CN1692076A - Surface-treated calcium carbonate, method for production thereof and resin composition comprising said calcium carbonate - Google Patents
Surface-treated calcium carbonate, method for production thereof and resin composition comprising said calcium carbonate Download PDFInfo
- Publication number
- CN1692076A CN1692076A CN 02827143 CN02827143A CN1692076A CN 1692076 A CN1692076 A CN 1692076A CN 02827143 CN02827143 CN 02827143 CN 02827143 A CN02827143 A CN 02827143A CN 1692076 A CN1692076 A CN 1692076A
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- China
- Prior art keywords
- calcium carbonate
- resin
- treated
- weight
- dxp
- Prior art date
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 title claims abstract description 456
- 229910000019 calcium carbonate Inorganic materials 0.000 title claims abstract description 219
- 239000011342 resin composition Substances 0.000 title claims abstract description 59
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 13
- 229920005989 resin Polymers 0.000 claims abstract description 95
- 239000011347 resin Substances 0.000 claims abstract description 95
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 41
- 238000004381 surface treatment Methods 0.000 claims abstract description 38
- 238000000576 coating method Methods 0.000 claims abstract description 32
- 239000011148 porous material Substances 0.000 claims abstract description 32
- 239000011248 coating agent Substances 0.000 claims abstract description 31
- 239000002002 slurry Substances 0.000 claims abstract description 26
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000009826 distribution Methods 0.000 claims abstract description 24
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052753 mercury Inorganic materials 0.000 claims abstract description 24
- 230000032683 aging Effects 0.000 claims abstract description 23
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 18
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims abstract description 15
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims abstract description 15
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 12
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 12
- 238000007664 blowing Methods 0.000 claims abstract description 3
- 239000002245 particle Substances 0.000 claims description 63
- -1 alkali metal salt Chemical class 0.000 claims description 58
- 239000012756 surface treatment agent Substances 0.000 claims description 27
- 239000002253 acid Substances 0.000 claims description 19
- 229910052783 alkali metal Inorganic materials 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 19
- 239000000126 substance Substances 0.000 claims description 19
- 239000000565 sealant Substances 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 15
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 10
- 238000001179 sorption measurement Methods 0.000 claims description 9
- 229920001944 Plastisol Polymers 0.000 claims description 8
- 150000003863 ammonium salts Chemical class 0.000 claims description 8
- 230000001186 cumulative effect Effects 0.000 claims description 8
- 238000000465 moulding Methods 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000004999 plastisol Substances 0.000 claims description 8
- 150000007513 acids Chemical class 0.000 claims description 7
- 150000001340 alkali metals Chemical class 0.000 claims description 7
- 230000004580 weight loss Effects 0.000 claims description 6
- 239000003945 anionic surfactant Substances 0.000 claims description 3
- 239000003093 cationic surfactant Substances 0.000 claims description 3
- 239000002736 nonionic surfactant Substances 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 claims description 2
- 230000000536 complexating effect Effects 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- 235000003441 saturated fatty acids Nutrition 0.000 claims description 2
- 150000004671 saturated fatty acids Chemical class 0.000 claims description 2
- 150000003460 sulfonic acids Chemical class 0.000 claims description 2
- 235000021122 unsaturated fatty acids Nutrition 0.000 claims description 2
- 150000004670 unsaturated fatty acids Chemical class 0.000 claims description 2
- 239000013256 coordination polymer Substances 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 claims 1
- 239000002184 metal Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 20
- 239000013585 weight reducing agent Substances 0.000 abstract description 3
- 238000002459 porosimetry Methods 0.000 abstract description 2
- 230000035515 penetration Effects 0.000 abstract 2
- 235000010216 calcium carbonate Nutrition 0.000 description 189
- 230000000052 comparative effect Effects 0.000 description 64
- 230000000704 physical effect Effects 0.000 description 34
- 238000012360 testing method Methods 0.000 description 24
- 239000000976 ink Substances 0.000 description 23
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 18
- 239000011164 primary particle Substances 0.000 description 18
- 238000003756 stirring Methods 0.000 description 17
- 235000011116 calcium hydroxide Nutrition 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 239000011163 secondary particle Substances 0.000 description 14
- 239000000203 mixture Substances 0.000 description 13
- 230000000694 effects Effects 0.000 description 12
- 238000001035 drying Methods 0.000 description 11
- 238000002156 mixing Methods 0.000 description 11
- 238000002360 preparation method Methods 0.000 description 11
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 11
- 101000679304 Homo sapiens T cell receptor gamma variable 2 Proteins 0.000 description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 102100022581 T cell receptor gamma variable 2 Human genes 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 description 10
- 238000007665 sagging Methods 0.000 description 10
- 229920000178 Acrylic resin Polymers 0.000 description 9
- 239000004925 Acrylic resin Substances 0.000 description 9
- 239000006185 dispersion Substances 0.000 description 9
- 235000013336 milk Nutrition 0.000 description 9
- 239000008267 milk Substances 0.000 description 9
- 210000004080 milk Anatomy 0.000 description 9
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- 235000011941 Tilia x europaea Nutrition 0.000 description 8
- 230000001070 adhesive effect Effects 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 239000004571 lime Substances 0.000 description 8
- 239000000654 additive Substances 0.000 description 7
- 239000000853 adhesive Substances 0.000 description 7
- 229910052791 calcium Inorganic materials 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- 229920003023 plastic Polymers 0.000 description 7
- 239000004033 plastic Substances 0.000 description 7
- 229920005749 polyurethane resin Polymers 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- 229920000180 alkyd Polymers 0.000 description 6
- 239000011575 calcium Substances 0.000 description 6
- 235000015165 citric acid Nutrition 0.000 description 6
- 239000003822 epoxy resin Substances 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 229920000647 polyepoxide Polymers 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000005299 abrasion Methods 0.000 description 5
- 238000013329 compounding Methods 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 230000005070 ripening Effects 0.000 description 5
- 229920002050 silicone resin Polymers 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000003381 stabilizer Substances 0.000 description 5
- 230000009974 thixotropic effect Effects 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 229920000877 Melamine resin Polymers 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 4
- 150000005215 alkyl ethers Chemical class 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 239000000123 paper Substances 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229920001807 Urea-formaldehyde Polymers 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 3
- QHIWVLPBUQWDMQ-UHFFFAOYSA-N butyl prop-2-enoate;methyl 2-methylprop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.COC(=O)C(C)=C.CCCCOC(=O)C=C QHIWVLPBUQWDMQ-UHFFFAOYSA-N 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 239000002274 desiccant Substances 0.000 description 3
- 239000003599 detergent Substances 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 239000005011 phenolic resin Substances 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
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- 239000011118 polyvinyl acetate Substances 0.000 description 3
- 239000005060 rubber Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000001509 sodium citrate Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 3
- 229940038773 trisodium citrate Drugs 0.000 description 3
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- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
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Landscapes
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
A surface-treated calcium carbonate, characterized in that it comprises calcium carbonate surface-treated with an organic agent for surface treatment, and has respective specific ranges of values for a BET specific surface area (Sw), a weight reduction by heat per unit specific surface area (As), an average pore diameter (Dxp) at which an increase in mercury penetration takes a maximum value in a specific range of pore diameter distribution by the mercury porosimetry, and an amount of the average pore diameter [a maximum value of the increase in mercury penetration (Dyp)/ an average pore diameter (Dxp)] and a method for producing the calcium carbonate which comprises adding a complex-forming material to a calcium hydroxide slurry, followed by blowing a carbon dioxide gas, to synthesize calcium carbonate, adjusting a calcium carbonate concentration, followed by aging, and treating the surface of the product with an organic agent for surface treatment. The surface-treated calcium carbonate is useful especially for a resin and can be used for producing a resin composition having improved adhesion to an article to be attached and forming a tough coating film.
Description
Technical Field
The present invention relates to calcium carbonate treated with an organic surface treatment agent, a method for producing the same, and a resin composition containing the same. More particularly, the present invention relates to a calcium carbonate treated with an organic surface-treating agent, a method for producing the same, and a resin composition characterized by being obtained by mixing the calcium carbonate with the surface-treated calcium carbonate, which provides a resin composition having excellent joint compatibility while having a tacky and thixotropic effect when used for a curable resin such as a sealant or an adhesive; for example, when mixed into a coating material, an ink or a plastisol, a resin composition is provided which not only has high gloss and high thixotropy, and sag resistance, but also can give a high-strength coating film.
Background
Calcium carbonate is widely used as a filler or pigment for plastics, paints, inks, sealants, adhesives, paper, rubber, and the like. For example, in the case of sealants, the sealants are widely used for waterproofing, sealing and the like in the fields of construction, automobiles, floor materials and the like, and there are many cases where the sealants are applied to vertical parts, and it is required that the sealants do not sag during the period from application to curing, and that the sealants have high viscosity and high thixotropy.
In order to solve the above problems, the present inventors have proposed a method for producing precipitated calcium carbonate (Japanese unexamined patent publication No. H10-72215), and in recent years, with further increase in demand, the demand for physical properties has been further increased.
For example, the demand for wall panels in individual housing is increasing dramatically, and in consideration of the repetition of drying and wetting of the wall panels and the movement of the components, a low modulus sealant is used, but the wall panels are subject to expansion and contraction due to the influence of temperature and humidity, and thus the sealant is required to have a tracking property for the joint. In order to impart these characteristics, colloidal calcium carbonate has been used so far, and it is possible to reduce the modulus after curing, to improve the following property to an adherend to some extent, and to finely adjust the tackiness, but there is a limit to conventional colloidal calcium carbonate for further adjustment of tackiness by reduction of the modulus and addition of a trace amount, and development of a finer highly dispersible substance has been desired.
Colloidal calcium carbonate has been used for paints and inks since a long time ago. In recent years, since a guarantee period such as 10-year guarantee is required for a coating material, a coating material having more excellent durability is required. In contrast, in the case of inks, there has been a problem that the transparency of the ink is lowered due to the difference in refractive index between calcium carbonate and the ink vehicle, and therefore, it is desired to reduce the amount of colloidal calcium carbonate to be mixed and to maintain the ink characteristics.
In addition, wollastonite and needle-like calcium carbonate are used for plastics to prevent the weld line strength of an injection molding machine from being low, but both of them have a particle size of several tens of micrometers to 200 micrometers and have a large particle size, which causes a problem of low impact strength. The existing colloidal calcium carbonate is difficult to inhibit the fusion line and has low strength and impact strength.
In addition, vinyl chloride-based resins are used in large amounts in plastisols, particularly for automobile bodies, and in recent years, acrylic resin-based materials have been studied as substitutes for these resins from the viewpoint of environmental issues. In particular, in the case of acrylic resins, film formation has been studied in consideration of not only weight reduction but also price difference from vinyl chloride resins, and it is necessary to add a small amount of a filler for imparting high viscosity, but conventional colloidal calcium carbonate cannot satisfy these requirements.
In view of the above circumstances, the present invention provides a calcium carbonate treated with an organic surface-treating agent, which has not only an effect of tackiness and thixotropy but also seam-following properties when used for a curable resin such as a sealant or an adhesive, a method for producing the same, and a resin composition containing the same; high gloss, excellent sag resistance, high film strength when used in, for example, coatings, inks, plastisols; when used in, for example, plastics, the strength of the weld line face can be prevented from being low, a resin composition having excellent impact strength can also be obtained, and weight can be reduced by reducing the amount added to the resin.
The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that: the present inventors have found that the above problems can be solved by adding a specific substance to conduct a carbonation reaction and then aging the resulting product at a specific concentration to obtain precipitated calcium carbonate having specific fineness and good dispersibility, and by treating the surface of the calcium carbonate with a specific amount of an organic surface-treating agent, the adhesion to an adherend can be improved, and the strength of the formed coating film itself can be improved.
Disclosure of Invention
That is, the first aspect of the present invention is a surface-treated calcium carbonate characterized in that: the calcium carbonate surface-treated with the organic surface-treating agent satisfies the following formulae (a), (b), (c) and (d).
(a)20≤Sw≤200 (m2/g)
(b)1.0≤As≤7.5 (mg/m2)
(c)0.003≤Dxp≤0.03 (μm)
(d)50≤Dyp/Dxp≤180
Wherein
Sw: BET specific surface area (m) by nitrogen adsorption2/g)
As: heat loss per unit specific surface area (mg/m) calculated by the following formula2) (Heat weight loss mg/g per 1g of calcium carbonate surface-treated at 200 ℃ to 500 ℃)/Sw
Dxp: in the mercury porosimetry, in the distribution of micropores in the range of 0.001-0.1 μm in micropore range, the average diameter (μm) of micropores when the mercury intrusion increment (cumulative (load) volume increment of micropores/log average diameter of micropores) is the maximum value (Dys)
Dyp: maximum value of mercury intrusion (mg/l)
Dyp/Dxp: average pore diameter
A second aspect of the present invention is a surface-treated calcium carbonate characterized by: the calcium carbonate surface-treated with the organic surface-treating agent satisfies the following formulae (a), (b), (e) and (f).
(a)20≤Sw≤200 (m2/g)
(b)1.0≤As≤7.5 (mg/m2)
(e)0.03≤Dxs≤1(μm)
(f) Dys ≤ 30% (by weight)
Wherein
Sw: BET specific surface area (m) by nitrogen adsorption2/g)
As: heat loss per unit specific surface area (mg/m) calculated by the following formula2) (Heat weight loss mg/g per 1g of calcium carbonate surface-treated at 200 ℃ to 500 ℃)/Sw
Dxs: in the particle size distribution measured by a laser diffractometer (SALD-2000, manufactured by Shimadzu corporation), the average particle diameter (. mu.m) was 50% by weight in total from the larger particle side
Dys: in the particle size distribution, the weight of the particle diameter exceeding 3 μm is accumulated (% by weight)
A third aspect of the present invention is a surface-treated calcium carbonate characterized by: comprising calcium carbonate surface-treated with an organic surface-treating agent, and satisfying the following formulas (a) to (f).
(a)20≤Sw≤200 (m2/g)
(b)1.0≤As≤7.5 (mg/m2)
(c)0.003≤Dxp≤0.03 (μm)
(d)50≤Dyp/Dxp≤180
(e)0.03≤Dxs≤1 (μm)
(f) Dys ≤ 30% (by weight)
Wherein
Sw: BET specific surface area (m) by nitrogen adsorption2/g)
As: heat loss per unit specific surface area (mg/m) calculated by the following formula2) (Heat weight loss mg/g per 1g of calcium carbonate surface-treated at 200 ℃ to 500 ℃)/Sw
Dxp: in the mercury intrusion method, in the distribution of micropores in the range of 0.001-0.1 μm in micropore range, the average diameter (μm) of micropores at which the mercury intrusion increment (cumulative micropore volume increment/log average micropore diameter) is the maximum value (Dys)
Dyp: maximum value of mercury intrusion (mg/l)
Dyp/Dxp: average pore diameter
Dxs: in the particle size distribution measured by a laser diffractometer (SALD-2000, manufactured by Shimadzu corporation), the average particle diameter (. mu.m) was 50% by weight in total from the larger particle side
Dys: in the above particle size distribution, the weight of the particle diameter exceeding 3 μm is integrated (% by weight)
The fourth aspect of the present invention is a method for producing surface-treated calcium carbonate, characterized in that: adding 0.5-15 wt% of a substance which forms a complex by complexing with metal ions to a calcium hydroxide slurry, carbonating by blowing carbon dioxide gas to synthesize calcium carbonate, adjusting the calcium carbonate concentration to 2.4-13.0 wt%, aging, and subjecting the obtained calcium carbonate to surface treatment with an organic surface treatment agent.
A fifth aspect of the present invention is a resin composition, characterized in that: the surface-treated calcium carbonate is mixed with a resin.
Best Mode for Carrying Out The Invention
The details of the present invention will be described below.
(a) The formula is the BET specific surface area of the surface-treated calcium carbonate of the present invention measured by nitrogen adsorption method, and is required to be 20 to 200m2(ii) in terms of/g. The specific surface area is less than 20m2At the time of/g, it is difficult to have a high viscosity which is the object of the present invention. And exceeds 200m2In the case of the solid content/g, the primary particles are preferably small, but the stability is deteriorated with time, and a problem occurs in dispersibility. Thus, it is preferably 30 to 150m2Per g, more preferably 40 to 120m2/g。
In addition, as a device for measuring the BET specific surface area, NOVA2000 model by Yuasa Ionics was used.
(b) The amount of the organic surface-treating agent represented by the formula (I) required per unit specific surface area of the surface-treated calcium carbonate of the present invention is 1.0 to 7.5mg/m As2. Among the existing calcium carbonates, there are many calcium carbonates on the market which have fine primary particles satisfying the formula (a), but the primary particles of these calcium carbonates aggregate to form secondary particles, and the secondary particles aggregate to form tertiary particles, so that the surface treatment amount of the coated calcium carbonate is less than 1.0mg/m2That is, the calcium carbonate of the present invention has a sufficient treatment amount, but it is difficult to sufficiently cover the surface because the formation of the tertiary particles is very small and the dispersibility of the formation of the secondary particles is extremely high, as compared with the conventional calcium carbonate. Therefore, when drying and powdering are performed in the case where the treatment amount is insufficient, tertiary aggregation is formed between the untreated surfaces, and the effect of the surface-treated calcium carbonate cannot be sufficiently exhibited. And exceeds 7.5mg/m2In the case of a large amount of the surface-treating agent, the surface-treating agent is released into the resin component or the plasticizing component, causing migration and surface roughening. Therefore, 1.5 to 5.0mg/m is preferable2More preferably 2.0 to 4.0mg/m2。
The heat loss per unit specific surface area was obtained as follows: about 100mg of the surface-treated calcium carbonate of type リガク was placed on a sample plate (made of platinum) having a diameter of 10mm, and the heat loss at 200 ℃ to 500 ℃ was measured at a temperature rise rate of 15 ℃ per minute to determine the heat loss rate (mg/g) per 1g of the surface-treated calcium carbonate, and the value was divided by the BET specific surface area value.
(c) The formulae (i) and (d) are indicators for knowing the dispersion state of the surface-treated calcium carbonate of the present invention.
(c) The formula is an average pore diameter (Dxp) at which the mercury intrusion increment is the maximum value (Dys) in the pore distribution in the range of 0.001 to 0.1 μm as measured by mercury intrusion method (porosimeter), and represents the fineness of the gaps between the surface-treated calcium carbonate particles. Therefore, it does not represent the fineness of the particles shown in the (nitrogen) adsorption method of the formula (a), but represents the average distance of the gaps between the primary particles, and is required to be 0.003 to 0.03. mu.m. When the average pore diameter is less than 0.003. mu.m, there arises a problem that the stability changes with time because the primary particles or the secondary particles are too fine. On the other hand, if the particle size exceeds 0.03. mu.m, the primary particles become too large, or secondary particle formation products in which the primary particles are strongly aggregated are present in a large amount, and the high-viscosity physical properties aimed at in the present invention cannot be obtained. Thus, it is preferably 0.005 to 0.025. mu.m, more preferably 0.006 to 0.020. mu.m.
The increase in mercury intrusion means an increase in micropore volume expressed by a calculation formula (cumulative micropore volume increase/log mean micropore diameter) (unit: ml/g). Of course, the maximum mercury intrusion (Dys) depends on the pore diameter, since the smaller the pore diameter, the smaller the pore volume.
(d) The number of the average pore diameter of the formula (c) is an index indicating high viscosity for the purpose of the present invention. As previously mentioned, the smaller the pore size, the smaller the pore volume and therefore, by adding together the maximum mercury intrusion increment (Dyp) and the average pore diameter (Dxp) of formula (c), the higher the number of Dyp/Dxp, the higher the viscosity, the amount (number) of pores required by the present invention can be derived. Therefore, the average pore size amount (Dyp/Dxp) of the present invention is required to be 50 to 180. When Dyp/Dxp is less than 50, the high viscosity which is the object of the present invention cannot be obtained. Whereas, if it exceeds 180, the average pore size is extremely small, and the stability of the primary particles or the secondary particles will be problematic with time. Therefore, it is preferably 60 to 150, more preferably 70 to 130.
When the surface-treated calcium carbonate of the present invention is outside the ranges of the formula (c) and the formula (d), for example, low gloss of a coating composition in which the calcium carbonate is mixed, low breaking strength of a sealer composition, and the like will occur.
The mercury intrusion device (porosimeter) used in the present invention and the main measurement conditions are as follows.
< measuring apparatus >
Shimadzu institute 9520 type
< Main measurement conditions >
Mercury purity 99.99%)
Mercury surface tension 480(dyns/cm)
The mercury contact angle is 135 DEG C
Conductance cell constant 10.79(μ l/pF)
Weight of sample: each weighed about 0.10g and measured
The surface-treated calcium carbonate of the present invention may be a substance satisfying the following formulas (e) to (f), and more preferably satisfies the following formulas (e) to (f) in addition to the above formulas (a) to (d).
(e)0.03≤Dxs≤1 (μm)
(f) Dys ≤ 30% (by weight)
Wherein,
dxs: in the particle size distribution measured by a laser diffractometer (SALD-2000, manufactured by Shimadzu corporation), the average particle diameter (. mu.m) was 50% by weight in total from the larger particle side
Dys: in the above particle size distribution, the weight of the particle diameter exceeding 3 μm is integrated (% by weight)
(e) The formula (f) is an index for knowing the dispersion state in the resin composition. Therefore, including the above formula as a consideration is preferable.
In addition, the particle size distribution was determined as follows: the following mixed materials (I) and (II) were weighed into a bottle containing 140ml of mayonnaise, stirred with a stainless steel spoon until visually dispersed, diluted with the mixed material (III), predispersed on an ultrasonic disperser, and the resultant was measured by a laser diffraction particle size distribution meter (manufactured by Shimadzu corporation: SALD-2000) as a sample.
(I) Neutral detergent (substance diluted 5 times with water) 2.0g
(II) calcium carbonate sample 0.4g
(III) Water 40g
It is particularly preferable that the mixing is adjusted as a pretreatment and then ultrasonic dispersion used as preliminary dispersion is carried out under a predetermined condition, and the ultrasonic dispersion device used in the examples of the present invention is one made by US-300T (manufactured by Nippon Seiko Seisaku-Sho Co., Ltd.) and is carried out under a predetermined condition of 100. mu.A-60 seconds. The neutral detergent is not particularly limited, and any commercially available detergent can be used, and ママレモン (manufactured by Lion corporation) is used in the present invention.
In the above-mentioned method for measuring the particle size distribution, when the average particle diameter (Dxs) of the present invention is less than 0.03. mu.m, the stability of the primary particles or the secondary particles may be lowered with time. On the other hand, if the particle diameter exceeds 1 μm, the amount of the tertiary particle formation tends to increase, and the dispersibility in the resin composition tends to deteriorate. Therefore, it is more preferably 0.05 to 0.8. mu.m, and still more preferably 0.08 to 0.5. mu.m.
If the cumulative weight (Dys) of the average particle diameters exceeding 3 μm exceeds 30% by weight, the dispersion state in the resin composition is not said to be sufficient, and it is difficult to obtain desired high-viscosity physical properties. Therefore, it is more preferably 25% by weight or less, and most preferably 20% by weight or less.
When the surface-treated calcium carbonate of the present invention is outside the ranges of the above-mentioned formulae (e) and (f), for example, the gloss of a coating composition containing the calcium carbonate is low, and problems such as the breaking strength of a sealer composition easily occur.
The surface-treated calcium carbonate of the present invention more preferably satisfies the following formulae (g) to (j). These define preferred ranges of the above formulae (c), (d), (e) and (f), respectively.
(g)0.005≤Dxp≤0.025(μm)
(h)60≤Dyp/Dxp≤150
(i)0.05≤Dxs≤0.8 (μm)
(j) Dys ≦ 25 (% by weight)
The surface-treated calcium carbonate of the present invention more preferably satisfies the following formula (k).
(k)0.1≤Sw·Dxp≤1.5
(k) The formula is a product of a BET specific surface area value (Sw) indicating the fineness of the primary particles of the surface-treated calcium carbonate and an average pore diameter (Dxp) indicating the fineness of the secondary particles. The primary particles and the secondary particles have been defined in the formulae (a) to (j), respectively, but are preferably not defined separately from each other, but are defined in a manner compatible with both of the formulae (k), which makes it easy to obtain desired viscosity properties. (k) When Sw. Dxp of the formula is less than 0.1, the stability of the primary or secondary particles decreases with time. When the amount exceeds 1.5, the amount of the tertiary particle formation tends to increase as described above. Therefore, it is more preferably 0.3 to 1.2, and still more preferably 0.5 to 1.0.
It is further preferred that the surface-treated calcium carbonate of the present invention satisfies the following formula (l).
(l)0.03≤Is≤3 (μmol/m2)
Wherein,
is: the alkali metal content per unit specific surface area calculated by the following formulaMetal content per 1g calcium carbonate (. mu. mol/g) }/Sw (m2/g)
(l) The formula (I) represents the alkali metal content in the surface-treated calcium carbonate, and is usually preferably 0.03 to 3. mu. mol/m2The range of (1). Among alkali metal compounds, particularly sodium compounds, are easily reacted with moisture outside the system because of high exothermic reactivity, so that if more than 3. mu. mol/m is present in calcium carbonate2The sodium compound in an amount of the above-mentioned component causes a problem in storage stability such as dispersion failure particularly in the use of a sealing material. When the alkali metal content is made to be 0.03. mu. mol/m2At a level of either less than 0.03. mu. mol/m2Then, it is necessary 1) to make the surface treatment amount extremely small; or 2) excessive washing after the surface treatment; or 3) using an acid such as a fatty acid or a resin acid as a surface treatment agent. 1) The above-mentioned physical properties are liable to be deteriorated, and 2) the cost is increased because a large amount of water is required. On the other hand, in the case of 3), since surface treatment at a temperature not lower than the melting point is required, not only the cost is liable to increase, but also the selectivity of the surface treatment agent is limited, more preferably 0.15 to 2. mu. mol/m2Further preferably 0.3 to 1.5. mu. mol/m2。
More preferably, in the calcium carbonate slurry before surface treatment, the characteristics of the slurry preferably satisfy the following formula (m).
(m)0.03≤Dx≤0.40
Wherein,
dx: particle size (. mu.m) at 50% weight accumulation in the particle size distribution measured by a centrifugal particle size distribution meter (manufactured by Shimadzu corporation: SA-CP4)
The formula (m) represents the average particle diameter of the secondary particles of the surface-treated calcium carbonate of the present invention before surface treatment, and is a particle size distribution index using a clear numerical value. The surface-treated calcium carbonate of the present invention satisfying the formula (m) can surely exhibit the high viscosity-imparting effect which is the object of the present invention. Therefore, when Dx is less than 0.03, the stability and dispersibility of the primary particles of calcium carbonate with time are likely to be problematic. On the other hand, if it exceeds 0.40. mu.m, the proportion of the tertiary particle formation increases as described above, and therefore, it is difficult to obtain the high viscosity-imparting effect intended by the present invention in the surface-treated calcium carbonate. Therefore, it is more preferably from 0.07 to 0.35. mu.m, still more preferably from 0.10 to 0.30. mu.m.
The shape of the primary particle of calcium carbonate is not particularly limited, and a spherical shape, a spindle shape, a needle shape, a block shape, a chain shape (a chain shape), or the like can be used, and among them, a chain shape is preferable not only in terms of imparting high viscosity but also in terms of imparting resin strength.
As a more preferable mode, the surface-treated calcium carbonate of the present invention preferably satisfies the following formula.
(n)VIS2≥400(Pa·s)
(o)VIS20≥80(Pa·s)
(p)VIS2/VIS20≥5.0
Wherein,
VIS 2: (ii) viscosity (Pa. s) at 2rpm of a mixed paste of diisononyl phthalate (DINP) and surface-treated calcium carbonate measured by a BH type viscometer
VIS 20: viscosity (Pa. s) of the above paste at 20rpm
(n) to (p) represent the tack properties in the resin component of the surface-treated calcium carbonate of the present invention. The method for preparing a mixed paste of DINP and the calcium carbonate is as follows.
50 parts by weight of calcium carbonate sample
DINP 30 parts by weight
DINP 30 parts by weight (super addition)
DINP 30 parts by weight (super addition)
(1) A1 liter paper cup was charged with 30g of DINP, followed by weighing 50g of calcium carbonate. The paper cup was placed on a planetary stirring device KK-502N (manufactured by クラボウ Co.), kneaded for 60 seconds at rotation 765rpm and revolution 765rpm, and then manually stirred for 180 seconds with a stainless steel spoon.
(2) 30g of DINP was additionally added to the cup, and kneaded for 60 seconds at 765rpm for rotation and 765rpm for revolution, and then stirred by hand with a stainless spoon for 180 seconds.
(3) 30g of DINP was added to the cup, and kneaded for 60 seconds at 765rpm for rotation and 765rpm for revolution, and then kneaded for 180 seconds by hand with a stainless spoon to prepare a paste.
The paste prepared by the above method was left to cool at 20 ℃ for 12 hours, and then the viscosities of 2rpm and 20rpm were measured by a BH type viscometer.
Preferably, the paste prepared by the above method has a viscosity satisfying the formulae (n) to (p).
When the VIS2 is less than 400Pa · s, sagging prevention properties and the like may be slightly different from those of conventional products. When the VIS20 is less than 80Pa · s, it is difficult to obtain the viscosity-imparting effect required in the present invention. When VIS2/VIS20 is less than 5.0, it is difficult to impart high thixotropy. Therefore, VIS 2. gtoreq.500, VIS 20. gtoreq.90, VIS2/VIS 20. gtoreq.5.5 are more preferable, and VIS 2. gtoreq.800, VIS 20. gtoreq.130, and VIS2/VIS 20. gtoreq.6 are still more preferable.
The method for producing calcium carbonate before surface treatment of the surface-treated calcium carbonate of the present invention is not particularly limited, but differs from a production method in which a reagent that forms a complex with calcium is added to milk of lime, and the milk is subjected to carbonation reaction and then slaked, for example, as described in japanese patent application laid-open No. 10-72215, which is a conventional method, in terms of dispersion method, for example, depending on the slaking concentration, slaking time, and the like. In the above-mentioned conventional methods, it is clear that dispersed fine particles are obtained by keeping the BET specific surface area after aging as high as possible, but a production method of further dispersing is required to achieve the object of the present invention, i.e., to provide high viscosity and light weight.
Preferred production conditions of the calcium carbonate used in the present invention are as follows.
(reaction conditions)
Concentration of lime milk: 3.5 to 10.2% by weight
② complex-forming substance: 0.5 to 15% by weight
Flow of carbon dioxide gas: 300-3000L/hr
Fourthly, gas concentration: 10 to 50 percent
(ripening conditions)
Fifth, the calcium carbonate concentration: 2.4-13.0% by weight
Sixthly, curing time: 24-240 hours
(surface treatment)
Surface treatment amount: 3.5 to 50% by weight
The preferred method for producing calcium carbonate used in the present invention is specifically described below.
(reaction conditions)
The concentration of lime milk of (i) is preferably 3.5 to 10.2% by weight. If the lime milk concentration is less than 3.5%, not only is the yield low and the cost high, but also the dispersibility cannot be improved even if the concentration is further diluted. On the other hand, if the content exceeds 10.2% by weight, aggregation of the primary particle diameter tends to occur after the reaction, and even if aging progresses, the average particle diameter of the secondary particles becomes larger, and it becomes difficult to obtain desired viscosity physical properties. Therefore, it is more preferably 5.0 to 9.0% by weight, and still more preferably 6.0 to 8.0% by weight.
② the complex-forming substance is preferably added in an amount of 0.5 to 15% by weight. When the amount added is less than 0.5% by weight, the fine particles aimed at in the present invention are hardly obtained, while when it exceeds 15% by weight, the primary particles after the reaction are too fine, and the particle diameter of the secondary particles after aging sometimes does not satisfy the range of the formula (f) which is a preferable dispersion state, and as a result, it is difficult to obtain a desired effect of imparting high viscosity. The addition time may be before or during the carbonation reaction, or may be both before and during the reaction.
Examples of the complex-forming substance include hydroxycarboxylic acids such as citric acid, oxalic acid and malic acid, and alkali metal salts, alkaline earth metal salts and ammonium salts thereof; polyhydroxy carboxylic acids such as gluconic acid and tartaric acid, and alkali metal salts, alkaline earth metal salts and ammonium salts thereof; aminopolycarboxylic acids such as iminodiacetic acid, ethylenediaminetetraacetic acid, nitrilotriacetic acid, and alkali metal salts, alkaline earth metal salts, and ammonium salts thereof; polyacetic acids such as hexametaphosphoric acid and tripolyphosphoric acid, and alkali metal salts, alkaline earth metal salts and ammonium salts thereof; ketones such as acetylacetone, methyl acetoacetate, and allyl acetoacetate; sulfuric acid and alkali metal salts, alkaline earth metal salts, ammonium salts and the like thereof, and these complex-forming substances may be used alone or in combination of two or more. Among them, hydroxycarboxylic acids have high binding properties to calcium, and citric acid is particularly preferably used.
The flow rate of carbon dioxide gas is usually 3000L/hr per 1Kg of calcium hydroxide 300-. If the amount is less than 300L/hr, the primary particles after the reaction tend to become large, and if it exceeds 3000L/hr, the cost of industrial production tends to increase, which is not preferable.
The oxygen concentration of (4) is preferably 10-50%. When the gas concentration is less than 10%, the primary particles after the reaction tend to become large, and when it exceeds 50%, the industrial production cost is undesirably increased.
(ripening conditions)
The calcium carbonate concentration of the fifth step is preferably 2.4 to 13.0% by weight. When the content is less than 2.4% by weight, the industrial productivity is low, while when the content exceeds 13.0% by weight, the dispersibility is improved by aging, and the structural viscosity of the system is increased, the uniform stirring of the system becomes difficult, and the average particle diameter of the secondary particles may not satisfy the range of the formula (f). As a result, it is difficult to obtain the desired high viscosity-imparting effect. Therefore, it is more preferably 4.0 to 11.0% by weight, and still more preferably 5.0 to 9.0% by weight.
As described above, the ripening concentration is likely to be an important index for improving the dispersibility, and therefore, the effect of diluting the concentration within a preferable range is more effective as the amount of particles is smaller.
The aging time of (c) is preferably such that the effect of imparting high viscosity, which is the object of the present invention, is easily obtained if aging is performed to such an extent that the formula (f) as a preferable range as an index of dispersibility is satisfied. Therefore, the above-mentioned preparation conditions are about the aging time, and the aging time is not particularly limited, but is preferably 24 to 240 hours in general. When the aging time is less than 24 hours, it is difficult to obtain desired dispersed particles, and when it exceeds 240 hours, the industrial cost increases. Therefore, it is more preferably from 30 to 200 hours, and still more preferably from 40 to 180 hours.
The preparation conditions other than the above can be carried out in the same manner as in the conventional method. For example, the synthesis temperature is usually in the range of 5 to 30 ℃ and the aging temperature is usually in the range of 30 to 70 ℃. The stirring conditions in the aging may be any stirring force capable of uniformly stirring the entire liquid system, but if the stirring force is a conventional stirring force, the concentration of the system must be lowered, which tends to increase the cost. As for the productivity, it is preferable that the stirring ability is higher than the conventional stirring ability, of course, from the viewpoint of improving the dispersibility. Further, the stirring machine generally uses a paddle, a turbine, a propeller, a high-speed impeller, or the like.
(surface treatment)
The amount of surface treatment of (c) is not particularly limited As long As it is within the range of As in the formula (b) since it varies depending on the specific surface area of the calcium carbonate raw material, and is usually 3.5 to 50% by weight. When the surface treatment amount is less than 3.5% by weight, the surface of the fine, highly dispersible calcium carbonate of the present invention may not be sufficiently covered. As a result, secondary aggregation is formed between the untreated surfaces during drying and powdering, and it is difficult to sufficiently exhibit the effect of the surface-treated calcium carbonate. On the other hand, if the amount exceeds 50% by weight, the surface treatment agent becomes too much, and the surface treatment agent is released into the resin component or the plasticizing component, which tends to cause a migration phenomenon or a surface roughening phenomenon. Therefore, it is more preferably 5 to 40% by weight, and still more preferably 7 to 35% by weight. The surface treatment method is not particularly limited, and may be any wet or dry method.
The organic surface treating agent used in the present invention may use the following acids alone or in combination of two or more: saturated fatty acids represented by caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, アラギン acid, unsaturated fatty acids represented by oleic acid, elaidic acid, linoleic acid, ricinoleic acid, alicyclic carboxylic acids represented by naphthenic acid, resin acids represented by abietic acid, pimaric acid, パラストリン acid, neoabietic acid, modified rosins represented by their disproportionated rosins, hydrogenated rosins, dimerized rosins, trimerized rosins, sulfonic acids represented by alkylbenzene sulfonic acids, and their alkali metal salts, alkaline earth metal salts, ammonium salts, amine salts, and anionic, cationic, nonionic surfactants exemplified below. In particular, alkali metal salts of fatty acids and alkali metal salts of resin acids are preferable in view of the adsorption reactivity with calcium carbonate.
Examples of the anionic surfactant include alkyl ether sulfuric acid such as polyoxyethylene alkyl ether sulfuric acid, alkyl ether phosphoric acid such as polyoxyethylene alkyl ether phosphoric acid, alkylaryl ether sulfuric acid such as polyoxyethylene alkylphenyl ether sulfuric acid, alkylaryl ether phosphoric acid such as polyoxyethylene alkylphenyl ether phosphoric acid, alkyl sulfate ester such as polyoxyalkyl sulfate ester, alkyl phosphate ester such as polyoxyalkyl phosphate ester, alkylaryl sulfate ester such as polyoxyalkyl phenyl sulfate ester, alkylaryl phosphate ester such as polyoxyalkyl phenyl phosphate ester, alkylamide sulfate ester such as fatty acid alkylolamide sulfate ester, alkylsulfonic acid such as polyoxyethylene alkylsulfonic acid, alkylbenzenesulfonic acid, alkylnaphthalenesulfonic acid, sulfosuccinic acid ester such as dialkylsulfosuccinic acid ester, alpha-olefinsulfonic acid, N-acylsulfonic acid and/or alkali metal salt, alkaline earth metal salt, amine salt thereof, alkali metal salt thereof, Anionic surfactants such as ammonium salts, anionic polymer dispersants such as (meth) acrylic acid esters having cyclohexyl groups, (meth) acrylic acid esters having α, β monoethylenically unsaturated hydroxy esters, polyalkylene glycol mono (meth) acrylic acid esters, vinyl aromatics, unsaturated nitriles, unsaturated dicarboxylic acid esters, vinyl ethers, conjugated dienes, chain olefins, cyclic olefins, copolymers formed from sulfo group-containing monomers, and the like, and salts thereof obtained by partial or complete neutralization with alkali metals, alkaline earth metals, ammonium, and the like.
Examples of cationic surfactants are: aliphatic amine salts such as stearylamine acetate and stearylamine hydrochloride, aliphatic quaternary ammonium salts such as lauryltrimethylammonium chloride and stearyltrimethylammonium chloride, aromatic quaternary ammonium salts such as alkylbenzyldimethylammonium chloride, cationic surfactants such as heterocyclic quaternary ammonium substances, cationic polymer dispersants having polar groups such as amino (primary), imino (secondary), tertiary, quaternary ammonium, and hydrazino groups, and monomers copolymerizable with these polar group-containing monomers, for example, α, β unsaturated monocarboxylic acids, α, β unsaturated dicarboxylic acids, alkyl methacrylates, (meth) propenyl ethers having alkoxy groups, (meth) acrylate having cyclohexyl groups, α, β monoethylenically unsaturated hydroxy esters, polyalkylene glycol mono (meth) acrylate, vinyl esters, vinyl aromatics, unsaturated nitriles, unsaturated dicarboxylic esters, polyalkylene glycol mono (meth) acrylate, vinyl esters, vinyl ethers, conjugated dienes, chain olefins, cyclic olefins, copolymers with monomers containing a sulfonic group, and salts thereof obtained by partially or completely neutralizing alkali metals, alkaline earth metals, ammonium, and the like.
Examples of the nonionic surfactant include polyoxyethylene and derivatives thereof, betaines such as carboxybetaine and sulfobetaine, aminocarboxylic acids, and imidazoline derivatives.
After the surface treatment, it is preferable to filter impurity ions such as alkali metal ions contained in the washing slurry so as to satisfy the above formula (f). The conductivity of the filtrate is not particularly limited, but is usually 10mS/cm or less, more preferably 1mS/cm or less, and still more preferably 300. mu.S/cm or less.
The washing method is not particularly limited, and washing and concentration may be carried out by using a thickener, Oliver filter, rotary filter, automatic filter press (Larox Co., Ltd.).
As described above, the surface-treated calcium carbonate of the present invention is particularly suitable for use in resins, for example, resins for molding, coating, ink, sealant, and adhesive, and can be blended with various resins to produce a resin composition having excellent properties and physical properties.
The molding resin is not particularly limited, and examples thereof include: thermoplastic resins typified by ABS resins, fluorine resins, polyethylene terephthalate, polycarbonate, polyethylene, polypropylene, ethylene/propylene copolymers, polyolefin resins such as copolymers of ethylene or propylene with other monomers, polystyrene resins, acrylic resins, methacrylic resins, vinyl chloride resins, 1-dichloroethylene resins, polyamide resins, polyether resins, polyvinyl acetate resins, polyvinyl alcohol resins, and the like; thermosetting resins typified by phenol resins, urea resins, melamine resins, epoxy resins, polyurethane resins, polyimide resins, and the like, and these resin components may be used alone or in combination of two or more.
The mixing ratio of the surface-treated calcium carbonate of the present invention and these resins is not particularly limited as long as it is appropriately determined according to the desired physical properties, and it is usually preferable that the surface-treated calcium carbonate is 1 to 100 parts by weight based on 100 parts by weight of the resin. Various additives such as a stabilizer may be added as needed.
The coating resin is not particularly limited, and examples thereof include: a solvent-based coating resin typified by alkyd resins, acrylic resins, polyvinyl acetate resins, polyurethane resins, silicone resins, fluorine resins, styrene resins, melamine resins, epoxy resins, and the like; the water-based paint is an emulsion resin for general paint represented by alkyd resin, acrylic resin, latex resin, polyvinyl acetate resin, polyurethane resin, silicone resin, fluororesin, styrene resin, melamine resin, epoxy resin, and the like; water-soluble resins for general coating materials represented by alkyd resins, amine resins, styrene/allyl alcohol resins, amino alkyd resins, polybutadiene resins, and the like; a dispersion resin for coating material, which is obtained by blending an emulsion resin and a water-soluble resin; a dispersion resin using a crosslinking type water-soluble resin as an emulsifier; acrylic hydrosols, and the like. These resin components may be used alone or in combination of two or more.
The mixing ratio of the surface-treated calcium carbonate of the present invention and these resins is not particularly limited as long as it is appropriately determined according to the desired physical properties, and it is usually preferable that the surface-treated calcium carbonate is 1 to 100 parts by weight based on 100 parts by weight of the resin. It is needless to say that various additives such as a plasticizer and a dispersant may be added as necessary.
Examples of the resin for plastisol include vinyl chloride sol, acrylic sol, water-soluble acrylic sol, polyurethane sol and the like, and these resin components may be used alone or in combination of two or more.
The mixing ratio of the surface-treated calcium carbonate of the present invention and these resins is not particularly limited as long as it is appropriately determined according to the desired physical properties, and it is usually preferable that the surface-treated calcium carbonate is 1 to 100 parts by weight based on 100 parts by weight of the resin. Various additives such as a stabilizer may be added as needed.
The ink resin is not particularly limited, and a rosin-modified phenol resin, a urea resin, a melamine resin, a ketone resin, a polyvinyl chloride-vinyl acetate copolymer, a butyral resin, a styrene-maleic acid resin, a chlorinated polypropylene, an acrylic resin, a coumarone-indene resin, a petroleum resin, a polyester resin, an alkyd resin, a polyamide resin, an epoxy resin, a polyurethane resin, a nitrocellulose, an ethyl cellulose, an ethyl hydroxy cellulose, a cyclized rubber, a chlorinated rubber, or the like may be used alone or in combination of two or more of these resin components.
The mixing ratio of the surface-treated calcium carbonate of the present invention and these resins is not particularly limited as long as it is appropriately determined according to the desired physical properties, and it is usually preferable that the surface-treated calcium carbonate is 1 to 100 parts by weight based on 100 parts by weight of the resin. It is needless to say that various additives such as a stabilizer and a drying agent may be added as necessary.
The sealant resin is not particularly limited, and examples thereof include a polyurethane resin, a polysulfide resin, a silicone resin, a modified silicone resin, a polyisobutylene resin, an epoxy resin, a polyester resin, and the like, and these resin components may be used alone or in combination of two or more.
The mixing ratio of the surface-treated calcium carbonate of the present invention and these resins is not particularly limited as long as it is appropriately determined according to the desired physical properties, and it is usually preferable that the surface-treated calcium carbonate is 1 to 100 parts by weight based on 100 parts by weight of the resin. Various additives such as a colorant and a stabilizer may be added as needed.
The binder resin is not particularly limited, and examples thereof include: urea resins, phenol resins, epoxy resins, silicone resins, acrylic resins, polyurethane resins, polyester resins, and the like, and these resins may be used alone or in combination of two or more.
The mixing ratio of the surface-treated calcium carbonate of the present invention and these resins is not particularly limited as long as it is appropriately determined according to the desired physical properties, and it is usually preferable that the surface-treated calcium carbonate is 1 to 100 parts by weight based on 100 parts by weight of the resin. Various additives such as a stabilizer and a plasticizer may be added as needed.
In the resin composition of the present invention, in addition to the surface-treated calcium carbonate of the present invention, fillers such as colloidal calcium carbonate, ground calcium carbonate, colloidal silica, talc, kaolin, zeolite, resin rings (balloons) and glass rings, plasticizers such as dioctyl phthalate and dibutyl phthalate, petroleum solvents such as toluene and xylene, ketones such as acetone and methyl ethyl ketone, solvents such as ether esters such as cellosolve acetate, silicone oil, fatty acid ester-modified silicone oil, and the like may be added, and various additives and colorants may be added as needed, and one kind or a combination of two or more kinds of these agents may be added for the purpose of adjusting viscosity and other physical properties.
The resin composition of the present invention is excellent in tack, thixotropy and seam tracking property in the case of a curable resin composition represented by, for example, a sealant or an adhesive. For example, in the case of a resin composition for coating materials and inks, the composition has excellent sagging resistance, high gloss, high transparency, and high coating film strength. Further, for example, in the case of a molding resin composition, the strength of the weld line surface can be prevented from being lowered, and the composition has excellent strength.
The present invention will be described in more detail by the following examples and comparative examples, but the present invention is not limited to these examples as long as it does not exceed the scope thereof.
In the following description,% means% by weight and parts means parts by weight unless otherwise specified.
Example 1
Citric acid as a complex-forming substance was added to 8% strength lime milk at 10 ℃ in an amount of 1.7% relative to calcium hydroxide, and 20% carbon dioxide gas was introduced into the slurry at a rate of 1700L/hr per 1kg of calcium hydroxide to prepare a calcium carbonate slurry. Then, the calcium carbonate slurry was adjusted to a concentration of 10%, and stirred and aged at a temperature of 45 to 50 ℃ for 50 hours. The average particle diameter (Dx) after aging was 0.20 μm. To this calcium carbonate slurry was added 10% sodium stearate thermally dissolved in warm water so that the content thereof was 15% based on the solid content of calcium carbonate, and the surface treatment agent was sufficiently adsorbed on the surface of calcium carbonate by stirring, followed by dehydration and drying to obtain a powder, and the BET specific surface area (Sw) of 48m was synthesized2Calcium carbonate/g formed by surface treatment with an organic surface treatment agent. Further, the heat loss rate (Tg) of the surface-treated calcium carbonate at 200 ℃ to 500 ℃ was 118 mg/g. Average pore diameter (D)xp) 0.016 μm and average pore size (Dyp/Dxp) 79. The physical property values of the obtained surface-treated calcium carbonate are shown in table 1.
Example 2
Calcium carbonate formed by surface treatment with an organic surface treatment agent was synthesized by the same preparation method as in example 1, except that the concentration of the calcium carbonate slurry was changed to 7%. The physical property values of the obtained surface-treated calcium carbonate are shown in table 1.
Example 3
Calcium carbonate formed by surface treatment with an organic surface treatment agent was synthesized by the same preparation method as in example 2, except that the aging time was changed to 120 hours. The physical property values of the obtained surface-treated calcium carbonate are shown in Table 1.
Example 4
After the surface treatment, calcium carbonate obtained by surface treatment with an organic surface treatment agent was synthesized by the same preparation method as in example 1, except that the calcium carbonate cake was washed with water and dehydrated by a filter press (Larox corporation) so that the electrical conductivity of the filtrate became 300 μ S/cm. The physical property values of the obtained surface-treated calcium carbonate are shown in Table 1.
Example 5
Calcium carbonate formed by surface treatment with an organic surface treatment agent was synthesized by the same preparation method as in example 1, except that the surface treatment amount was changed to 25%. The physical property values of the obtained surface-treated calcium carbonate are shown in Table 1.
Example 6
Citric acid as a complex-forming substance was added to lime milk at a temperature of 10 ℃ and a concentration of 5% relative to calcium hydroxide in an amount of 10%, and 20% carbon dioxide gas was introduced into the slurry at a rate of 1700L/hr per 1kg of calcium hydroxide to prepare a calcium carbonate slurry. The calcium carbonate slurry was adjusted to a concentration of 30% and aged at 45 to 50 ℃ for 150 hours with stirring. The average particle diameter (Dx) after aging was 0.38 μm. To the calcium carbonateAdding 10% sodium stearate dissolved in warm water under heating to make it 35% of calcium carbonate solid content, stirring to make the surface treating agent fully adsorbed on the calcium carbonate surface, dewatering, drying to obtain powder, and synthesizing BET specific surface area (Sw) 125m2Calcium carbonate/g formed by surface treatment with an organic surface treatment agent. Further, the heat loss rate (Tg) of the surface-treated calcium carbonate at 200 ℃ to 500 ℃ was 296 mg/g. The average pore size (Dxp) was 0.005 μm, and the average pore size amount (Dyp/Dxp) was 148. The physical property values of the obtained surface-treated calcium carbonate are shown in table 1.
Example 7
Calcium carbonate surface-treated with an organic surface-treating agent was synthesized in the same manner as in example 1 except that trisodium citrate as a complex-forming substance was added so that the content of trisodium citrate was 3% based on the amount of calcium hydroxide. The physical property values of the obtained surface-treated calcium carbonate are shown in Table 1.
Example 8
Calcium carbonate formed by surface treatment with an organic surface treatment agent was synthesized by the same preparation method as in example 1, except that the organic surface treatment agent was changed to lauric acid. The physical property values of the obtained surface-treated calcium carbonate are shown in table 1.
Example 9
Calcium carbonate formed by surface treatment with an organic surface treatment agent was synthesized by the same preparation method as in example 1, except that the organic surface treatment agent was changed to sodium laurate. The physical property values of the obtained surface-treated calcium carbonate are shown in Table 2.
Example 10
Calcium carbonate formed by surface treatment with an organic surface treatment agent was synthesized by the same preparation method as in example 1, except that the organic surface treatment agent was changed to sodium palmitate. The physical property values of the obtained surface-treated calcium carbonate are shown in Table 2.
Example 11
Calcium carbonate surface-treated with the organic surface-treating agent was synthesized in the same manner as in example 1, except that the organic surface-treating agent was changed to sodium stearate and potassium resinate at a ratio of 3: 2. The physical property values of the obtained surface-treated calcium carbonate are shown in Table 2.
Example 12
Calcium carbonate formed by surface treatment with an organic surface treatment agent was synthesized by the same preparation method as in example 1, except that the organic surface treatment agent was changed to potassium resinate. The physical property values of the obtained surface-treated calcium carbonate are shown in Table 2.
Example 13
Calcium carbonate surface-treated with the organic surface-treating agent was synthesized in the same manner as in example 1, except that the organic surface-treating agent was changed to sodium stearate/sodium alkylbenzenesulfonate at a ratio of 3: 1. The physical property values of the obtained surface-treated calcium carbonate are shown in Table 2.
Comparative example 1
Calcium carbonate surface-treated with an organic surface-treating agent was synthesized in the same manner as in example 1, except that the amount of the organic surface-treating agent added was changed to 5%. The physical property values of the obtained surface-treated calcium carbonate are shown in Table 2.
Comparative example 2
Citric acid as a complex-forming substance was added to lime milk at a temperature of 10 ℃ and a concentration of 4% in an amount of 18% relative to calcium hydroxide, and 20% carbon dioxide gas was introduced into the slurry at a rate of 17000L/hr per 1kg of calcium hydroxide to prepare a calcium carbonate slurry. Then, the calcium carbonate slurry was adjusted to a concentration of 2%, and stirred and aged at a temperature of 45 to 50 ℃ for 200 hours. The average particle diameter (Dx) after aging was 2.3 μm. Sodium stearate (10% in weight) dissolved in warm water under heating was added to the calcium carbonate slurry to make the content of sodium stearate 45% to the solid content of calcium carbonate, and the mixture was stirred to sufficiently absorb the surface treatment agentAttaching to the surface of calcium carbonate, dehydrating, drying, making into powder, and synthesizing BET specific surface area (Sw) ═ 175m2Calcium carbonate/g formed by surface treatment with an organic surface treatment agent. Further, the heat loss rate (Tg) of the surface-treated calcium carbonate at 200 ℃ to 500 ℃ was 402 mg/g. The average pore size (Dxp) was 0.003 μm, and the average pore size (Dyp/Dxp) was 47. The physical property values of the obtained surface-treated calcium carbonate are shown in Table 2.
Comparative example 3
As described in example 1 of Japanese patent application laid-open No. H10-72215, trisodium citrate as a complex-forming substance was added to lime milk at a temperature of 10 ℃ and a concentration of 11.8% in an amount of 3% relative to calcium hydroxide, and 20% carbon dioxide gas was introduced into the slurry at a rate of 1700L/hr per 1kg of calcium hydroxide to prepare a calcium carbonate slurry. Then, the calcium carbonate slurry was subjected to aging with stirring at 45 to 50 ℃ for 50 hours at a calcium carbonate concentration of 14.9% without adjusting the concentration. The average particle diameter (Dx) after aging was 0.50 μm. Adding 10% sodium stearate thermally dissolved in warm water to the calcium carbonate slurry to make the content of sodium stearate be 15% of the solid content of calcium carbonate, sufficiently adsorbing the surface treating agent on the surface of calcium carbonate by strong stirring, dehydrating, drying to obtain powder, and synthesizing the powder with BET specific surface area (Sw) of 42m2Calcium carbonate/g formed by surface treatment with an organic surface treatment agent. Further, the heat loss rate (Tg) of the surface-treated calcium carbonate at 200 ℃ to 500 ℃ was 101 mg/g. The average pore size (Dxp) was 0.018 μm, and the average pore size amount (Dyp/Dxp) was 27. The physical property values of the obtained surface-treated calcium carbonate are shown in Table 2.
Comparative example 4
Citric acid as a complex-forming substance was added to lime milk at a temperature of 10 ℃ and a concentration of 11.8% in an amount of 0.2% relative to calcium hydroxide, and 20% carbon dioxide gas was introduced into the slurry at a rate of 1700L/hr per 1kg of calcium hydroxide to prepare calcium carbonate. Then, the calcium carbonate slurry was subjected to aging with stirring at 45 to 50 ℃ for 50 hours at a calcium carbonate concentration of 14.9% without adjusting the concentration. After curing, the mixture isThe average particle diameter (Dx) of (2) was 0.49. mu.m. Adding 10% sodium stearate thermally dissolved in warm water to the calcium carbonate slurry to make the content of sodium stearate 5% to the solid content of calcium carbonate, sufficiently adsorbing the surface treating agent on the surface of calcium carbonate by strong stirring, dehydrating, drying to obtain powder, and synthesizing the powder with BET specific surface area (Sw) of 17m2Calcium carbonate/g formed by surface treatment with an organic surface treatment agent. Further, the heat loss rate (Tg) of the surface-treated calcium carbonate at 200 ℃ to 500 ℃ was 42 mg/g.
The average pore size (Dxp) was 0.042 μm, and the average pore size amount (Dyp/Dxp) was 38. The physical property values of the obtained surface-treated calcium carbonate are shown in Table 2.
Comparative example 5
Calcium carbonate formed by surface treatment with an organic surface treatment agent was synthesized by the same preparation method as in comparative example 3, except that the organic surface treatment agent was changed to potassium resinate. The physical property values of the obtained surface-treated calcium carbonate are shown in Table 2.
TABLE 1
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Example 7 | Example 8 | |
| (a)Sw(m2/g)(b)As(mg/m2)(c)Dxp(μm)(d)Dyp/Dxp | 482.50.01679 | 512.40.01686 | 532.40.01599 | 482.40.01591 | 435.00.01253 | 1252.40.005148 | 442.80.01671 | 492.30.01680 |
| (e)Dxs(μm)(f)Dys(％) | 0.2512 | 0.155 | 0.110 | 0.239 | 0.5324 | 0.8323 | 0.8728 | 0.259 |
| (k)Sw·Dxp | 0.77 | 0.82 | 0.80 | 0.72 | 0.52 | 0.63 | 0.70 | 0.78 |
| (l)Is(μmol/m2) | 1.68 | 1.61 | 1.60 | 0.36 | 4.21 | 1.61 | 3.39 | 2.57 |
| (m)Dx(μm) | 0.20 | 0.11 | 0.08 | 0.23 | 0.23 | 0.38 | 0.42 | 0.20 |
| (n)VIS2(Pa·s)(o)VIS20(Pa·s)(p)VIS2/VIS20 | 11501706.8 | 13501956.9 | 14802107.0 | 9701556.3 | 14302954.8 | 16202456.6 | 5551154.8 | 12001756.9 |
| Concentration of milk of lime (%) | 8.0 | 8.0 | 8.0 | 8.0 | 8.0 | 5.0 | 8.0 | 8.0 |
| ② concentration of complex formation (%) | 1.7 | 1.7 | 1.7 | 1.7 | 1.7 | 10 | 3.0 | 1.7 |
| Complex-forming materials | Citric acid | Citric acid | Citric acid | Citric acid | Citric acid | Citric acid | Trisodium citrate | Citric acid |
| ③ amount of carbon dioxide gas (L/hr) | 1700 | 1700 | 1700 | 1700 | 1700 | 1700 | 1700 | 1700 |
| Concentration of gas (%) | 20 | 20 | 20 | 20 | 20 | 20 | 20 | 20 |
| Fifthly, the concentration of calcium carbonate (%) | 10 | 7.0 | 7.0 | 10 | 10 | 3.0 | 10 | 10 |
| Ripening time (hr) | 50 | 50 | 120 | 50 | 50 | 150 | 50 | 50 |
| Surface treatment amount (%) | 15 | 15 | 15 | 15 | 25 | 35 | 15 | 15 |
| Surface treating agent | Sodium stearate | HardSodium aliphatate | Sodium stearate | Sodium stearate | Sodium stearate | Sodium stearate | Sodium stearate | Lauric acid |
| Conductivity of the filtrate (μ S/cm) | 2000 | 2000 | 2000 | 300 | 3600 | 2200 | 1900 | 200 |
TABLE 2
| Examples9 | Example 10 | Example 11 | Example 12 | Example 13 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | |
| (a)Sw(m2/g)(b)As(mg/m2)(c)Dxp(μm)(d)Dyp/Dxp | 502.50.016110 | 472.50.01680 | 472.40.01677 | 472.30.01669 | 462.30.01675 | 510.80.03127 | 1752.30.00347 | 422.40.01827 | 172.50.04238 | 443.00.01826 |
| (e)Dxs(μm)(f)Dys(％) | 0.257 | 0.3113 | 0.2915 | 0.3618 | 0.318 | 0.7635 | 8.668 | 1.344 | 0.5622 | 1.758 |
| (k)Sw·Dxp | 0.80 | 0.75 | 0.75 | 0.75 | 0.74 | 1.58 | 0.53 | 0.76 | 0.71 | 0.79 |
| (l)Is(μmol/m2) | 2.57 | 1.97 | 2.09 | 1.94 | 1.85 | 0.61 | 1.64 | 2.84 | 2.45 | 2.80 |
| (m)Dx(μm) | 0.20 | 0.20 | 0.20 | 0.20 | 0.20 | 0.58 | 2.3 | 0.50 | 0.49 | 0.50 |
| (n)VIS2(Pa·s)(o)VIS20(Pa·s)(p)VIS2/VIS20 | 12501757.1 | 9851556.4 | 9851556.4 | 8901505.9 | 9751556.3 | 390755.2 | 95156.3 | 325804.1 | 245703.5 | 275703.9 |
| Concentration of milk of lime (%) | 8.0 | 8.0 | 8.0 | 8.0 | 8.0 | 8.0 | 4.0 | 11.8 | 11.8 | 11.8 |
| ② concentration of complex-forming substance (%) | 1.7 | 1.7 | 1.7 | 1.7 | 1.7 | 1.7 | 18 | 3.0 | 0.2 | 3.0 |
| Complex-forming materials | Citric acid | Citric acid | Citric acid | Citric acid | Citric acid | Citric acid | Citric acid | Trisodium citrate | Citric acid | Trisodium citrate |
| ③ amount of carbon dioxide gas | 1700 | 1700 | 1700 | 1700 | 1700 | 1700 | 1700 | 1700 | 1700 | 1700 |
| Concentration of gas (%) | 20 | 20 | 20 | 20 | 20 | 20 | 20 | 20 | 20 | 20 |
| Fifthly, the concentration of calcium carbonate (%) | 10 | 10 | 10 | 10 | 10 | 10 | 2.0 | 14.9 | 14.9 | 14.9 |
| Ripening time (hr) | 50 | 50 | 50 | 50 | 50 | 50 | 200 | 50 | 50 | 50 |
| Surface treatment amount (%) | 15 | 15 | 15 | 15 | 15 | 5 | 45 | 15 | 5 | 13 |
| Surface treating agent | Sodium laurate (NaLaurus acid) | Sodium palmitate | Sodium stearate and potassium resinate are 3: 2 | Resin potassium salt | Sodium stearate DBS-Na is 3: 1 | Sodium stearate | Sodium stearate | Sodium stearate | Sodium stearate | Resin potassium salt |
| Conductivity of the filtrate (μ S/sm) | 800 | 2000 | 2200 | 2200 | 2200 | 800 | 3800 | 2000 | 1400 | 2100 |
Examples 14 to 20 and comparative examples 6 to 9
Using the surface-treated calcium carbonates synthesized in examples 1 to 7 and comparative examples 1 to 4, resin compositions for molding were prepared in the following proportions. The evaluation results of the obtained molding resin composition are shown in Table 3.
(ratio)
Surface-treated calcium carbonate 15 parts
85 parts of polypropylene resin
The above two components were dry-blended in a Henschel mixer (manufactured by カワタ Co.), pelletized in an extrusion molding machine (NEXT T-60 manufactured by Kobe Steel Co., Ltd.), and then made into dumbbell-shaped pieces by an injection molding machine, and the tensile strength, flexural modulus and impact strength were tested. The test piece for measuring the strength of the weld line surface was injected from two gates, and a weld line interface was formed in the center. The test piece for other physical property measurements was injected from one gate.
Various properties of the test piece thus obtained were measured and evaluated by the following methods.
(tensile Strength, flexural Strength, impact Strength)
The tensile strength was measured by the plastic tensile test method of JIS K7113, the flexural strength was measured by the flexural test method of hard plastics of JIS K7203, and the impact strength was measured by the charpy impact test method of hard plastics of JIS K7111.
(scratch resistance test)
A plastic plate molded into a thickness of 30mm X80 mm and 1mm was subjected to a scratch resistance test using a scratch resistance tester (manufactured by Toyo Seiki Seisaku-Sho Ltd.), and the state thereof was evaluated according to the following criteria.
Very good: excellent (no scratch at all)
O: good (hardly scratch)
And (delta): common (with some scratch)
X: badness (with many scratches)
TABLE 3
| Surface-treated calcium carbonate for use | Tensile strength of the usual part (N/mm)2) | Tensile Strength at weld line interface (N/mm)2) | Bending Strength of common parts (N/mm)2) | Bending Strength (N/mm) of weld line interface2) | Impact Strength (N.cm/cm)2) | Scratch resistance test | |
| Example 14 example 15 example 16 example 17 example 18 example 19 example 20 | Example 1 example 2 example 3 example 4 example 5 example 6 example 7 | 34363734294130 | 32333332303529 | 47495046445442 | 36373835324133 | 43454543364938 | ○◎◎○△～○○○ |
| Comparative example 6 comparative example 7 comparative example 8 comparative example 9 | Comparative example 1 comparative example 2 comparative example 3 comparative example 4 | 19131621 | 17111519 | 34222924 | 24152119 | 27192523 | ×××× |
From the results in table 3, it is understood that the molding resin composition containing the surface-treated calcium carbonate of the present invention is excellent not only in tensile strength, flexural strength and impact strength, but also in the prevention of the decrease in the weld line strength, and thus is excellent in adhesion to an adherend. Further, the amount of calcium carbonate added was reduced by about 5% as compared with the conventional amount, and it was found that the amount was effective also in terms of weight reduction.
Examples 21 to 27 and comparative examples 10 to 13
Using the surface-treated calcium carbonates synthesized in examples 1 to 7 and comparative examples 1 to 4, resin compositions for coating materials were prepared in the following proportions.
(ratio)
50 parts of surface-treated calcium carbonate
Ground calcium carbonate (Super-SSS manufactured by pill tail calcium Co., Ltd.)
41 portions of
Alkyd resin
(Large Japanese ink (インキ) Beccozol P-470-70, manufactured by chemical industries, Ltd.)
250 portions of
120 parts of titanium dioxide (TIPAQUE R-820 available from Stone Ltd.)
70 portions of petroleum solvent (mineral spirit)
14 portions of drying agent
1.5 parts of anti-skinning agent
350 parts of glass beads
The above mixture was dispersed with an SG mill until the size measured by a fineness meter was 20 μm or less, glass beads were taken out to prepare a coating resin composition, and various properties were measured and evaluated by the following methods. The results are shown in Table 4.
(gloss and gloss retention after Water repellency test)
Each coating resin composition was applied to one surface of a glass plate by a 100 μm coater, dried at room temperature for 24 hours, and then measured for 60 ℃ gloss by a Millon gloss meter. Thereafter, the glass plate was immersed in water, and the gloss retention after 3 days was measured.
(sagging property)
Each coating resin composition was diluted with a petroleum solvent to adjust the KU value to 78, coated on a total black measurement paper with a 250, 200, 150 or 100 μm coater, and immediately after coating, the coated surface was vertically set up and left to stand at room temperature for 24 hours, and the sagging state was evaluated according to the following criteria.
O: good (no sagging at all)
□: common (with some sagging)
X: failure (sagging)
(scratch test of coating film)
Each coating resin composition was applied to one surface of a glass plate with a 1000 μm applicator, dried at room temperature for 1 week, and then subjected to a scratch test with a scratch tester (manufactured by toyoyo seiki) to evaluate the state thereof according to the following criteria.
Very good: excellent (no scratch at all)
O: good (hardly scratch)
And (delta): common (with some scratch)
X: badness (with many scratches)
TABLE 4
| Surface-treated calcium carbonate for use | Initial gloss at 60 ° | 60 ℃ gloss after Water repellency test | Gloss retention% | Sagging property | Scratch resistance test of coating film | ||||
| 250μm | 200μm | 150μm | 100μm | ||||||
| Example 21 example 22 example 23 example 24 example 25 example 26 example 27 | Example 1 example 2 example 3 example 4 example 5 example 6 example 7 | 90.592.593.090.087.593.588.5 | 87.089.090.087.085.585.584.5 | 96969795989195 | △△○△○○△ | ○○○○○○△ | ○○○○○○○ | ○○○○○○○ | ○○◎○○◎○ |
| Comparative example 10 comparative example 11 comparative example 12 comparative example 13 | Comparative example 1 comparative example 2 comparative example 3 comparative example 4 | 85.588.084.578.5 | 74.568.575.573.5 | 87788994 | ×△×× | ×△×× | ×○△× | △○△× | ×△△× |
From the results in table 4, it is understood that the coating resin composition containing the surface-treated calcium carbonate of the present invention has excellent anti-sagging properties, thereby having high thixotropy, and excellent gloss retention after a water resistance test, thereby having high durability and strong coating film strength.
Examples 28 to 34 and comparative examples 14 to 17
Plastisol resin compositions, prepared according to the following formulation ratios, were prepared using the surface-treated calcium carbonates synthesized in examples 1 to 7 and comparative examples 1 to 4.
(ratio)
300 parts of surface-treated calcium carbonate
Acrylic Resin Zeon Acrylic Resin F345 (New first salt ビ, manufactured by Kokusan Co., Ltd.)
250 portions of
Blocked (ブロツク) polyurethane resin curing agent (manufactured by Mitsui Wutian chemical Co., Ltd.) 120 parts
DINP 500 parts
Turpentine 80 parts
6 parts of polyurethane curing agent (manufactured by Sanjing Wutian chemical Co., Ltd.)
The respective compounding agents were kneaded in a 5L universal mixer (manufactured by Dulton) at normal temperature until no pellets were formed, to prepare an acrylic sol resin composition, and various properties were evaluated by the following measurement methods. The results are shown in Table 5.
(viscosity, thixotropy)
The viscosity of the acrylic sol adjusted based on the above compounding ratio was measured at 2rpm and 20rpm by a BH type viscometer, and the thixotropy was expressed by the viscosity at 2rpm/20 rpm.
(chipping resistance)
The coating film applied and cured on the plating spray plate under the above-mentioned drying conditions was fixed at an angle of 60 ° to the horizontal, the spray surface was made to face upward, the M-4 nut was dropped according to the JIS nut (nut) drop test method in such a manner that the spray surface was broken until the cumulative weight of the nut exposed to the base surface, aligned with the lower end of a 2M long tube standing vertically on the coating film surface, and the chipping resistance was represented by the cumulative weight of the nut.
TABLE 5
| Acrylic acid soluble adhesive Property | Chipping resistance (g) | ||||
| 2rpm(Pa·s) | 20rpm(Pa·s) | Thixotropic 2rpm/20rpm | |||
| Example 28 | Example 1 | 650 | 95 | 6.8 | 82 |
| Example 29 | Example 2 | 680 | 105 | 6.5 | 86 |
| Example 30 | Example 3 | 770 | 115 | 6.7 | 90 |
| Example 31 | Example 4 | 620 | 90 | 6.9 | 88 |
| Example 32 | Example 5 | 550 | 105 | 5.2 | 68 |
| Example 33 | Example 6 | 920 | 145 | 6.3 | 76 |
| Example 34 | Example 7 | 540 | 85 | 6.4 | 72 |
| Comparative example 14 | Comparative example 1 | 330 | 60 | 5.5 | 48 |
| Comparative example 15 | Comparative example 2 | 180 | 40 | 4.5 | 34 |
| Comparative example 16 | Comparative example 3 | 280 | 55 | 5.1 | 42 |
| Comparative example 17 | Comparative example 4 | 140 | 35 | 4.0 | 32 |
From the results in table 5, it is understood that the plastisol resin compositions formed by mixing the surface-treated calcium carbonate of the present invention are significantly improved in viscosity and strength (chipping resistance).
Examples 35 to 46 and comparative examples 18 to 21
Using the surface-treated calcium carbonates synthesized in examples 1 to 11 and 13 and comparative examples 1 to 4, various properties of the obtained cured resin compositions were evaluated by adjusting the following compounding ratios. The results are shown in tables 6 and 7.
(ratio)
(substrate)
Surface treated calcium carbonate 400 parts
500 parts of resin (MS Polymer S810 manufactured by Brillouin chemistry)
345 parts of DOP
400 portions of heavy calcium carbonate (Super S made from pellet tail calcium)
Aminosilane 5 parts
(curing agent)
20 portions of colloidal calcium carbonate (Calfine 200M made by calcium from pill tail)
6 parts of tin octylate
1 part of laurylamine
DOP 11 parts
28 parts of ground calcium carbonate (Super SSS prepared from pellet tail calcium)
Each mixture was sufficiently kneaded in a 5L universal mixer (manufactured by Dulton) until no granules were formed, a base material and a curing agent were prepared, and various characteristics were evaluated by measurement by the following methods. The results are shown in Table 6.
(viscosity, thixotropy)
The viscosity of the substrate of the cured resin composition adjusted based on the above compounding ratio was measured at 1rpm and 10rpm with a BS type viscometer, and the thixotropy was expressed as 1rpm viscosity/10 rpm viscosity.
(storage stability test)
The cured resin composition was allowed to stand at 20 ℃ for 2 weeks in a thermostat device, and then the substrate viscosity was measured.
(type H tensile Strength and elongation test)
A resin composition of type H was prepared and evaluated by thoroughly defoaming and mixing the base material and curing agent at a ratio of 10: 1 in accordance with JIS A57576.11 tensile stress and elongation tests.
(adhesion test)
In the H-type tensile strength test, the adhesiveness was evaluated according to the following criteria.
O: good (material failure occurred)
And (delta): in general (slight interfacial peeling, but also material destruction)
X: failure (occurrence of interfacial peeling)
(tracking test followed by type H tensile test and adhesion test)
In the H-type tensile strength test, the cured product was fixed in a state of being elongated by 50% for 1 week, and then H-type tensile strength (residual stress) was measured in the same manner, and the tracking property of the sealant to the joint was evaluated by evaluating the adhesiveness.
TABLE 6
| Surface-treated calcium carbonate for use | Viscosity of freshly prepared substrate | Viscosity of base material at 20 ℃ for 2 weeks | |||||
| 1rpm(Pa·s) | 10rpm(Pa·s) | Thixotropic 1rpm/10rpm | 1rpm(Pa·s) | 10rpm(Pa·s) | Thixotropic 1rpm/10rpm | ||
| Example 35 example 36 example 37 example 38 example 39 example 40 example 41 example 42 example 43 example 44 example 45 example 46 | Example 1 example 2 example 3 example 4 example 5 example 6 example 7 example 8 example 9 example 10 example 11 example 13 | 440045504650430046006490395041004500390040504150 | 640650660630780980670590630610620620 | 6.97.07.06.85.96.65.96.97.16.46.56.7 | 516054305580445078507850515042505450512048904520 | 76078082065013501180950630770830770710 | 6.87.06.86.85.86.75.46.77.16.26.46.4 |
| Comparative example 18 comparative example 19 comparative example 20 comparative example 21 | Comparative example 1 comparative example 2 comparative example 3 comparative example 4 | 157019502780820 | 325385530170 | 4.85.15.24.8 | 2040245038901000 | 390510740225 | 5.24.85.34.4 |
TABLE 7
| Surface-treated calcium carbonate for use | Initial physical Properties | Physical Properties after traceability test | |||||
| Tensile Strength at 50% elongation (N/mm)2) | Tensile Strength at Break (N/mm)2) | Elongation (%) | Adhesion Property | Tensile Strength at Break (N/mm)2) | Adhesion Property | ||
| Example 35 example 36 example 37 example 38 example 39 example 40 example 41 example 42 example 43 example 44 example 45 example 46 | Example 1 example 2 example 3 example 4 example 5 example 6 example 7 example 8 example 9 example 10 example 11 example 13 | 0.230.210.190.230.280.170.250.240.220.250.230.23 | 1.050.151.201.000.801.300.950.951.100.901.001.00 | 890920930910720980870900900850880880 | ○○○○○○○○○○○○ | 0.901.051.100.950.751.250.800.800.900.850.850.85 | △△△△△△△△△△○△ |
| Comparative example 18 comparative example 19 comparative example 20 comparative example 21 | Comparative example 1 comparative example 2 comparative example 3 comparative example 4 | 0.480.330.280.13 | 0.550.600.750.85 | 430780640550 | ×△△× | 0.380.450.620.55 | ×××× |
From the results in tables 6 and 7, it is understood that the cured resin compositions represented by sealants and adhesives containing the surface-treated calcium carbonate of the present invention have high breaking strength and excellent adhesion to an adherend, and the above effects are maintained even in a tracking test.
From examples 4 and 8, it is understood that the storage stability of calcium carbonate is excellent by reducing the alkali metal content in calcium carbonate by washing with water.
Example 47 and comparative example 22
Using the surface-treated calcium carbonates synthesized in the above example 12 and comparative example 5, ink resin compositions based on the following formulation were prepared. The evaluation results of the obtained ink resin compositions are shown in table 8.
(ratio)
25 parts of surface-treated calcium carbonate
35 parts of rosin modified phenolic resin
20 parts of linseed oil
Refined light oil 17 parts
3 portions of drying agent
The above mixture was dispersed by a three-roll kneader (manufactured by UK corporation) until the particle size measured by a particle size meter was 5 μm or less, to prepare an ink resin composition.
(viscosity, thixotropy)
The viscosity of the ink resin composition adjusted based on the above compounding ratio was measured at 1rpm and 10rpm with a BS type viscometer, and thixotropy was expressed as 1rpm viscosity/10 rpm viscosity.
(transparency)
The ink resin composition adjusted based on the above formulation was applied to one surface of a glass plate using a 25 μm applicator, dried at room temperature for 24 hours, and then measured for light transmittance of 550 μm using a photoelectric spectrophotometer (manufactured by Shimadzu corporation).
(gloss)
The ink resin composition was applied in the same manner as described above, dried at room temperature for 24 hours, and then measured for 60 ℃ gloss using a cunea gloss meter.
(Friction resistance test)
Each resin composition was applied to one surface of a total black measurement paper by a 25 μm applicator, dried at room temperature for 24 hours, and then evaluated by an S-type abrasion Tester (Sutherland' S Rub Tester) according to the following criteria in accordance with the abrasion resistance test of JISK 5701.
O: good (no wear)
And (delta): common (slight abrasion)
X: failure (extensive wear)
(adhesiveness)
After coating and drying in the same manner as described above, a tape (celltap (registered trademark)) [ T405A-18 manufactured by Nichiban corporation ] was attached to the surface of the film, and the film was rapidly peeled off, and the peeled state of the ink was evaluated according to the following criteria.
Very good: excellent (no peeling at all)
O: good (almost no peeling)
And (delta): general (slight peeling)
X: failure (peeling occurred in large quantity)
(scratch resistance)
After coating and drying in the same manner as described above, a scratch resistance test was carried out using a scratch resistance tester (manufactured by Toyo Seiki Seisaku-Sho Ltd.), and the state thereof was evaluated according to the following criteria.
Very good: excellent (no scratch at all)
O: good (hardly scratch)
And (delta): common (with some scratch)
X: badness (with many scratches)
TABLE 8
| Viscosity of | Transparency of | 60 degree gloss | Abrasion resistance | Adhesion Property | Scratch resistance | ||||
| 1rpm(Pa·s) | 10rpm(Pa·s) | Thixotropic 1rpm/10rpm | |||||||
| Example 47 | Example 12 | 1380 | 410 | 3.4 | 88.5 | 87.0 | ○ | ◎ | ○ |
| Comparative example 22 | Comparative example 5 | 560 | 230 | 2.4 | 72.0 | 73.5 | × | △ | × |
From the results in table 8, it is understood that the ink resin composition containing the surface-treated calcium carbonate of the present invention is excellent in viscosity and thixotropy-imparting effect, and has high gloss and transparency. And is excellent in abrasion resistance and scratch resistance, and also excellent in high coating film strength and excellent in adhesion to an adherend. As a result, the amount of calcium carbonate added can be reduced as compared with the prior art, and the ink composition is effective in stabilizing ink characteristics.
Industrial applicability
As described above, the calcium carbonate having a specific particle size characteristic, which is surface-treated with the organic surface-treating agent of the present invention, is particularly useful for resin applications, and when it is mixed into a resin, the adhesion of the resin composition to an adherend can be improved, and a tough coating film can be formed.
The surface-treated calcium carbonate of the present invention can prevent the strength of the weld line surface from decreasing when used in a resin composition for molding, for example, and can be used in a resin composition having excellent impact strength when used in a coating material or ink, for example; when a resin composition having high gloss and excellent sagging resistance, high film strength is used for example for a resin composition for plastisol; when the resin composition having excellent tackiness, thixotropy and chipping resistance is used for, for example, a curable resin represented by a sealant, an adhesive, a resin composition having excellent tackiness, thixotropy and seam tracing properties can be provided.
Claims (17)
1. Surface-treated calcium carbonate characterized by: comprising calcium carbonate surface-treated with an organic surface-treating agent, satisfying the following formulae (a), (b), (c) and (d),
(a)20≤Sw≤200 (m2/g)
(b)1.0≤As≤7.5 (mg/m2)
(c)0.003≤Dxp≤0.03 (μm)
(d)50≤Dyp/Dxp≤180
wherein
Sw: BE measured by nitrogen adsorption methodT specific surface area (m)2/g)
As: the thermal loss per unit specific surface area (mg/m) calculated by the following equation2) (Heat weight loss mg/g per 1g of calcium carbonate surface-treated at 200 ℃ to 500 ℃)/Sw
Dxp: in the mercury intrusion method, in the distribution of micropores in the range of 0.001-0.1 μm in micropore range, the average diameter (μm) of micropores at which the mercury intrusion increment (cumulative micropore volume increment/log average micropore diameter) is the maximum value (Dys)
Dyp: maximum value of mercury intrusion (mg/l)
Dyp/Dxp: average pore size.
2. Surface-treated calcium carbonate characterized by: the calcium carbonate surface-treated with the organic surface-treating agent satisfies the following formulae (a), (b), (e) and (f),
(a)20≤Sw≤200 (m2/g)
(b)1.0≤As≤7.5 (mg/m2)
(e)0.03≤Dxs≤1 (μm)
(f) dys ≤ 30% (by weight)
Wherein
Sw: BET specific surface area (m) by nitrogen adsorption2/g)
As: the thermal loss per unit specific surface area (mg/m) calculated by the following equation2) (Heat weight loss mg/g per 1g of calcium carbonate surface-treated at 200 ℃ to 500 ℃)/Sw
Dxs: in the particle size distribution measured by a laser diffractometer (SALD-2000, manufactured by Shimadzu corporation),
from the large particle side, the weight is 50% of the average particle diameter (. mu.m)
Dys: in the particle size distribution, the weight of the particle diameter exceeding 3 μm is integrated (% by weight).
3. Surface-treated calcium carbonate characterized by: comprising calcium carbonate surface-treated with an organic surface-treating agent, satisfying the following formulae (a) to (f),
(a)20≤Sw≤200 (m2/g)
(b)1.0≤As≤7.5 (mg/m2)
(c)0.003≤Dxp≤0.03 (μm)
(d)50≤Dyp/Dxp≤180
(e)0.03≤Dxs≤1 (μm)
(f) dys ≤ 30% (by weight)
Wherein
Sw: BET specific surface area (m) by nitrogen adsorption2/g)
As: the thermal loss per unit specific surface area (mg/m) calculated by the following equation2) (Heat weight loss mg/g per 1g of calcium carbonate surface-treated at 200 ℃ to 500 ℃)/Sw
Dxp: in the mercury intrusion method, in the distribution of micropores in the range of 0.001-0.1 μm in micropore range, the average diameter (μm) of micropores at which the mercury intrusion increment (cumulative micropore volume increment/log average micropore diameter) is the maximum value (Dys)
Dyp: maximum value of mercury intrusion (mg/l)
Dyp/Dxp: average pore diameter
Dxs: in the particle size distribution measured by a laser diffractometer (SALD-2000, manufactured by Shimadzu corporation), the average particle diameter (. mu.m) was 50% by weight in total from the larger particle side
Dys: in the particle size distribution, the weight of the particle diameter exceeding 3 μm is integrated (% by weight).
4. The surface-treated calcium carbonate according to any one of claims 1 to 3, wherein the calcium carbonate surface-treated with the organic surface-treating agent satisfies the following formulae (g) to (j),
(g)0.005≤Dxp≤0.025 (μm)
(h)60≤Dyp/Dxp≤150
(i)0.05≤Dxs≤0.8 (μm)
(j) dys ≦ 25 (% by weight).
5. The surface-treated calcium carbonate according to any one of claims 1 to 4, wherein the calcium carbonate surface-treated with the organic surface-treating agent satisfies the following formula (k),
(k)0.1≤Sw·Dxp≤1.5。
6. the surface-treated calcium carbonate according to any one of claims 1 to 5, wherein an alkali metal salt contained in the calcium carbonate surface-treated with the organic surface-treating agent satisfies the following formula (1),
(1)0.03≤Is≤3 (μmol/m2)
wherein,
is: alkali Metal content per unit specific surface area { Metal content per 1g calcium carbonate (mmol/g) }/Sw (m) calculated by the following formula2/g)。
7. The surface-treated calcium carbonate according to any one of claims 1 to 6, wherein the calcium carbonate slurry before (after aging) surface-treatment with the organic surface-treating agent satisfies the following formula (m),
(m)0.03≤Dx≤0.40 (μm)
wherein,
dx: the particle size (. mu.m) was calculated from the larger particle size side in the particle size distribution measured by a centrifugal particle size distribution meter (SA-CP 4, manufactured by Shimadzu corporation).
8. The surface-treated calcium carbonate according to any one of claims 1 to 7, wherein the organic surface-treating agent is at least one member selected from the group consisting of saturated fatty acids, unsaturated fatty acids, resin acids, sulfonic acids, alkali metal salts, alkaline earth metal salts, ammonium salts, amine salts, cationic surfactants, anionic surfactants and nonionic surfactants of these acids.
9. A method for producing surface-treated calcium carbonate, characterized by comprising: adding 0.5-15 wt% of a substance which forms a complex by complexing with metal ions to a calcium hydroxide slurry, carbonating by blowing carbon dioxide gas to synthesize calcium carbonate, adjusting the calcium carbonate concentration to 2.4-13.0 wt%, aging, and subjecting the obtained calcium carbonate to surface treatment with an organic surface treatment agent.
10. A resin composition characterized by: the surface-treated calcium carbonate of any one of claims 1 to 8 mixed into a resin.
11. The resin composition of claim 10, wherein the resin is a molding resin.
12. The resin composition of claim 10, wherein the resin is a coating resin.
13. The resin composition of claim 10, wherein the resin is a resin for plastisols.
14. The resin composition of claim 10, wherein the resin is a resin for ink.
15. The resin composition of claim 10 wherein the resin is a sealant resin.
16. The resin composition of claim 10, wherein the resin is a binder resin.
17. The resin composition according to any one of claims 10 to 16, wherein the surface-treated calcium carbonate is mixed in an amount of 1 to 100 parts by weight relative to 100 parts by weight of the resin.
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