CN107074564A - Hydrophobic silica and its manufacture method - Google Patents
Hydrophobic silica and its manufacture method Download PDFInfo
- Publication number
- CN107074564A CN107074564A CN201580045419.1A CN201580045419A CN107074564A CN 107074564 A CN107074564 A CN 107074564A CN 201580045419 A CN201580045419 A CN 201580045419A CN 107074564 A CN107074564 A CN 107074564A
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- Prior art keywords
- silicone oil
- silica
- hydrophobic silica
- mentioned
- hydrophobic
- Prior art date
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 407
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 199
- 238000000034 method Methods 0.000 title claims abstract description 119
- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 116
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 41
- 229920002545 silicone oil Polymers 0.000 claims abstract description 124
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 70
- 230000008569 process Effects 0.000 claims abstract description 47
- -1 salt compound Chemical class 0.000 claims abstract description 22
- 238000004090 dissolution Methods 0.000 claims abstract description 21
- 239000011248 coating agent Substances 0.000 claims abstract description 19
- 125000005372 silanol group Chemical group 0.000 claims abstract description 19
- 238000000576 coating method Methods 0.000 claims abstract description 18
- 239000002253 acid Substances 0.000 claims abstract description 17
- 230000007935 neutral effect Effects 0.000 claims abstract description 13
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 9
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical group [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 13
- 235000011152 sodium sulphate Nutrition 0.000 claims description 10
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 9
- 239000011734 sodium Substances 0.000 claims description 8
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 6
- 241000790917 Dioxys <bee> Species 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- 229910003978 SiClx Inorganic materials 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 239000005864 Sulphur Substances 0.000 claims description 3
- 239000001103 potassium chloride Substances 0.000 claims description 3
- 235000011164 potassium chloride Nutrition 0.000 claims description 3
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 3
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 3
- 235000011151 potassium sulphates Nutrition 0.000 claims description 3
- 238000005660 chlorination reaction Methods 0.000 claims 1
- 235000015424 sodium Nutrition 0.000 claims 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 13
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 abstract description 11
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 54
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 29
- 239000010408 film Substances 0.000 description 26
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- 239000000843 powder Substances 0.000 description 18
- 235000002639 sodium chloride Nutrition 0.000 description 14
- 239000002585 base Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 235000011121 sodium hydroxide Nutrition 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 238000012545 processing Methods 0.000 description 9
- 239000003921 oil Substances 0.000 description 8
- 229910052710 silicon Inorganic materials 0.000 description 8
- 239000010703 silicon Substances 0.000 description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 239000006224 matting agent Substances 0.000 description 6
- 238000010979 pH adjustment Methods 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000003973 paint Substances 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 239000002981 blocking agent Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 150000003376 silicon Chemical class 0.000 description 4
- 238000004381 surface treatment Methods 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000004205 dimethyl polysiloxane Substances 0.000 description 3
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- 238000004448 titration Methods 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000008033 biological extinction Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 229940008099 dimethicone Drugs 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000013500 performance material Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000009738 saturating Methods 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical class [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 235000019795 sodium metasilicate Nutrition 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- PANBYUAFMMOFOV-UHFFFAOYSA-N sodium;sulfuric acid Chemical compound [Na].OS(O)(=O)=O PANBYUAFMMOFOV-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910020175 SiOH Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 210000004276 hyalin Anatomy 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- VDGJOQCBCPGFFD-UHFFFAOYSA-N oxygen(2-) silicon(4+) titanium(4+) Chemical compound [Si+4].[O-2].[O-2].[Ti+4] VDGJOQCBCPGFFD-UHFFFAOYSA-N 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
- 238000004078 waterproofing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/28—Compounds of silicon
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/12—Treatment with organosilicon compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/90—Other properties not specified above
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Silicon Compounds (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
It the present invention relates to the use of hydrophobic silica obtained from silicone oil is surface-treated to damp process synthetic silica.Silicone oil stripping quantity of the above-mentioned hydrophobic silica (i) in toluene is less than 0.2% relative to hydrophobic silica quality, wherein, above-mentioned stripping quantity is to be dispersed in 2% concentration in toluene, 20 DEG C after 24 hours with it is scattered before contrasted obtained from silicone oil dissolution rate.It the present invention relates to the use of the manufacture method for the hydrophobic silica that silicone oil is surface-treated to damp process synthetic silica.This method includes：In the Surface coating silicone oil for the damp process synthetic silica that there are the neutral salt compound of strong acid and strong base type, next for the silicone oil that is coated with conditions of the silanol group formation siloxanes key of damp process synthetic silica, obtaining hydrophobic silica.The present invention provides hydrophobic silica, the hydrophobization degree shown by M values, DBA adsorbances can be maintained desired value by the hydrophobic silica after silicic acid anhydride, while the silanol group and unreacted silicone oil that there occurs free, dissolution silica surface can be reduced.
Description
Technical field
The present invention relates to hydrophobic silica and its manufacture method.It is more particularly related to which silicone oil is free
The hydrophobic silica and its manufacture method being suppressed.
Association request it is cross-referenced
The priority for the Japanese patent application 2014-250355 submitted this application claims on December 10th, 2014, its is complete
Record and quoted in this manual as specifically disclosed in portion.
Background technology
The surface of hydrophily powder pigment (is hereinafter recited as using hydrophobic dimethyl polysiloxane compound
" silicone oil ") cladding, surface-hydrophobicized pigment is widely known by the people.Particularly surface utilizes silicone oil hydrophobization
The hydrophobic synthetic silica of damp process (being hereinafter recited as " hydrophobic silica ") is widely used as defoamer, painting
The matting agent of material, anti-blocking agent of film etc..
In the case that hydrophobic silica is used for into coating applications, in addition to existing extinction performance, additionally it is possible to carry
The water proofing property of high film coated surface, assigns anti-pollution function, alkaline-resisting function, chemical-resistant resistance function, moreover, additionally it is possible to improves and applies
The resistance to flaw characteristic on film surface.For such characteristic, nearest hydrophobic silica particularly for be applied to household electrical appliances or
The plastic paint on electronic equipment surface is increased with the application in matting agent purposes.
In addition, by by the average grain diameter micronized of hydrophobic silica, being used in hyaline membrane or glass surface coating agent
In way, in addition to the above-described functions, also it is used for the purpose (such as patent document 1) for assigning anti-glare.
In addition, in the case where filling is into resin or membrane material, compared with untreated damp process synthetic silica,
Adsorption moisture is few, thus has the advantages that handling ease, the transparency are improved, and are attract attention.
Only the synthetic silica of the damp process of raw material is mixed with silicone oil can also produce with hydrophobic function
Hydrophobic silica, but have studied various methods for the purpose for improving hydrophobic performance.
For example, in patent document 2, will have 50 centistoke's Si (units：CSt the silicone oil of viscosity) is sprayed to wet type
Method synthetic silicic acid, heats about 1/2~2 hour in 250 DEG C~350 DEG C of temperature, has obtained hydrophobic silica.
In addition, as the method for the hydrophobic silica for obtaining more high hydrophobicity, having been recorded in patent document 3 wet
The hydroxide (sodium hydroxide) that alkali metal is added in formula method synthetic silica is used as the method for catalyst.And then, in patent
Proposed in document 4 and ammonia or amine etc. are used as catalyst, 60 DEG C~150 DEG C in relatively low temperature carry out heat-treating methods.
Proposed in patent document 5 using relative to SiO2100 parts by weight are with Al2O3Conversion meter contains aluminium more than 0.5 parts by weight
Silica, the method that the low temperature in normal temperature~100 DEG C or so carries out hydrophobization.
In the above method for the purpose of to hydrophilic damp process silica hydrophobic property energy, raising hydrophobic performance
In, be by using hydrophobic silicone oil cover be present in damp process silica surface hydrophilic silanol group (-
SiOH) purpose is realized.
It is used as the technology of higher hydrophobization, it is also known that have that a part for the siloxanes key (- Si-O-Si-) in silicone oil is logical
The operation cut-out such as heating is crossed, occurs dehydration condensation with the silanol group of wet silicon dioxide and carries out the side of chemical bonding
Method.It is believed that particular by the hydrophobization that surface is reacted and carried out as Fig. 1.
[changing 1]
The reaction of polysiloxanes and silica
As the method for the hydrophobization degree on the surface for knowing hydrophobic silica, adsorbed using DBA (di-n-butylamine)
Amount and M values.
Below to utilizing DBA adsorbance (units：Mmol/kg) represent that the principle of hydrophobicity degree is illustrated.
There is substantial amounts of silanol group in its surface in common silica (silica before hydrophobization), DBA with
Ionic bonding mode is adsorbed on the silanol group on silica particles.In surface treated hydrophobic silica
In, the silanol group for being present in silica surface is coated or reacted and disappeared by silicone oil.If remaining in hydrophobicity
The silanol group on the surface of silica, then be bonded with DBA, remaining silanol base unit weight understood by bonded amount.Therefore, it is made
To know that the means of silicon dioxide drainage degree are used.The numerical value of DBA adsorbances is low, represents that silanol group becomes and turns to
Siloxanes key, generally means that hydrophobization degree is high.
On the other hand, M values are the capacity % of the methanol moistened by handling powder in the mixed solution in water and methanol
The concentration of expression.The value of M values is higher, it is meant that hydrophobization degree is higher (maximum is about 70%).
These DBA values and M values embody the hydrophobization state of hydrophobic silica, but both values are not represented
Unique dependency relation.For example, in the hydrophobic silica for only mixing hydrophilic silicon oxides and a large amount of silicone oil or only
The surface of agglomerate is carried out in the hydrophobic silica of silicic acid anhydride, the remaining quantity of silanol group is more, DBA adsorbances show
High level is shown.But, because silicone oil covers silica surface, thus M values are high level.So as to hydrophobic in order to hold well
Property silica hydrophobization state, preferably monitor both DBA values and M values.
It should be noted that the neutralization reaction that the damp process synthetic silica that raw material is used passes through sodium metasilicate and inorganic acid
To synthesize, if substantially distinguishing, there are the precipitation method synthetic silica synthesized in basic region and the gel synthesized in acidic region
Method synthetic silica.
Patent document 1：No. 3504338 publications of Japanese Patent No.
Patent document 2：Japanese Japanese Patent Publication 42-26179 publications
Patent document 3：Japanese Unexamined Patent Application 47-12770 publications
Patent document 4：Japanese Japanese Patent Publication 57-2641 publications
Patent document 5：Japanese Unexamined Patent Publication 6-316408 publications
Patent document 6：Japanese Unexamined Patent Publication 8-176462 publications
Whole record of patent document 1~6 is quoted in this manual as specifically disclosed.
The content of the invention
Invent problem to be solved
For hydrophobic silica, variation, multifunction due to user's request are above-mentioned in that can occur more
Prior art is difficult to the situation of situation about tackling.
For example, in the case where hydrophobic silica is used for into coating applications as matting agent, as described above, can assign
Give anti-pollution function, alkaline-resisting function, chemical-resistant resistance function, resistance to flaw characteristic.But, it is cured as coating formation film
Stage, unreacted oily a part of dissolution to film coated surface, it may occur that the problem of so-called color is uneven occur.
In addition, in film field, after hydrophobic silica is applied into film, if carrying out batching for film, batching
When free silicone oil be moved to the inside of film, it also occur that the problems such as pollution.
Similarly as film anti-blocking agent use in the case of, have by using hydrophobic silica and improve saturating
The advantage of bright property, but (ブ リ ー De is oozed out due to silicone oil) and the different part of the local mist degree (Tan degree) for film occur, also turn into
The reason for the problems such as overall quality of film is impaired.
In these phenomenons, remaining unreacted silicone oil is oozed out as reason, implys that the silicon of silica surface
Silane alcohol base is not bonded completely with silicone oil.
But, it there occurs that the hydrophobic silica of above mentioned problem shows high m values, DBA adsorbances are also displayed as filling
Divide low value, in the case of using M values and DBA adsorbances as index, it may be said that be the high hydrophobicity titanium dioxide of hydrophobization degree
Silicon, actual conditions can not be held on the influential unreacted of the performance of hydrophobic silica merely with M values and DBA adsorbances
Silicone oil amount.In addition, to reduction unreacted silicon oil mass, then prolonged heat treatment is needed, it is unfavorable in commodity production.
The present inventor is studied the method for merely reducing silicone oil treating capacity to solve the above problems.But,
If using such method, hydrophobization is insufficient, even and if (such as thinking with existing method on heating condition
Method) will necessarily also there is unreacted silicone oil, problem cannot be solved.It for example have also been attempted portion described in patent document 6
Divide hydrophobization.But, even if reduce the silicone oil amount that is handled, it can not realize and subtract as the unreacted silicone oil of dissolved element
Few, problem cannot be solved.
In addition, as other methods, also having carried out following researchs：The silicone oil for selecting molecular weight big, reduces Unit Weight
Molecular number, to reduce unreacted silicone oil amount.But, the viscosity of the big silicone oil of molecular weight increases, and is uniformly mixed with silica
Itself it is highly difficult.
It is above-mentioned in the prior art, adding alkali metal in damp process synthetic silicic acid described in patent document 3 and 4
Hydroxide, in the method that uses as catalyst of ammonia, amine, silica is alkalescence, and weakly alkaline wet type synthesizes dioxy
The surface texture change such as specific surface area reduction occurs over time for SiClx, with can not give play to asking for stability
Topic.
In addition, the method described in patent document 5 has the advantages that to be surface-treated at low temperature.But, its
It is that the hydrophobic silica after being handled using such method has silicone oil for the purpose of M values, the raising of DBA values
Stripping quantity instead increased can be inclined to.
It specify that in other research process, in order that the chemical bonding of silicone oil and silanol group is completely and 350
DEG C~400 DEG C of high temperature is when carrying out the long heat treatment of more than 6 hours, the dissolution of silicone oil can be reduced.But, due to processing
Heat can make a part for silicone oil itself decompose, go bad, thus can not give play to desired performance.In addition, high temperature and length
The processing of time only can cause the notable deterioration of production efficiency and the increase of cost, impracticable.
In general, the BET specific surface area of former powder silica dioxide granule is high, and with micropore, and the size of particle is micro- for number
Meter Shui Ping size, thus be difficult to carrying out the silicone oil with viscosity into uniform treatment on a molecular scale, even if using existing skill
Any method of art also can not effectively suppress the generation of free silicone oil.
Therefore, the present inventor has made intensive studies to provide following hydrophobic silicas, the hydrophobicity dioxy
The hydrophobization degree shown by M values, DBA adsorbances can be maintained desired value by SiClx after silicic acid anhydride, while can
Reduction there occurs the silanol group and unreacted silicone oil of free, dissolution silica surface.
The means to solve the problem
Its result is found, is closed by the way that the neutral salt compound of strong acid and strong base type using sodium sulphate as representative is attached into damp process
Into the surface of silica, the neutral salt has given play to the effect of catalyst in the formation of silanol group and the siloxanes key of silicone oil
Really, the effect of free silicone oil is significantly reduced with the processing by comparing low temperature, the free silicone oil of reduction is very in the prior art
Difficult.Its result successfully have developed in low temperature and effectively the few hydrophobicity of stripping quantity of silicone oil under conditions of the short time
Silica, so as to complete the present invention.
The present invention is as follows.
[1]
A kind of hydrophobic silica, it is that damp process synthetic silica is surface-treated using silicone oil and obtained
Hydrophobic silica, wherein,
The characteristic of above-mentioned hydrophobic silica is as follows：
(i) silicone oil stripping quantity of the hydrophobic silica in toluene is less than relative to hydrophobic silica quality
0.2%, wherein, above-mentioned stripping quantity is to be dispersed in 2% concentration in toluene, is carried out at 20 DEG C after 24 hours and before disperseing
Silicone oil dissolution rate obtained from contrast.
[2]
Hydrophobic silica as described in [1], wherein, in above-mentioned hydrophobic silica, the content of sodium composition
With Na2O conversions are calculated as 0.20wt%~1.20wt%, and the content of sulphur composition is with SO3Conversion is calculated as 0.25wt%~1.30wt%.
[3]
Hydrophobic silica as described in [1] or [2], it is characterised in that every relative to starting silica
100m2/ g BET specific surface area, the treating capacity of silicone oil is 3 parts~9 parts.
[4]
Hydrophobic silica as described in [1] or [2], wherein,
(ii) M values are more than 20%, and/or
(iii) DBA adsorbances are less than 100mmol/kg.
[5]
A kind of manufacture method of hydrophobic silica, it is to carry out surface to damp process synthetic silica using silicone oil
The manufacture method of the hydrophobic silica of processing, wherein, this method includes：
In the Surface coating silicone oil for the damp process synthetic silica that there are the neutral salt compound of strong acid and strong base type, connect down
Under conditions of for the silanol group of the silicone oil coated and damp process synthetic silica formation siloxanes key, obtain hydrophobic
Property silica.
[6]
Manufacture method as described in [5], wherein, the neutral salt compound of above-mentioned strong acid and strong base type be sodium sulphate, sodium chloride,
Potassium sulfate, potassium chloride or their mixture.
[7]
Manufacture method as described in [5] or [6], wherein, the above-mentioned strong acid on the surface of damp process synthetic silica
The scope that the amount of strong base neutrality salt compound is 0.3%~3.0%.
[8]
Manufacture method as any one of [5]~[7], wherein, silicon of the above-mentioned hydrophobic silica in toluene
Oily stripping quantity is less than 0.2% relative to hydrophobic silica quality, wherein, above-mentioned stripping quantity is by above-mentioned hydrophobicity titanium dioxide
Silicon is dispersed in toluene with 2% concentration, 20 DEG C after 24 hours with it is scattered before contrasted obtained from silicone oil dissolution
Rate.
[9]
Manufacture method as any one of [5]~[7], wherein,
Above-mentioned hydrophobic silica
(i) M values are more than 20%, and/or
(ii) DBA adsorbances are less than 100mmol/kg.
[10]
Manufacture method as any one of [5]~[9], wherein, above-mentioned silicone oil is that kinematic viscosity is 500 centistokes (unit of kinematic viscosity)
Silicone oil below this.
The effect of invention
In accordance with the invention it is possible to provide a kind of hydrophobic silica being surface-treated using silicone oil, added
Be added in coating, be coated to be formed after film, silicone oil also will not dissolution to surface, the film coated surface that can be stablized.This
The hydrophobic silica of invention can be used for metallic paint, the matting agent of plastic paint, the coating in antiglare film, tree well
In fat filler, film anti-blocking agent etc..
Embodiment
[hydrophobic silica of the invention]
The hydrophobic silica of the present invention is that damp process synthetic silica is surface-treated using silicone oil and obtained
The hydrophobic silica arrived, it is the hydrophobic silica for meeting following (i).
(i) the silicone oil stripping quantity in toluene is less than 0.2% relative to hydrophobic silica quality.Wherein, it is above-mentioned molten
Output is to be dispersed in above-mentioned hydrophobic silica in toluene with 2% concentration, 20 DEG C after 24 hours with it is scattered before
Silicone oil dissolution rate obtained from being contrasted.
<Silicone oil stripping quantity>
The silicone oil stripping quantity of the hydrophobic silica of the present invention is compared with the state before scattered relative to hydrophobicity dioxy
SiClx is integrally less than 0.2%, and the silicone oil stripping quantity is to be dispersed in 2% concentration in toluene solution, small by 24 at normal temperatures
When after silicone oil stripping quantity in toluene solution.The silicone oil stripping quantity be more than 0.2% when, as coating formation film and by
The stage of solidification, a unreacted oily part in film coated surface dissolution, as color it is uneven the reason for；Or it is being applied to film
Afterwards, if being batched to film, the problems such as free silicone oil is moved to the inside of film and polluted when take-up can cause
The deterioration of characteristic is oozed out as the generation of the above-mentioned various problems of representative using oil.In order to further solve problem, above-mentioned silicone oil it is molten
Output is preferably smaller than 0.15%, more preferably less than 0.10% and then more preferably less than 0.08%.
When being dispersed in coating etc., the measure of the stripping quantity of silicone oil during compounded resin is difficult to use Direct Analysis side
Method, by selecting hydrophobic silica being dispersed in toluene solvant, is obtained by warp dissolution later in 24 hours into toluene
Silicone oil amount method, unreacted silicone oil amount can be determined simply and exactly.
The hydrophobic silica of the present invention is the hydrophobic silica for meeting above-mentioned (i), under further preferably meeting
State (ii) and/or (iii).
(ii) M values are more than 20%.
(iii) DBA adsorbances are less than 100mmol/kg.
, as described above can be with DBA adsorbances and M values come table on the state of the surface treatment of hydrophobic silica
Show, in the hydrophobic silica of the present invention, from the aspect of the physical property for meeting hydrophobic silica all the time,
It is preferred that M values, which are more than 20%, DBA adsorbances, is less than 100mmol/kg.
<M values>
M values (the M values handled in the mixed solution in water and methanol powder start moistening methanol capacity % come table
Show) it is less than in the case of 20%, the hydrophobization degree for typicallying represent silica is very low (remaining hydrophilic radical) in itself, the M values
Preferably more than 20%.The present invention hydrophobic silica M values be more preferably more than 40%, be more preferably 55% with
On.
<DBA adsorbances>
In DBA adsorbances, (it represents the silanol group (hydrophilic radical) in the remained on surface of raw material hydrophilic silicon oxides
Amount) be more than 100mmol/kg in the case of, substantial amounts of hydrophilic group is mostly remained generally in hydrophobic silica
Group.(easily being produced in the case where heat treatment described later is insufficient, also result in the dissolution of silicone oil) is if DBA adsorbances are less than
100mmol/kg, then when being dispersed in solvent system coating, will not produce pigment due to the interaction between hydrophilic radical
Or the absorption of curing agent, it will not also turn into and occur cohesion etc. when viscosity abnormality after just scattered rises or mixture is in resin
The producing cause of deleterious situation.The value of the DBA adsorbances of the hydrophobic silica of the present invention is more preferably less than 60mmol/
Kg, it is further preferably no larger than 20mmol/kg.
It is not particularly limited for the species of damp process synthetic silica and physical property used in the present invention.The precipitation method two
Silica and gel silica are used without problem.
The BET specific surface area of usual precipitated silica is 20m2/ g~300m2/ g, gel silica BET ratios
Surface area is 250m2/ g~700m2/ g, but in the case of hydrophobization, relative to every 100m2The silicone oil of/g BET specific surface area
Treating capacity is necessary for 3~9 parts.If for example, BET specific surface area is 300m2/ g silica, then the treating capacity of silicone oil is suitable
For 9~27 parts.
For the hydrophobic silica of the present invention, the purpose in the dissolution for preventing silicone oil, surface can not also
Must hydrophobization completely, as long as silicone oil treating capacity is relative to every 100m2/ g BET specific surface area is 3~9 parts of scope, can also
Necessary treating capacity is selected according to purposes purpose.Usual treating capacity is fewer, then it represents that more incomplete hydrophobic to silica surface
The state of change；Otherwise treating capacity is more, then it represents that the state of more complete hydrophobization.By making silicone oil treating capacity relative to every
100m2/ g BET specific surface area is more than 3 parts, and hydrophobization degree is reduced in itself, so as to fully obtain as hydrophobicity titanium dioxide
The efficiency of silicon.On the other hand, be also not in the silicone oil superfluous relative to silica surface if treating capacity is less than 9 parts,
Fully exist for the silanol group on the damp process synthetic silica surface that is bonded with silicone molecule, can not only suppress not anti-
The remaining quantity for the silicone oil answered, and stripping quantity can be suppressed, it can promote and reach the purpose of the present invention.It is preferred that the treating capacity of silicone oil is relative
In 100m2/ g BET specific surface area is suitably 4 parts~8 parts of scope, can within the range according to purposes or purpose change at
Reason amount.
The purpose of the present invention is mainly used in by the coating applications of representative or resin filler of coating or cement, film it is anti-
In adhesion agent etc., thus hydrophobic silica can in the same manner as untreated wet type synthetic silica according to purpose in base
Suitably flexibly used in the range of the average grain diameter of laser method is 1 μm~15 μm.It is most in the case where average grain diameter is small
It is used to the delustring of clear dope or the delustring of paint for plastics etc. require the field of fine extinction performance, require higher saturating
In the resin filler of bright property or the anti-blocking agent of film etc.；In the case where particle diameter is big, majority is used for metallic paint or building materials
Delustring with coating etc. requires the field of high delustring.The adjustment of average grain diameter is generally adjusted by carrying out crushing and classification, is adjusted
It is whole to be carried out after feed stage, silicic acid anhydride, it can also carry out based on the adjustment shared.
Adjusted by the degree carried out as feed stage, be micro-adjusted to adjust granularity, energy after silicic acid anhydride
Enough precision produce the silica with purpose particle diameter well.
As long as silicone oil used in the present invention can be mixed with damp process synthetic silica, its species is not limited
It is fixed.General use only there is methyl, the commercially available dimethicone of phenyl (to be commonly referred to as pure silicon oil (ス ト レ ー ト シ リ コ ー Application オ イ
Le)), the modified version silicone oil on the silicon atoms with Organic substituent can also be used in addition.As the example of substituent, with
Polyethers, epoxy, amine, carboxyl are representative, and most modified version silicone oil is commercially available.As modified version silicone oil, for example, it can enumerate
Following products.
<The modified silicon oil of chemical industry society of SHIN-ETSU HANTOTAI manufacture>
KF-868、865、859、393、250、889、2001、2004、99、9901、8010、8012、8008、105、6000、
6001、6002、6003、6123、2200、9701、2012、857、8001、858、351A、353、354L、355A、945、640、
642、643、644、6020、6204、6011、6015、6017、412、413、414、4003、4917、7235B、50、53、54、
54SS、X-22-343、2000、2046、4741、4039、4015、161A、161B、9490、163、163A、163B、163C、
169AS、169B、164、164AS、164A、164B、164C、164E、4952、4272、167B、167C、162C、5841、2445、
1602、168AS、168A、168B、173BX、173DX、170BX、170DX、176DX、176GX-A、174ASX、174BX、2426、
2475、3710、2516、821、822、7322、3265、
<The modified silicon oil of TorayDow Corning Co., Ltd. manufacture>
SF 8417、BY 16-205、BY 16-213、BY 16-871、BY 16-893、SF 8411、BY 16-880、SF
8427、BY 16-201、SF 8428、BY 16-846、SF 8419、FS 1265、SH 510、SH 550、SH 710、SH
8400、FZ-77、L-7604、
<The modified silicon oil of Momentive Performance Materials companies manufacture>
TSF4440、4441、4445、4446、4452、4460、4700、4701、XF42-B0970、
<The modified silicon oil of Wacker-Chemie companies manufacture>
L03、033、066、L653、655、656、662、WT1250、65000VP、AP100、150、200、500、AR20、
200、
For silicone oil, because the damp process synthetic silica low with accumulation relative density is mixed, thus using
, it is necessary to try to use using the dilution such as solvent in the case of the silicone oil that molecular weight is high, viscosity is high.Therefore it is usually preferred to make
With the silicone oil that viscosity is the relatively low viscosity of 500 centistokes (unit of kinematic viscosity) Si (500cSt) below.Kinematic viscosity is below 500 centistokes (unit of kinematic viscosity) Si
Silicone oil can for example enumerate following products.
<The silicone oil of Shin-Etsu Chemial Co., Ltd's manufacture>
KF-96-10cs、20cs、30cs、50cs、100cs、200cs、300cs、350cs、500cs、
<The silicone oil of TorayDow Corning Co., Ltd. manufacture>
SH200-0.65cs、1cs、1.5cs、2cs、3cs、5cs、10cs、20cs、50cs、100cs、
200cs、350cs、500cs、
<The silicone oil of Momentive Performance Materials companies manufacture>
TSF451-0.65、5A、10、20、30、50、100、200、300、350、500、
<The silicone oil of Wacker-Chemie companies manufacture>
AK0.65、1、10、35、50、100、350、500
[manufacture method of hydrophobic silica of the invention]
The hydrophobic silica that the present invention is surface-treated using silicone oil to damp process synthetic silica
Manufacture method.The manufacture method includes：It there are the damp process synthetic silica of the neutral salt compound of strong acid and strong base type
Surface coating silicone oil, next for the silanol group formation siloxanes key of the silicone oil and damp process synthetic silica that are coated
Under conditions of, obtain hydrophobic silica.
Before being surface-treated using silicone oil, implementation adds strong acid in the damp process synthetic silica as former powder
Strong base neutrality salt compound (strong acid and strong base type neutrality salt compound is used as the material as catalyst), such as sodium sulphate
(Na2SO4) composition etc. pre-treatment.On the neutral salt compound of strong acid and strong base type, in addition to sodium sulphate, example can also be enumerated
Such as sodium chloride, potassium sulfate, potassium chloride and their mixture.The strong acid and strong base type on the surface of damp process synthetic silica is neutral
The amount of salt compound is appropriate for example in 0.3%~3.0% scope.Method on pre-treatment is not limited especially
It is fixed, following methods can be enumerated：Washing is carried out when the synthetic reaction of silica is terminated until as the sulphur of byproduct of reaction
Sour sodium (Na2SO4) ormal weight is reached, pH adjustment can be implemented afterwards and utilized；With slurry form after sufficiently wash
Add the sodium sulphate (Na of ormal weight2SO4), the method for carrying out pH adjustment using alkali such as sodium hydroxides (NaOH) as needed；First
Sulfuric acid (the H of ormal weight is only added into silica slurry2SO4), the side of pH adjustment is carried out using sodium hydroxide (NaOH) afterwards
Method；Etc..
Thereafter by drying, crushing, be classified process, the damp process synthetic silica with purpose particle diameter is made.Now
It is adjusted to as Na compositions contained in the damp process synthetic silica of former powder with Na2O conversion meters are substantially in 0.3wt%
Purpose scope, S compositions near~1.4wt% are adjusted to SO3Conversion meter is substantially near 0.36wt%~1.44wt%
Purpose scope.These values represent the impurity level in former powder, with contain in the hydrophobic silica as end article it is miscellaneous
Quality has the slightly different tendency of numerical value.If Na2O amounts are few, then reduced as the effect of catalyst；Conversely, in Na2O amounts increase
When, not only it could not be expected that catalytic effect is significantly improved, and also largely contain salt in silica, be undesirable.Separately
Outside, S and SO3It is that, for suppressing to become due to Na alkaline acid ingredient, by being above range, deviation can be suppressed
Alkalescence.
Before implementing merely with alkaline components such as sodium hydroxides (NaOH) to the damp process synthetic silica as former powder
In the case of processing or merely with sulfuric acid (H2SO4) etc. acid ingredient to as former powder damp process synthetic silica implement before
In the case of processing, damp process synthetic silica composition respectively becomes alkalescence, acid, thus not preferably, it is necessary to make two kinds into
Balance-dividing exists well and pH is near neutral.On the pH of the damp process synthetic silica as former powder, if from
On the way, from the aspect of purpose, then it is preferably in 5.5~8.0 scope of near neutral.If particularly alkalescence enhancing, titanium dioxide
The surface of silicon can go bad over time, modified, the problem of occurring different from this research purpose, thus not preferred.
In addition, in the case of damp process synthetic silica, sometimes containing the aluminium system from raw material natural crystal
Impurity, in damp process synthetic silica as impurity aluminum amount more than in the case of, although its reason still do not know, observation
The tendency of catalytic effect reduction is arrived.By rule of thumb, it can be said that being used as the aluminum amount contained in the damp process synthetic silica of former powder
With Al2O3Conversion meter is preferably smaller than 0.5wt%.
Implemented for the damp process synthetic silica as former powder obtained like this using silicone oil after silicic acid anhydride,
As the impurity level in hydrophobic silica entirety, Na compositions are with Na2O conversion meter must be 0.20wt%~1.20wt%, S into
Divide with SO3Conversion meter must be 0.25wt%~1.30wt%.Producing difference with former powder content scope is due to, in silicic acid anhydride
When add the weight of silicone oil so that impurity weight % reductions shared in silica entirety.
Surface treatment side for carrying out silicic acid anhydride to the damp process synthetic silica as former powder using silicone oil
Method is also not particularly limited, as shown below example, the processing usually carried out using dry type mixing.First by FM blenders
The dry type mixing such as (Henschel mixer) dispersal device mixes the silicone oil of the silica of drying regime and ormal weight equal
It is even come implement surface treatment.As described above, it is effective heat treatment to be carried out after surface treatment, but to specific heat treatment side
Method is not particularly limited.Generally by using annealing devices such as electric furnace, Nesco heaters, drying ovens at 250 DEG C~400 DEG C
The silanol group of the heat treatment of implementation 0.5 hour~4.0 hours or so, silicone oil and silica surface is chemically bonded, thus energy
Enough maintain prolonged hydrophobization.
It should be noted that because silicone oil has with methyl (- CH3) it is the organic group of representative, thus implementing hydrophobic
After change processing, by being measured to the carbon amounts (C amounts) in hydrophobic silica, it can also be obtained by inverse operation at silicone oil
Reason amount.
In the case of the hydrophobic silica of the present invention, imitated using the catalysis of the neutral salt compound of strong acid and strong base type
Really, even in low temperature, the few hydrophobic silica of dissolution silicone oil also can be effectively produced under conditions of the short time.
Purposes for the hydrophobic silica of the present invention is not also limited, and mainly can be used as matting agent or the tree of coating
Fat filler, antiblocking agent of film etc..
Particularly it is being coated on the matting agent of the coating (comfortable feel coating) of frosting or is requiring the transparency and delustring
The film coating applications (such as antiglare film, anti-dazzle (the ア Application チ グ レ ア) film for being pasted onto liquid crystal surfactant) of property these two aspects
In, solvent-borne type, no-solvent type are used in which can be more suitable for.
Embodiment
The present invention is described in more detail below based on embodiment.But embodiment is the illustration of the present invention, the present invention is not
It is intended to be limited in embodiment.
Various physical property measurements and experiment in embodiment and comparative example are carried out by following methods.
1) DBA adsorbances
Accurate weighing dries sample 250mg, and N/500 di-n-butylamine solution (petroleum ether (oil ベ Application ジ is added thereto
Application) solvent) 50ml, is placed about 2 hours at 20 DEG C.Chloroform 5ml, indicator (crystal violet) 2~3 are added into its supernatant 25ml
Drop, untill being titrated to purple change au bleu using N/100 perchloric acid solution (acetic anhydride solvent), if titration value now is
Aml。
If the titration value for being additionally carried out blank titration is Bml, DBA adsorbances are calculated by following formula.
DBA adsorbances (mmol/kg)=80 (B-A) f
Wherein, f is the titer of N/100 perchloric acid solution
2) M values
Methanol concentration is prepared with the methanol and the mixed solution of water of 5 capacity % interval variation, in volume 10ml experiment
The 5ml mixed solutions are added in pipe.Next 0.1g~0.2g is added for examination powder, is vibrated and is observed after mixing, standing, knows powder
The minimum methanol concentration that body suspends, as M values.
3) silicone oil stripping quantity
The silica 1 .0g that silicic acid anhydride has been carried out using silicone oil etc. is added in toluene 50g, 1 is carried out,
After the homomixer of 000rpm × 30 minute is scattered, it is transferred in centrifuge tube, stands 15 hours at normal temperatures.In the stage silicon
In the case that oily dissolution is into toluene, it was observed that foamed phenomenon.Entered using whizzer under conditions of 3,000rpm, 5min
After the centrifugation of row centrifuge tube, supernatant liquor is abandoned.It is centrifuged after adding toluene dissolving again.Carry out 2 times again
Toluene is abandoned, the operation being centrifuged after n-hexane dissolution is added.Abandon after separating liquid, dried in 80 DEG C of drier
More than 15 hours, the carbon content analysis of the solid constituent remained.Carbon amounts also for the silica of blank is analyzed, and is led to
Cross following formula and obtain silicone oil amount of the dissolution into toluene and n-hexane.
(formula)
Silicone oil amount (%) after silicone oil amount (%)-toluene dissolution before toluene dissolution silicone oil amount=toluene dissolution
4) carbon content analysis
The carbon content analysis used in the measure of silicone oil stripping quantity uses solid carbon analytical equipment (device name：Carbon
Analyzer, model EMIA-110, hole make the manufacture of society of institute) flow into pressure 0.07MPa, minute 90s in 1,250 DEG C, oxygen
Under conditions of be measured.Calculated using following formula by the carbon amounts tried to achieve and obtain silicone oil treating capacity.
(formula)
Carbon amounts in silicone oil treating capacity (%)=carbon analysis measured value (%) × silicone molecule amount/silicone oil
5) impurity level
Use sweep type fluorescent x-ray analyzer (model：ZSX PrimusII, Rigaku companies manufacture) carry out each member
The quantitative analysis of element.Measurement result is converted into oxide amount to export.
6) BET specific surface area
Use full-automatic specific area measuring device (model：Macsorb(R)HM model-1200, Co., Ltd.
Mountech societies manufacture) it is measured by one point method.
7)pH
Use pH meter (model：D-50 holes make the manufacture of society of institute) to the damp process synthetic silica progress as former powder
Determine.(※ hydrophobic silicas and water not affinity, thus can not determine)
[embodiment 1]
Sodium metasilicate is set to be reacted with sulfuric acid, synthesis BET specific surface area is 130m2/ g precipitated silica.To institute
The precipitated silica of synthesis is filtered, washed, and obtains silica filter cake.Water is added into the silica filter cake,
While redisperse is carried out using reciprocating rotary mixer (manufacture of Dao Qi engineering companies), while according to Na2O conversions are calculated as
0.50wt%, with SO3Conversion is calculated as 0.60wt% addition sodium sulphate (Na2SO4), further add sodium hydroxide (NaOH) and be used for
PH adjustment is carried out, the silica slurry that pH is 7.5 is made.The silica slurry is utilized into spray dryer (great river originalization
Gong Ji societies manufacture) dry, obtain the precipitated silica that average grain diameter is 6.3 μ by crushing, being classified process.It is subsequently added into
10 parts (relative to BET specific surface area 100m2/ g is 7.7 parts) dimethicone KF96-50CS (manufacture of chemical company of SHIN-ETSU HANTOTAI), profit
10 minutes mixed processings are carried out with Henschel mixer (Mitsui Mining Co Ltd. BJ Offc manufactures).After mixing, muffle furnace is utilized
(manufacture of Yamato scientific companies) carries out heating for 1 hour after implementing granularity adjustment, obtaining hydrophobic wet type at 300 DEG C
Method silica.Physical property after the physical property and hydrophobization of former powder, stripping quantity are listed in table 1.
[embodiment 2]
In embodiment 1, according to Na2O conversions are calculated as 0.32wt%, with SO3Conversion is calculated as 0.38wt% to add sulfuric acid
Sodium (Na2SO4), obtain hydrophobic silica using method same as Example 1 in addition.
[embodiment 3]
In embodiment 1, silicone oil treating capacity is changed to relative to BET specific surface area 100m2/ g be 3.8 parts, except this with
It is outer to obtain hydrophobic silica using method same as Example 1.
[embodiment 4]
In embodiment 1, according to Na2O conversions are calculated as 0.90wt%, with SO3Conversion is calculated as 1.08wt% to add sulfuric acid
Sodium (Na2SO4), obtain hydrophobic silica using method same as Example 1 in addition.
[embodiment 5]
Starting silica is changed to commercially available sedimentation silica Nipsil N-300A (BET specific surface areas
150m2/ g), silicone oil treating capacity is changed to relative to BET specific surface area 100m2/ g is 6.7 parts, is utilized in addition and implementation
The identical method of example 1 obtains hydrophobic silica.
[embodiment 6]
The silicone oil treating capacity of the precipitated silica of embodiment 5 is changed to relative to BET specific surface area 100m2/ g is
3.3 parts, obtain hydrophobic silica using method same as Example 1 in addition.
[embodiment 7]
Starting silica is changed to commercially available gel silica NIPGEL AZ-200 (BET specific surface areas
300m2/ g), silicone oil treating capacity is changed to relative to BET specific surface area 100m2/ g is 5.3 parts, is utilized in addition and implementation
The identical method of example 1 obtains hydrophobic silica.
[embodiment 8]
Starting silica is changed to commercially available gel silica NIPGEL BY-601 (BET specific surface areas
500m2/ g), silicone oil treating capacity is changed to relative to BET specific surface area 100m2/ g is 3.0 parts, is utilized in addition and implementation
The identical method of example 1 obtains hydrophobic silica.
[comparative example 1]
In embodiment 1, without sodium sulphate (Na2SO4), adjust without pH, in addition all of with embodiment
Identical method obtains hydrophobic silica.
[comparative example 2]
In comparative example 1, addition sodium hydroxide (NaOH) is used for carrying out pH adjustment, and the silica slurry that pH is 10.8 is made
Material, obtains hydrophobic silica all of with the identical method of comparative example 1 in addition.
[comparative example 3]
In embodiment 5, without sodium sulphate (Na2SO4), adjust without pH, in addition all of with embodiment
5 identical methods obtain hydrophobic silica.
[comparative example 4]
In comparative example 3, sulfuric acid (H is added2SO4) be used for carrying out pH adjustment, the silica slurry that pH is 3.2 is made, removes
Beyond this hydrophobic silica is obtained all of with the identical method of comparative example 3.
[comparative example 5]
As the example of commercially available hydrophobic silica, Nipsil SS-50B are used.
[comparative example 6]
In embodiment 7, without sodium sulphate (Na2SO4), adjust without pH, in addition all of with embodiment
7 identical methods obtain hydrophobic silica.
[comparative example 7]
As the example of commercially available hydrophobic silica, Nipsil SBY-61 are used.
Industrial applicibility
The present invention is useful for the manufacture method of hydrophobic silica.
Claims (10)
1. a kind of hydrophobic silica, it is obtained from being surface-treated using silicone oil to damp process synthetic silica
Hydrophobic silica, wherein,
Above-mentioned hydrophobic silica
(i) the silicone oil stripping quantity in toluene is less than 0.2% relative to hydrophobic silica quality, wherein, above-mentioned stripping quantity
It is to be dispersed in above-mentioned hydrophobic silica in toluene with 2% concentration, is carried out at 20 DEG C after 24 hours and before disperseing
Silicone oil dissolution rate obtained from contrast.
2. hydrophobic silica as claimed in claim 1, wherein, in above-mentioned hydrophobic silica, sodium composition contains
Amount is with Na2O conversions are calculated as 0.20wt%~1.20wt%, and the content of sulphur composition is with SO3Conversion be calculated as 0.25wt%~
1.30wt%.
3. hydrophobic silica as claimed in claim 1 or 2, it is characterised in that relative to starting silica per 100m2/
G BET specific surface area, the treating capacity of silicone oil is 3 parts~9 parts.
4. hydrophobic silica as claimed in claim 1 or 2, wherein,
(ii) M values are more than 20%, and/or
(iii) DBA adsorbances are less than 100mmol/kg.
5. a kind of manufacture method of hydrophobic silica, it is that damp process synthetic silica is carried out at surface using silicone oil
The manufacture method of the hydrophobic silica of reason, wherein, this method includes：
In the Surface coating silicone oil for the damp process synthetic silica that there are the neutral salt compound of strong acid and strong base type, next supply
Under conditions of silanol group formation siloxanes key of the silicone oil coated with damp process synthetic silica, hydrophobicity two is obtained
Silica.
6. manufacture method as claimed in claim 5, wherein, the neutral salt compound of above-mentioned strong acid and strong base type is sodium sulphate, chlorination
Sodium, potassium sulfate, potassium chloride or their mixture.
7. the manufacture method as described in claim 5 or 6, wherein, the above-mentioned strong acid on the surface of damp process synthetic silica
The scope that the amount of strong base neutrality salt compound is 0.3%~3.0%.
8. the manufacture method as any one of claim 5~7, wherein, above-mentioned hydrophobic silica is in toluene
Silicone oil stripping quantity is less than 0.2% relative to hydrophobic silica quality, wherein, above-mentioned stripping quantity is by above-mentioned hydrophobicity dioxy
SiClx is dispersed in toluene with 2% concentration, 20 DEG C after 24 hours with it is scattered before contrasted obtained from silicone oil it is molten
Extracting rate.
9. the manufacture method as any one of claim 5~7, wherein,
Above-mentioned hydrophobic silica
(i) M values are more than 20%, and/or
(ii) DBA adsorbances are less than 100mmol/kg.
10. the manufacture method as any one of claim 5~9, wherein, above-mentioned silicone oil is that kinematic viscosity is 500 centistokes
Silicone oil below lentor.
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| JP2014250355A JP6393177B2 (en) | 2014-12-10 | 2014-12-10 | Hydrophobic silica and method for producing the same |
| JP2014-250355 | 2014-12-10 | ||
| PCT/JP2015/084377 WO2016093221A1 (en) | 2014-12-10 | 2015-12-08 | Hydrophobic silica and method for producing same |
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| CN107074564B CN107074564B (en) | 2020-07-10 |
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| JP (1) | JP6393177B2 (en) |
| KR (1) | KR102422958B1 (en) |
| CN (1) | CN107074564B (en) |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110202893A (en) * | 2019-05-29 | 2019-09-06 | 安徽集友新材料股份有限公司 | Dumb light transfer paper and preparation method thereof and dumb light shift extrusion coating paper |
| CN110204979A (en) * | 2019-05-29 | 2019-09-06 | 安徽集友新材料股份有限公司 | Dumb paint and preparation method thereof |
| CN116554943A (en) * | 2023-03-29 | 2023-08-08 | 安徽沸点新材料有限公司 | High-temperature-resistant silicone oil composite lubricating ester and preparation method thereof |
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| EP3813972A4 (en) * | 2018-06-15 | 2022-03-23 | W. R. Grace & Co.-Conn | Defoamer active, manufacturing method thereof, and defoaming formulation |
| KR102214188B1 (en) * | 2020-12-24 | 2021-02-08 | 전순분 | Opv composition for overprinting on packing film |
| KR102605531B1 (en) * | 2021-11-02 | 2023-11-22 | (재)울산테크노파크 | Epoxy adhesive composition and manufacturing method thereof |
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Also Published As
| Publication number | Publication date |
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| JP6393177B2 (en) | 2018-09-19 |
| KR20170091577A (en) | 2017-08-09 |
| MY176249A (en) | 2020-07-24 |
| WO2016093221A1 (en) | 2016-06-16 |
| KR102422958B1 (en) | 2022-07-20 |
| CN107074564B (en) | 2020-07-10 |
| JP2016113305A (en) | 2016-06-23 |
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