110 ℃, carried out 1 hour.
Embodiment 13 to 23, and the comparative example 12 to 22
The powder that is obtained by embodiment 1 to 9,11,12 and comparative example 1 to 7,9 to 11 was 150 ℃ of dryings 5 hours, prepare modified polyorganosiloxane one-pack type Encapulant composition by following mixture ratio and kneading method, by the described performance of following test evaluation.Simultaneously, the powder among the comparative example 21 was 120 ℃ of dryings 5 hours.Described result is displayed in Table 1.50 parts of 50 parts of (weight) samples of (weight) plasticizer DOP of [mixture ratio] resin (by the MS polymkeric substance S203 of Kaneka company production): 2 parts of (weight) [kneading methods] of 120 parts of (weight) catalyzer of surface-treated pearl filler (by Nitto Kasei Co., the NEOSTANN U220 that Ltd. produces)
Mediate above-mentioned preparation of compositions sealing material by using small-sized kneader.Thus obtained sealing material is packed in the columniform tube tightly as the one-pack type sealing material.[shelf-stable property testing]
Viscosity to (50 ℃ * 2 week in baking oven) after (20 ℃ * 1 day) after mediating instant viscosity and the lapse of time is estimated.[measuring method of viscosity]
Measure by using B8U type viscometer (rotating shaft: No. 7).[slump resistance]
According to following standard, the state when estimating described sealing material and vertically apply with bore hole:
Zero: good
△: poor slightly
*: poor
Table 1
See clearly that from table 1 composition that contains described surface-treated pearl filler of the present invention is being excellent aspect package stability, thixotropy and the slump resistance.Embodiment 24 to 42, and the comparative example 23 to 35
150 ℃ of dryings 5 hours, prepare polyurethane monocomponent type Encapulant composition by following mixture ratio and kneading method, by the powder of embodiment 1 to 9,11,12 and comparative example's 1 to 7,9 to 11 gained by its performance of following test evaluation.Simultaneously, the powder among the comparative example 32 was 120 ℃ of dryings 5 hours.The result is displayed in Table 2.
In addition, change the mixture ratio of the surface-treated pearl filler of gained in embodiment 3,4 and comparative example 10,11, measure the storage period of polyurethane monocomponent type sealing material.The result is displayed in Table 3.[mixture ratio] resin (by Takeda Chemical Industeies, the TAKENATE L1078 that Ltd. produces)
120 parts of (weight) samples: 80 parts of (weight) [kneading methods] of surface-treated pearl filler
Mediate above-mentioned preparation of compositions sealing material by using small-sized kneader.Thus obtained sealing material is packed in the columniform tube tightly as the one-pack type sealing material.[shelf-stable property testing]
Viscosity to (40 ℃ * 2 week in baking oven) after (20 ℃ * 1 day) after mediating instant viscosity and the lapse of time is estimated.[measuring method of viscosity]
Measure by using B8U type viscometer (rotating shaft: No. 7).[slump resistance]
According to following standard, the state when estimating described sealing material and vertically apply with bore hole:
Zero: good
△: poor slightly
*: poor [curing performance]
Required time is estimated when not adhering to the degree of pointing by being cured to after described sealing material is extruded from described under 20 ℃.
Zero: be solidificated in 3 hours and finish.
*: be solidificated in 3 hours and can not finish.[set time]
Measure the time when under 20 ℃, being cured to the degree that does not adhere to finger after described sealing material is extruded from described.
Table 2
Table 3
| Sample | Set time (hour) | |
| Embodiment 35 embodiment 36 embodiment 37 embodiment 38 embodiment 39 embodiment 40 embodiment 41 embodiment 42 | 40 parts of (weight)+comparative examples' 11 of sample of 60 parts of (weight) embodiment 4 of sample of 60 parts of (weight)+comparative examples 11 of sample of 40 parts of (weight) embodiment 4 of sample of 80 parts of (weight)+comparative examples 11 of sample of 80 parts of (weight) embodiment 4 of sample of 40 parts of (weight)+comparative examples 10 of sample of 60 parts of (weight) embodiment 3 of sample of 60 parts of (weight)+comparative examples 10 of sample of 40 parts of (weight) embodiment 3 of sample of 80 parts of (weight)+comparative examples 10 of sample of 120 parts of (weight) embodiment 3 of sample of 120 parts of (weight) embodiment 4 of the sample of embodiment 3 80 parts in sample (weight) | ????2.0 ????2.5 ????3.5 ????5.5 ????7.5 ????4.0 ????6.0 ????8.0 |
| Comparative example 34 comparative examples 35 | 120 parts of (weight) comparative examples' 11 of comparative example 10 sample 120 parts in sample (weight) | ????9.0 ????10.0 |
See clearly that from table 2 composition that contains described surface-treated pearl filler of the present invention is being significantly excellent aspect package stability, thixotropy and the slump resistance.
Also clearly see from table 3,, can solve the shortcoming of described conventional filler length set time and shorten described set time if surface-treated pearl filler of the present invention is used in combination with described traditional surface treatment pearl filler.Embodiment 43 to 53, and the comparative example 36 to 43
Use prepares polychlorovinyl sheet material by the powder of embodiment 1 to 9,11,12 and comparative example's 1 to 7,9 to 11 gained by following mixture ratio and kneading method, by its performance of following test evaluation.The result is displayed in Table 4.[mixture ratio] polyvinyl chloride (PVC) RESINS is (by Nippon Vinyl Co., Ltd. the S-1001 of Sheng Chaning) 100 parts of 50 parts of (weight) ternarys of (weight) DOP alkali are (by Kikuchi Shikiso Co., Ltd. 1 part of (weight) sample of 3 parts of (weight) lead stearates (by Kikuchi Shikiso Co., the NS-100 that the Ltd. produces) TS-100 of Sheng Chaning): 50 parts of (weight) [methods that prepare polychlorovinyl sheet material] of surface-treated pearl filler
The roll of use under 165 ℃ mediated described composition 6 minutes, took out the sheet material of thick 2mm.The sheet material that takes out is inserted between two iron plates, be heated to 170 ℃ of preheatings in following 7 minutes by pitcher pump after, at 7.8Mpa (80Kg/cm
2) pressure under exert pressure and kept 3 minutes.After cooling off described iron plate, take out described sheet material.The thickness of described sheet material is 1mm.[volume resistance test]
Measure the volume resistance of the sheet material of gained according to JISK6723.[dispersed test]
According to following standard, the surface of the sheet material that gets with bore hole observation post:
Zero: good
△: poor slightly
*: poor
Table 4
See clearly that from table 4 composition that contains described surface-treated pearl filler of the present invention is being significantly excellent aspect dispersed and the insulativity.Embodiment 54, and the comparative example 44
Use the powder of sand mill kneading by following mixture ratio, preparation water-based ink resin composition by embodiment 10 and comparative example's 8 gained.By its performance of following test evaluation.The result is displayed in Table 5.[mixture ratio] resin (by Johnson Polymer Co., the JOHNCRYL J-69 that Ltd. produces)
0.8 part of (weight) tinting material of 18 parts of (weight) polysiloxane defoamers of 100 parts of (weight) water is (by Dainippon Ink﹠amp; Chemicals, the FASTOGEN TGR that Inc. produces)
20 parts of (weight) samples: 15 parts of (weight) [water resistance tests] of surface-treated pearl filler
Use wire bar applicator that each water-based printing ink composition is deployed on the RengoCRC White Board (by Rengo Co., Ltd. produces)., down with rub described expansion paper 5 times of aqueous cloth ink transfer is estimated to the degree of described cloth at load 2.0N (200g).
Zero: do not have ink transfer to described cloth.
*: printing ink is transferred on the described cloth in a large number.
Table 5
See obviously that from table 5 ink composite that contains described surface-treated pearl filler of the present invention is excellent aspect water tolerance.Embodiment 55 to 65, and the comparative example 45 to 52
By using sand mill to disperse by the powder that embodiment 1 to 9,11,12 and comparative example 1 to 7,9 obtain, be not more than 25 μ m up to particle diameter, and preparation Synolac paint composite, by its performance of following test evaluation.The result is displayed in Table 6.[mixture ratio] Synolac is (by Dainippon Ink﹠amp; Chemicals, Inc. 250 parts of (weight) titanium dioxide (Titan dioxide) (by Ishihara Sangyo Kaisha, the TIPAQUER-820 that Ltd. produces) the BECKOSOL P-470-70 of Sheng Chaning)
120 parts of (weight) water-ground limestones (by Maruo Calcium Co., the Super SSS that Ltd. produces)
14 parts of (weight) antis of 70 parts of (weight) siccative of 33 parts of (weight) solvent oils (by Kusumoto Kasei Co., the DISPARLON#501 that Ltd. produces)
1.5 part 350 parts of (weight) samples of (weight) granulated glass sphere: 58 parts of (weight) [gloss and water resistance tests] of surface-treated pearl filler
With spreader each Synolac paint composite is applied on the surface of sheet glass, thickness is 4 mils, at room temperature dry 24 hours, and with the gloss of Murakami gloss device measurement at 60 °.Described sheet glass immersed in water 3 day postevaluation its gloss characteristic thereafter.
Table 6
See clearly that from table 6 composition that contains described surface-treated pearl filler of the present invention is excellent aspect water tolerance.[total evaluation]
Surface treatment pearl filler from aforesaid test result overall merit embodiment 1 to 12 and comparative example 1 to 11.The result is displayed in Table 7.
◎: show very excellent performance.
Zero: show excellent performance.
△: although they can use, performance does not improve.
*: performance reduces.
Table 7
| Total evaluation | |
| Embodiment 1 embodiment 2 embodiment 3 embodiment 4 embodiment 5 embodiment 6 embodiment 7 embodiment 8 embodiment 9 embodiment 10 embodiment 11 embodiment 12 | ??○ ????○ ????◎ ????◎ ????◎ ????◎ ????◎ ????◎ ????○ ????◎ ????◎ ????◎ |
| Comparative example 1 comparative example 2 comparative examples 3 comparative examples 4 comparative examples 5 comparative examples 6 | ??× ????× ????△ ????× ????△ ????△ |
| Comparative example 7 comparative examples 8 comparative examples 9 comparative examples 10 comparative examples 11 | ??△ ????△ ????△ ????△ ????△ |
Industrial applicability
As described above, surface-treated pearl filler of the present invention is especially suitable for use as the filler of resin, for example, when being used for curable resin composition, thixotropy and slump resistance and the good bin stability of the heat resistance of excellence, excellence when demonstrating drying when being used for plastics, show excellent dispersiveness and insulating properties, when being used for paint and printing ink, show excellent resistance to water.
Claims (16)
1. surface-treated pearl filler, the surface of wherein said lime carbonate is with the surface treatment of wetting of at least a surface treatment agent that is selected from saturated fatty acid, unsaturated fatty acids, alicyclic carboxylic acid and resinous acid.
2. surface-treated pearl filler, the surface of wherein said lime carbonate is with the surface treatment of wetting of the surface treatment agent of the metallic soap of the metallic soap of at least a metallic soap that is selected from saturated fatty acid, unsaturated fatty acids, alicyclic carboxylic acid's metallic soap and resinous acid, and alkali-metal content is no more than 1.0 * 10
-3Mol/100gCaCO
3
3. claim 1 or 2 surface-treated pearl filler, the BET specific surface area of wherein said lime carbonate are 3 to 120m
2/ g.
4. method of producing the surface-treated pearl filler of claim 1 or 3 said method comprising the steps of:
Add in the aqueous slurry calciferous at least a surface treatment agent that is selected from saturated fatty acid, unsaturated fatty acids, alicyclic carboxylic acid and resinous acid and
The mixture of heating gained is to the temperature that is not less than these sour fusing points, thus the described lime carbonate of surface treatment.
5. method of producing the surface-treated pearl filler of claim 2 or 3 said method comprising the steps of:
In aqueous slurry calciferous, add (A) at least a surface treatment agent that is selected from saturated fatty acid, unsaturated fatty acids, alicyclic carboxylic acid and resinous acid, (B) metal hydroxides or metal oxide, described metal hydroxides or metal oxide can by with (A) reaction produce the water-insoluble metallic soap and
With by (A) and (B) the metallic soap surface treatment lime carbonate of reaction (A) that obtain.
6. method of producing the surface-treated pearl filler of claim 2 or 3 said method comprising the steps of:
Be added at least a surface treatment agent that is selected from saturated fatty acid metallic soap, unsaturated fatty acids metallic soap, alicyclic carboxylic acid's metallic soap and resinous acid metallic soap in the organic solvent slurry in the aqueous slurry calciferous,
The dehydration and the slurry of dry gained and
The mixture of heating gained is to the temperature of the fusing point that is not less than adding metallic soap wherein, thus the described lime carbonate of surface treatment.
7. method of producing the surface-treated pearl filler of claim 2 or 3 said method comprising the steps of:
The surface treatment agent that adds an alkali metal salt of an alkali metal salt, alicyclic carboxylic acid's an alkali metal salt of (C) at least a an alkali metal salt that is selected from saturated fatty acid, unsaturated fatty acids and resinous acid in the aqueous slurry calciferous,
With the described lime carbonate of described surface treatment agent surface treatment and
Wash the lime carbonate of described processing with water, be no more than 1.0 * 10 thereby control alkali-metal content
-3Mol/100gCaCO
3
8. method of producing the surface-treated pearl filler of claim 2 or 3 said method comprising the steps of:
The surface treatment agent that adds an alkali metal salt of an alkali metal salt, alicyclic carboxylic acid's an alkali metal salt of (C) at least a an alkali metal salt that is selected from saturated fatty acid, unsaturated fatty acids and resinous acid in the aqueous slurry calciferous,
With the described lime carbonate of described surface treatment agent surface treatment,
Adding can be by producing the metallic compound of metallic soap with an alkali metal salt of described (C) reaction, thus carry out double decomposition generate (C) metallic soap and
Wash the lime carbonate of described processing with water, be no more than 1.0 * 10 thereby control alkali-metal content
-3Mol/100gCaCO
3
9. resin combination, described resin combination comprise 1 to 3 each surface-treated pearl filler with resin alloy.
10. the resin combination of claim 9, wherein said resin is the resin that is used to paint.
11. the resin combination of claim 9, wherein said resin are the resins that is used for printing ink.
12. the resin combination of claim 9, wherein said resin are the resins that is used for plastics.
13. the resin combination of claim 9, wherein said resin are the resins that is applied to seal gum.
14. the resin combination of claim 9, wherein said resin is a cured resin.
15. the resin combination of claim 9, wherein said resin are the moisture-curable resins.
16. moisture-curable resin combination, described resin combination comprise with the claim 1 to 3 of resin alloy each the surface-treated pearl filler and (D) carry out surface-treated lime carbonate with the have compound and at least a carboxylic acid, sulfonic acid and their metal-salt of being selected from that are not less than 50 ℃ of fusing points of fatty acid ester and/or following formula (1) representative:
A removes the residual group of isocyanate groups or removes the residual group that deaminizes from aminocompound from isocyanate compound in the formula, and n is 1 to 4 integer, and R is an alkyl, and wherein at least one R has the alkyl that is no less than 8 carbon atoms.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10213099A JP3151196B2 (en) | 1998-04-10 | 1999-04-09 | Surface-treated calcium carbonate filler, method for producing the same, and resin composition containing the filler |
| JP102130/1999 | 1999-04-09 |
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|---|---|---|---|
| CNB2003101143926A Division CN1244644C (en) | 1999-04-09 | 1999-11-25 | Surface treated calcium carbonate filling process for producing the same filling and resin composition containing the same filling |
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| CN1334848A true CN1334848A (en) | 2002-02-06 |
| CN1144846C CN1144846C (en) | 2004-04-07 |
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| CNB998160539A Expired - Lifetime CN1144846C (en) | 1999-04-09 | 1999-11-25 | Surface-treated calcium carbonate filler, process for producing same, and resin composition contg. said filler |
| CNB2003101143926A Expired - Lifetime CN1244644C (en) | 1999-04-09 | 1999-11-25 | Surface treated calcium carbonate filling process for producing the same filling and resin composition containing the same filling |
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| CNB2003101143926A Expired - Lifetime CN1244644C (en) | 1999-04-09 | 1999-11-25 | Surface treated calcium carbonate filling process for producing the same filling and resin composition containing the same filling |
Country Status (4)
| Country | Link |
|---|---|
| KR (1) | KR100623906B1 (en) |
| CN (2) | CN1144846C (en) |
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|---|---|---|---|---|
| JPS55118985A (en) * | 1979-03-07 | 1980-09-12 | Nippon Petrochem Co Ltd | Oil chaulking material |
| JPS591571A (en) * | 1982-06-28 | 1984-01-06 | Shiraishi Chuo Kenkyusho:Kk | Production of finely divided calcium carbonate pigment |
| JPS59168084A (en) * | 1983-03-14 | 1984-09-21 | Maruo Calcium Kk | Hardening of sealant |
| JPS59191764A (en) * | 1983-04-14 | 1984-10-30 | Maruo Calcium Kk | Production of surface-treated calcium carbonate highly affinitive with organic vehicle |
| JPS6069011A (en) * | 1983-09-26 | 1985-04-19 | Miyoshi Kasei:Kk | Treatment of pigment with metal soap |
| JPS617363A (en) * | 1984-06-20 | 1986-01-14 | Maruo Calcium Kk | Solvent-type coating |
| JPS6197363A (en) * | 1984-10-17 | 1986-05-15 | Okutama Kogyo Kk | Production of calcium carbonate filler |
| JPH10245221A (en) * | 1997-03-03 | 1998-09-14 | Yokohama Rubber Co Ltd:The | Surface-treated calcium carbonate and one-pack moisture-curing type resin composition |
| JP3151196B2 (en) * | 1998-04-10 | 2001-04-03 | 丸尾カルシウム株式会社 | Surface-treated calcium carbonate filler, method for producing the same, and resin composition containing the filler |
-
1999
- 1999-11-25 KR KR1020017007920A patent/KR100623906B1/en active IP Right Grant
- 1999-11-25 ID IDW00200101707A patent/ID29587A/en unknown
- 1999-11-25 WO PCT/JP1999/006568 patent/WO2000061690A1/en active IP Right Grant
- 1999-11-25 CN CNB998160539A patent/CN1144846C/en not_active Expired - Lifetime
- 1999-11-25 CN CNB2003101143926A patent/CN1244644C/en not_active Expired - Lifetime
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100419032C (en) * | 2005-01-05 | 2008-09-17 | 上海东升新材料有限公司 | Heavy calcium carbonate filling preparation method |
| CN100336974C (en) * | 2005-06-16 | 2007-09-12 | 陕西科技大学 | Modifying method using talcum powder as paper filler and adhesive-applying agent |
| CN102702944A (en) * | 2012-06-29 | 2012-10-03 | 惠州市长润发涂料有限公司 | Double-component PU (Polyurethane) water drop effect decorative paint and preparation method thereof |
| CN104736646A (en) * | 2012-10-16 | 2015-06-24 | 欧米亚国际集团 | Process of controlled chemical reaction of a solid filler material surface and additives to produce a surface treated filler material product |
| CN105349020A (en) * | 2015-02-20 | 2016-02-24 | 上海埃菲东多胶粘技术有限公司 | Low viscosity moisture cured polymer compositions with tensile and creep properties for Industrial coatings,adhesives and sealant applications |
| CN107429079A (en) * | 2015-03-23 | 2017-12-01 | 丸尾钙株式会社 | Curable resin composition surface treatment pearl filler and the curable resin composition containing the filler |
| 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 |
| CN108359274A (en) * | 2018-02-07 | 2018-08-03 | 广西大学 | Rosin derivative chelates calcium modified Nano or lightweight CaCO3Powder preparation method |
| CN109678697A (en) * | 2018-12-19 | 2019-04-26 | 安徽省宣城市华纳新材料科技有限公司 | A method of recycling fatty acid surface inorganic agent in calcium carbonate production |
| CN112175565A (en) * | 2019-07-01 | 2021-01-05 | 三键有限公司 | Moisture-curable resin composition and cured product |
Also Published As
| Publication number | Publication date |
|---|---|
| KR100623906B1 (en) | 2006-09-13 |
| KR20010099886A (en) | 2001-11-09 |
| CN1144846C (en) | 2004-04-07 |
| WO2000061690A1 (en) | 2000-10-19 |
| CN1506409A (en) | 2004-06-23 |
| ID29587A (en) | 2001-09-06 |
| CN1244644C (en) | 2006-03-08 |
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