JP2021070822A - Filler for oil-based ink and pigment composition for oil-based ink - Google Patents
Filler for oil-based ink and pigment composition for oil-based ink Download PDFInfo
- Publication number
- JP2021070822A JP2021070822A JP2020177530A JP2020177530A JP2021070822A JP 2021070822 A JP2021070822 A JP 2021070822A JP 2020177530 A JP2020177530 A JP 2020177530A JP 2020177530 A JP2020177530 A JP 2020177530A JP 2021070822 A JP2021070822 A JP 2021070822A
- Authority
- JP
- Japan
- Prior art keywords
- oil
- based ink
- filler
- amorphous silica
- mass
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000945 filler Substances 0.000 title claims abstract description 30
- 239000000049 pigment Substances 0.000 title claims description 20
- 239000000203 mixture Substances 0.000 title claims description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 75
- 238000000034 method Methods 0.000 claims abstract description 29
- 239000002245 particle Substances 0.000 claims abstract description 20
- 238000000790 scattering method Methods 0.000 claims abstract description 5
- 239000012463 white pigment Substances 0.000 claims description 23
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 22
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 22
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 12
- 238000001556 precipitation Methods 0.000 claims description 12
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 10
- 239000000460 chlorine Substances 0.000 claims description 10
- 229910052801 chlorine Inorganic materials 0.000 claims description 10
- 239000011787 zinc oxide Substances 0.000 claims description 6
- 238000007561 laser diffraction method Methods 0.000 claims description 4
- 238000007650 screen-printing Methods 0.000 claims description 3
- 238000004062 sedimentation Methods 0.000 abstract description 10
- 239000000976 ink Substances 0.000 description 36
- 238000000576 coating method Methods 0.000 description 21
- 239000011248 coating agent Substances 0.000 description 19
- 238000011156 evaluation Methods 0.000 description 16
- 239000002253 acid Substances 0.000 description 14
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 13
- 239000003973 paint Substances 0.000 description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 229910052500 inorganic mineral Inorganic materials 0.000 description 8
- 239000011707 mineral Substances 0.000 description 8
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 6
- 230000032683 aging Effects 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- 238000009736 wetting Methods 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000011246 composite particle Substances 0.000 description 4
- 239000010419 fine particle Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 239000004115 Sodium Silicate Substances 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000011164 primary particle Substances 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- -1 salt Chemical compound 0.000 description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052911 sodium silicate Inorganic materials 0.000 description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229910020175 SiOH Inorganic materials 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910021485 fumed silica Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 125000005372 silanol group Chemical group 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000007646 gravure printing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- XONPDZSGENTBNJ-UHFFFAOYSA-N molecular hydrogen;sodium Chemical compound [Na].[H][H] XONPDZSGENTBNJ-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 235000011008 sodium phosphates Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- ZSDSQXJSNMTJDA-UHFFFAOYSA-N trifluralin Chemical compound CCCN(CCC)C1=C([N+]([O-])=O)C=C(C(F)(F)F)C=C1[N+]([O-])=O ZSDSQXJSNMTJDA-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical group [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
Images
Abstract
Description
本発明は沈降法非晶質シリカからなる油性インク用填剤に関するものであり、さらには、該油性インク用填剤が配合された油性インク用顔料組成物にも関する。 The present invention relates to an oil-based ink filler made of precipitated amorphous silica, and further relates to an oil-based ink pigment composition containing the oil-based ink filler.
シリカ粒子のインク用填剤への配合は従来行われていたが、艶消し調や梨地調を付与する目的での配合に過ぎなかった（特許文献１参照）。 Conventionally, silica particles have been blended into an ink filler, but they have only been blended for the purpose of imparting a matte tone or a satin finish (see Patent Document 1).
一方、インクが透明な記録媒体又は着色された記録媒体に印刷される場合、透明記録媒体の透過性を低減したり、着色記録媒体の色を隠蔽したりして印刷する必要がある。このような隠蔽性が求められる場合、酸化チタン等の顔料が用いられる。 On the other hand, when the ink is printed on a transparent recording medium or a colored recording medium, it is necessary to reduce the transparency of the transparent recording medium or conceal the color of the colored recording medium for printing. When such concealment is required, a pigment such as titanium oxide is used.
インクの隠蔽性を高めたい場合、顔料の配合量を増やすことで対応可能であるが、酸化チタン等の顔料は沈降性が高いため、多量の配合は避けたいのが実情である。例えば、特許文献２には、酸化チタン及び／または酸化亜鉛粒子を含む隠蔽性複合粒子が、粒径が０．００８〜０．０５μｍの超微細な無機微粒子（例えばヒュームドシリカ）が分散されている溶液に配合されている隠蔽性インキ組成物が開示されている。 If you want to improve the hiding power of the ink, you can do it by increasing the blending amount of the pigment, but since pigments such as titanium oxide have high sedimentation properties, it is the actual situation that you want to avoid blending a large amount. For example, in Patent Document 2, concealing composite particles containing titanium oxide and / or zinc oxide particles are dispersed with ultrafine inorganic fine particles (for example, fumed silica) having a particle size of 0.008 to 0.05 μm. The concealing ink composition contained in the solution is disclosed.
しかしながら、特許文献２の隠蔽性インキ組成物において、超微細な無機微粒子は、粒径の大きな隠蔽性複合粒子の沈降を防止するために使用されているものであり、かかる無機微粒子の使用により、隠蔽性複合粒子をインク中に均一に分散でき、安定した隠蔽力を発揮できるとしても、隠蔽性複合粒子の使用量を低減させて高い隠蔽性を発現させることはできない。 However, in the concealing ink composition of Patent Document 2, ultrafine inorganic fine particles are used to prevent sedimentation of concealing composite particles having a large particle size, and by using such inorganic fine particles, Even if the hiding composite particles can be uniformly dispersed in the ink and a stable hiding power can be exhibited, it is not possible to reduce the amount of the hiding composite particles used to exhibit high hiding power.
従って本発明の目的は、高い隠蔽性を示す油性インク用填剤を提供することにある。
本発明の他の目的は、白色顔料と組み合わせで使用されたとき、高価な白色顔料の使用量を低減させながら高い隠蔽力を確保することが可能な油性インク用填剤を提供することにある。
本発明のさらに他の目的は、上記油性インク用填剤と白色顔料とを含む油性インク用顔料組成物を提供することにある。
Therefore, an object of the present invention is to provide a filler for an oil-based ink that exhibits high hiding power.
Another object of the present invention is to provide an oil-based ink filler capable of ensuring high hiding power while reducing the amount of expensive white pigment used when used in combination with a white pigment. ..
Still another object of the present invention is to provide a pigment composition for an oil-based ink containing the above-mentioned filler for an oil-based ink and a white pigment.
本発明によれば、レーザ回折散乱法で測定した体積基準平均粒径（Ｄ５０）が０．８〜４．０μｍであり、ＢＥＴ比表面積が５〜３００ｍ２／ｇの範囲にある、沈降法非晶質シリカからなる油性インク用填剤が提供される。 According to the present invention, the sedimentation method has a volume-based average particle diameter (D 50 ) measured by the laser diffraction / scattering method of 0.8 to 4.0 μm and a BET specific surface area in the range of 5 to 300 m 2 / g. An oil-based ink filler made of amorphous silica is provided.
本発明の油性インク用填剤においては、
（１）前記ＢＥＴ比表面積が５〜２００ｍ２／ｇであること、
（２）塩素含有量が２００〜３０００ｐｐｍの範囲にあること、
（３）前記沈降法非晶質シリカは、４％以上の強熱減量（１０５０℃、１ｈｒ）を有していること、
が好ましい。
In the filler for oil-based ink of the present invention,
(1) The BET specific surface area is 5 to 200 m 2 / g.
(2) The chlorine content is in the range of 200 to 3000 ppm.
(3) The sedimentation method amorphous silica has a ignition loss (1050 ° C., 1 hr) of 4% or more.
Is preferable.
本発明によれば、また、上記の油性インク用填剤と白色顔料とを含む油性インク用顔料組成物が提供される。 According to the present invention, there is also provided a pigment composition for an oil-based ink containing the above-mentioned filler for an oil-based ink and a white pigment.
上記の油性インク用組成物においては、
（１）前記白色顔料１００質量部当り５〜２００質量部の量で、前記沈降法非晶質シリカが配合されていること、
（２）前記白色顔料が、酸化チタンまたは酸化亜鉛であること、
（３）スクリーン印刷に使用される油性インクに配合されること、
が好適である。
In the above composition for oil-based ink,
(1) The precipitation method amorphous silica is blended in an amount of 5 to 200 parts by mass per 100 parts by mass of the white pigment.
(2) The white pigment is titanium oxide or zinc oxide.
(3) Being mixed with oil-based ink used for screen printing,
Is preferable.
本発明の油性インク用填剤（沈降法非晶質シリカ）は、高い隠蔽性を示し、特に白色顔料と組み合わせで使用されたとき、高価な白色顔料の使用量を低減させながら高い隠蔽力を確保することができる。このような高い隠蔽力は、多くの実験により現象として見出されたものであり、その理由を正確に解明するには至っていないが、本発明者等は次のように推定している。 The filler for oil-based inks (precipitation method amorphous silica) of the present invention exhibits high hiding power, and particularly when used in combination with a white pigment, provides high hiding power while reducing the amount of expensive white pigment used. Can be secured. Such a high hiding power has been found as a phenomenon by many experiments, and the reason has not been clarified accurately, but the present inventors presume as follows.
即ち、本発明において、油性インク用填剤として使用される非晶質シリカは、沈降法で得られるものであることから、乾式法で得られる超微細シリカ（ヒュームドシリカ）等と比較して体積基準の平均粒子径は大きく、０．８〜４．０μｍの範囲にあり、このような大きさの粒子の集合体は、光が粒子内部に入射しやすく、ひいては光が粒子内部で散乱しやすくなり、この結果として、高い隠蔽力が発揮されるものと推定される。 That is, in the present invention, the amorphous silica used as the filler for oil-based ink is obtained by the precipitation method, so that it is compared with the ultrafine silica (fumed silica) obtained by the dry method. The average particle size on a volume basis is large and ranges from 0.8 to 4.0 μm. In an aggregate of particles of such a size, light easily enters the inside of the particle, and thus light is scattered inside the particle. As a result, it is presumed that high hiding power is exhibited.
また、この沈降法非晶質シリカは、上記のような平均粒径に関連して、ＢＥＴ比表面積が比較的大きく、５〜３００ｍ２／ｇ、特に５〜２００ｍ２／ｇの範囲にある。即ち、表面に多くのＳｉＯＨ基が分布していることに関連して、その高い濡れ性を示し、この結果、酸化チタンや酸化亜鉛等の白色顔料との親和性が向上し、これらの白色顔料が該非晶質シリカ表面に分布し、白色顔料が嵩増しされ、白色顔料の配合量を低減させながら、高い隠蔽力が確保されるのではないかと思われる。 Further, this sedimentation amorphous silica has a relatively large BET specific surface area in relation to the average particle size as described above, and is in the range of 5 to 300 m 2 / g, particularly 5 to 200 m 2 / g. That is, it exhibits high wettability in relation to the distribution of many SiOH groups on the surface, and as a result, the affinity with white pigments such as titanium oxide and zinc oxide is improved, and these white pigments. Is distributed on the surface of the amorphous silica, the white pigment is bulky, and it is considered that a high hiding power is ensured while reducing the blending amount of the white pigment.
従って、本発明の油性インク用填剤は、白色顔料と混合して油性インクに配合されることにより、その特性を最大限に発揮することができる。 Therefore, the filler for oil-based ink of the present invention can maximize its characteristics by being mixed with a white pigment and blended with the oil-based ink.
［沈降法非晶質シリカ］
本発明において油性インク用填剤として用いられる沈降法非晶質シリカは、ＢＥＴ比表面積が５〜３００ｍ２／ｇ、好ましくは５〜２００ｍ２／ｇ、特に好ましくは５０〜１００ｍ２／ｇの範囲にある。また、ＢＥＴ比表面積から算出される一次粒子径が８〜３００ｎｍ、好ましくは８〜３０ｎｍ、特に好ましくは１５〜３０ｎｍの範囲にある。
また、前記沈降法非晶質シリカは、レーザ回折散乱法で測定した体積基準での平均粒径（Ｄ５０）が０．８〜４．０μｍ、好ましくは０．８〜３．１μｍの範囲にある。
[Precipitation method amorphous silica]
The settling amorphous silica used as a filler for oil-based ink in the present invention has a BET specific surface area in the range of 5 to 300 m 2 / g, preferably 5 to 200 m 2 / g, and particularly preferably 50 to 100 m 2 / g. It is in. The primary particle size calculated from the BET specific surface area is in the range of 8 to 300 nm, preferably 8 to 30 nm, and particularly preferably 15 to 30 nm.
Further, the sedimentation method amorphous silica has an average particle size (D 50 ) measured by a laser diffraction / scattering method on a volume basis in the range of 0.8 to 4.0 μm, preferably 0.8 to 3.1 μm. is there.
例えば、上記の平均粒径が上記範囲よりも小さく或いはＢＥＴ比表面積が上記の範囲を上回ると、光が入射しづらくなり、ひいては光が粒子内部で散乱しづらくなり、隠蔽力が低下する。一方、平均粒径が上記範囲よりも大きい場合には、白色顔料や油性インクに対する分散性が損なわれ、安定した隠蔽力を発揮することが困難となる。また、ＢＥＴ比表面積が上記の範囲を下回ったとしても格別の利点はなく、経済的に不利になるに過ぎない。 For example, if the average particle size is smaller than the above range or the BET specific surface area exceeds the above range, it becomes difficult for light to enter, and eventually it becomes difficult for light to scatter inside the particles, resulting in a decrease in hiding power. On the other hand, when the average particle size is larger than the above range, the dispersibility in white pigments and oil-based inks is impaired, and it becomes difficult to exhibit stable hiding power. Further, even if the BET specific surface area falls below the above range, there is no particular advantage and it is only economically disadvantageous.
また、本発明において、上記の沈降法非晶質シリカは、その製法に由来して、食塩等の塩化物が使用される場合が多く、その場合、塩素含有量が２００〜３０００ｐｐｍの範囲にある。即ち、沈降法で得られる非晶質シリカであっても、塩化物を使用せずに得られるものは、塩素含有量は、用いる原料（例えばケイ酸アルカリなど）に含まれる不可避的不純物に由来するものであるため、その塩素含有量は、上記範囲よりも低い。 Further, in the present invention, the above-mentioned precipitated amorphous silica is often produced by a chloride such as salt, and in that case, the chlorine content is in the range of 200 to 3000 ppm. .. That is, even if the amorphous silica is obtained by the precipitation method, the chlorine content of the amorphous silica obtained without using chloride is derived from the unavoidable impurities contained in the raw material used (for example, alkali silicate). The chlorine content is lower than the above range.
沈降法は、ケイ酸アルカリを主原料としての所謂湿式法であるため、得られる非晶質シリカは、特許文献２等に記載されている乾式法の超微細シリカとは異なり、強熱減量が４％以上、特に５％以上と大きい（１０５０℃、１ｈｒ）。このような大きな強熱減量は、高い濡れ性をもたらす要因の一つではないかと思われる。
さらに、従来使用されている沈降法では、一旦生成したシリカのゾル粒子の表面シラノール基にケイ酸イオンが結合してゆっくり生長するものであり、そのためこの非晶質シリカは強熱減量が３％以下となる。これに対して、本発明の非晶質シリカ系填剤では、濃い電解質塩溶液中にケイ酸アルカリと鉱酸とを同時注加する。生成する低分子量のケイ酸イオン種が鉱酸イオンと電解質塩による強力な塩析作用によって、急激な脱水縮合を起こして重合し、シリカのゾル粒子を経由することなく、シリカの微粒子ゲルである高分子ケイ酸へと生長する。これによりシラノール基数が増え、得られる本発明の非晶質シリカは、強熱減量が４％以上、特に５％以上と大きくなる（１０５０℃、１ｈｒ）。このような大きな強熱減量は、高い濡れ性をもたらす要因の一つではないかと思われる。
Since the precipitation method is a so-called wet method using alkali silicate as a main raw material, the obtained amorphous silica has a loss on ignition unlike the ultrafine silica of the dry method described in Patent Document 2 and the like. It is as large as 4% or more, especially 5% or more (1050 ° C., 1 hr). Such a large ignition loss seems to be one of the factors that bring about high wettability.
Further, in the conventionally used precipitation method, silicate ions are bonded to the surface silanol groups of the once-generated silica sol particles and slowly grow, so that this amorphous silica has a strong heat loss of 3%. It becomes as follows. On the other hand, in the amorphous silica-based filler of the present invention, alkali silicate and mineral acid are simultaneously poured into a concentrated electrolyte salt solution. The low molecular weight silicate ion species to be produced undergoes rapid dehydration condensation due to the strong salting out action of mineral acid ions and electrolyte salts, and polymerizes, and is a fine particle gel of silica without passing through silica sol particles. It grows into high molecular weight silicic acid. As a result, the number of silanol groups increases, and the obtained amorphous silica of the present invention has an ignition loss of 4% or more, particularly 5% or more (1050 ° C., 1 hr). Such a large ignition loss seems to be one of the factors that bring about high wettability.
この沈降法非晶質シリカは、その製法に由来して比較的嵩密度が小さく、例えば、鉄シリンダー法による嵩密度（ＪＩＳ Ｋ ６２２０−１ ７．８．２：２０１５）が０．１６〜０．３６ｇ／ｃｍ３、好ましくは０．１６〜０．２２ｇ／ｃｍ３、特に好ましくは０．１８〜０．２２ｇ／ｃｍ３の範囲にある。このような嵩密度は、光の散乱をもたらし、大きな隠蔽力発現の要因の一つとなっていると考えられる。 This precipitation method amorphous silica has a relatively low bulk density due to its manufacturing method. For example, the bulk density by the iron cylinder method (JIS K 6220-1 7.8.2: 2015) is 0.16 to 0. It is in the range of .36 g / cm 3 , preferably 0.16 to 0.22 g / cm 3 , and particularly preferably 0.18 to 0.22 g / cm 3 . Such bulk density causes light scattering and is considered to be one of the factors for developing a large hiding power.
前記沈降法非晶質シリカは、吸油量（ＪＩＳ Ｋ ５１０１−１３−１：２００４）が１８０ｍｌ／１００ｇ以下、好ましくは１５０ｍｌ／１００ｇ以下、特に好ましくは１００ｍｌ／１００ｇ以下である。この吸油量が高いと、インク溶液に添加したとき、溶液が増粘し、塗工性が低下してしまう。 The sedimentation method amorphous silica has an oil absorption amount (JIS K 5101-13-1: 2004) of 180 ml / 100 g or less, preferably 150 ml / 100 g or less, and particularly preferably 100 ml / 100 g or less. If this oil absorption amount is high, when added to the ink solution, the solution thickens and the coatability deteriorates.
［沈降法非晶質シリカの製法］
油性インク用填剤として使用される本発明の非晶質シリカは、既に述べたように、沈降法で得られる。
概説すると、この方法は、ケイ酸アルカリと酸とを中和してシリカ粒子を析出させるというものであるが、例えば、ケイ酸アルカリと鉱酸とを水もしくは電解質水溶液に攪拌下に注加し、中和反応を行うことにより行われる。
[Precipitation method Amorphous silica manufacturing method]
The amorphous silica of the present invention used as a filler for oil-based inks can be obtained by a precipitation method as described above.
Generally speaking, this method neutralizes alkali silicate and acid to precipitate silica particles. For example, alkali silicate and mineral acid are added to water or an aqueous electrolyte solution with stirring. , It is carried out by carrying out a neutralization reaction.
ケイ酸アルカリとしては、例えば、下記式（１）；
Ｍ２Ｏ・ｎＳｉＯ２ （１）
式中、Ｍは、Ｎａ、Ｋ等のアルカリ金属であり、
ｎは１〜３．８の数である、
で表されるモル組成のケイ酸アルカリの水溶液を用いる。経済的見地からは、ｎの数が３．０〜３．４の範囲にある所謂３号ケイ酸ソーダを用いることが好ましい。
反応に用いるケイ酸アルカリ水溶液の濃度は特に制限はないが、一般に５〜３５質量％の濃度で用いるのがよい。
As the alkali silicate, for example, the following formula (1);
M 2 O · nSiO 2 (1)
In the formula, M is an alkali metal such as Na, K, and the like.
n is a number from 1 to 3.8,
An aqueous solution of an alkali silicate having a molar composition represented by is used. From an economic point of view, it is preferable to use so-called sodium silicate No. 3 having a number of n in the range of 3.0 to 3.4.
The concentration of the alkaline silicate aqueous solution used in the reaction is not particularly limited, but it is generally preferable to use it at a concentration of 5 to 35% by mass.
また、鉱酸としては、塩酸、硝酸、硫酸、リン酸等の水溶液が使用されるが、一般的には塩酸や硫酸水溶液が使用されるが、本発明では、表面のＳｉＯＨ基の濃度を高めるという観点から塩酸が最適である。酸水溶液の酸濃度は、通常、５〜２０質量％程度である。 Further, as the mineral acid, an aqueous solution of hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid or the like is used. Generally, an aqueous solution of hydrochloric acid or sulfuric acid is used, but in the present invention, the concentration of SiOH groups on the surface is increased. From this point of view, hydrochloric acid is the most suitable. The acid concentration of the acid aqueous solution is usually about 5 to 20% by mass.
さらに、上記のケイ酸アルカリ及び鉱酸が注加される電解質水溶液としては、特に制限されるものではないが、燐酸ナトリウム、硫酸アンモニウム、塩化ナトリウムや硫酸ナトリウム、塩化リチウム、硫酸リチウム、炭酸ナトリウム、炭酸水素ナトリウムなどの電解質塩の水溶液が使用され、好適には、塩化ナトリウムが使用される。このような電解質の使用により、シリカ粒子の凝集成長が促進され、目的とする物性の非晶質シリカを得ることができる。
かかる電解質塩水溶液の濃度は、通常、中和反応開始時点で、１質量％以上、特に５〜１５質量％程度の濃度であればよい。
Further, the aqueous electrolyte solution into which the above-mentioned alkali silicate and mineral acid are added is not particularly limited, but is not particularly limited, but is sodium phosphate, ammonium sulfate, sodium chloride or sodium sulfate, lithium chloride, lithium sulfate, sodium carbonate, and carbonate. An aqueous solution of an electrolyte salt such as sodium hydrogen hydrogen is used, preferably sodium chloride. By using such an electrolyte, the cohesive growth of silica particles is promoted, and amorphous silica having the desired physical characteristics can be obtained.
The concentration of the aqueous electrolyte salt solution is usually 1% by mass or more, particularly about 5 to 15% by mass at the start of the neutralization reaction.
中和反応に際してのケイ酸アルカリと鉱酸の注加順序は、ケイ酸アルカリ水溶液と酸水溶液とを同時注加する方法が好適であるが、ケイ酸アルカリ水溶液の注加後、酸水溶液を注加することもできる。この反応段階でｐＨを制御することが好ましい。例えば、同時注加の間中ｐＨを、６乃至１０、好ましくは８乃至９．５の範囲に維持するのがよい。かかる範囲よりもｐＨが高いと、複分解反応が進行せず、核となるシリカ粒子の生成が困難となる。一方、上記範囲よりもｐＨが低いと、反応が一挙に進行し、シリカ粒子が一挙に析出し、目的とする特性の非晶質シリカを得ることができなくなるおそれがある。また、この工程での反応温度は、通常、４０乃至９０℃の範囲が好適である。 As for the order of adding alkali silicate and mineral acid during the neutralization reaction, it is preferable to add the alkali silicate aqueous solution and the acid aqueous solution at the same time. However, after the alkali silicate aqueous solution is added, the acid aqueous solution is poured. You can also add. It is preferable to control the pH at this reaction stage. For example, the pH may be maintained in the range of 6 to 10, preferably 8 to 9.5 during simultaneous injection. If the pH is higher than this range, the metathesis reaction does not proceed and it becomes difficult to generate silica particles as nuclei. On the other hand, if the pH is lower than the above range, the reaction may proceed at once, silica particles may be precipitated at once, and amorphous silica having the desired characteristics may not be obtained. The reaction temperature in this step is usually preferably in the range of 40 to 90 ° C.
上記の反応終了後、熟成を行い、非晶質シリカの粒子を析出させる。この熟成時のｐＨは、一般に、４乃至１０、特に５乃至８の範囲とするのがよい。このときのｐＨが上記範囲をはずれると、析出が有効に進行せず、目的とする特性のシリカ粒子を得ることが困難となるおそれがある。尚、この段階でのｐＨ調整は、例えばケイ酸アルカリの注加停止後、所定量の鉱酸をそのまま注加することによっても容易に行われる。また、この熟成は、ケイ酸アルカリの使用量等によっても異なるが、一般には、５０乃至１００℃の温度で約３０分乃至６０分間程度である。 After completion of the above reaction, aging is carried out to precipitate amorphous silica particles. The pH at the time of aging is generally preferably in the range of 4 to 10, particularly 5 to 8. If the pH at this time deviates from the above range, precipitation may not proceed effectively, and it may be difficult to obtain silica particles having desired characteristics. The pH adjustment at this stage can be easily performed, for example, by injecting a predetermined amount of mineral acid as it is after stopping the addition of alkali silicate. Further, this aging varies depending on the amount of alkali silicate used and the like, but is generally about 30 to 60 minutes at a temperature of 50 to 100 ° C.
熟成後、次いで、生成したシリカを含むシリカスラリー（通常、ＳｉＯ２濃度が１〜１０質量％）を、脱アルカリ、ろ過、水洗、乾燥及び粉砕の工程に付することにより、目的とする非晶質シリカを得ることができる。
脱アルカリ、ろ過及び水洗は、副生するアルカリ塩、或いは電解質塩等を除去するものであり、定法にしたがって行われる。例えば脱アルカリは、鉱酸の添加によりｐＨを２乃至４程度の領域に調整することにより行うことができる。
After aging, the silica slurry (usually having a SiO 2 concentration of 1 to 10% by mass) containing the produced silica is subjected to steps of dealkaliization, filtration, washing with water, drying and pulverization to obtain the desired amorphous material. Quality silica can be obtained.
De-alkali, filtration and washing with water remove by-produced alkali salts, electrolyte salts and the like, and are carried out according to a conventional method. For example, dealkaliization can be performed by adjusting the pH to a range of about 2 to 4 by adding a mineral acid.
なお、前述した金属塩として塩化ナトリウムを使用し、中和の為の酸として塩酸を使用した場合、得られる非晶質シリカは、塩素含有量が多くなり、例えば、最大で３０００ｐｐｍにも達することがある。この塩素含有量を低下させるには、水洗を徹底的に行えばよい。水洗を徹底的に行うことにより、塩素含有量を２００ｐｐｍ程度にまで低下せることができる。また、このような徹底的な水洗により比表面積が若干増大する傾向があり、例えば、２００ｍ２／ｇ程度のＢＥＴ比表面積が３００ｍ２／ｇ程度に増大する。 When sodium chloride is used as the metal salt and hydrochloric acid is used as the acid for neutralization, the obtained amorphous silica has a high chlorine content, for example, reaching 3000 ppm at the maximum. There is. In order to reduce the chlorine content, it is necessary to thoroughly wash with water. By thoroughly washing with water, the chlorine content can be reduced to about 200 ppm. The specific surface area by such thorough washing tends to increase slightly, for example, BET specific surface area of about 200 meters 2 / g is increased to about 300m 2 / g.
乾燥は、１００乃至３００℃程度の熱処理により行われ、洗浄乾燥後の非晶質シリカは、所定の粒度にまで粉砕し分級することにより製品とされる。このような粉砕は、ジェット粉砕機、衝撃式粉砕機、振動式粉砕機などが使用され、また分級は、重力式風力分級機、慣性式風力分級機、遠心式風力分級機、機械式風力分級機などが使用される。 Drying is performed by heat treatment at about 100 to 300 ° C., and the amorphous silica after washing and drying is pulverized to a predetermined particle size and classified into a product. Jet crushers, impact crushers, vibration crushers, etc. are used for such crushing, and classification is performed by gravity type wind classifiers, inertial wind classifiers, centrifugal wind classifiers, mechanical wind classifiers, etc. Machines are used.
［油性インク］
インクに隠蔽性が求められる場合、顔料としては、通常、白色顔料が用いられる。ゆえに、本発明の填剤は、白色顔料と併用されることが好ましい。
例えば、白色顔料１００質量部当り、５〜２００質量部、特に２０〜１００質量部の量割合で白色顔料と混合して顔料組成物を調製し、これを油性インク溶液に配合することが好適である。これにより、高価な白色顔料の使用量を低減させながら、高い隠蔽性を確保することができる。
[Oil-based ink]
When the ink is required to have a hiding property, a white pigment is usually used as the pigment. Therefore, the filler of the present invention is preferably used in combination with a white pigment.
For example, it is preferable to prepare a pigment composition by mixing it with a white pigment in an amount ratio of 5 to 200 parts by mass, particularly 20 to 100 parts by mass per 100 parts by mass of the white pigment, and blend this in an oil-based ink solution. is there. As a result, high hiding power can be ensured while reducing the amount of expensive white pigment used.
白色顔料としては、金属酸化物、硫酸バリウム、炭酸カルシウム等の金属化合物が挙げられる。また、金属酸化物としては、酸化チタン、酸化亜鉛、アルミナ、酸化マグネシウム等が挙げられる。隠蔽性の高さ等の観点から、本発明の填剤と併用される白色顔料は、酸化チタン、酸化亜鉛が好ましく、酸化チタンが最適である。 Examples of the white pigment include metal compounds such as metal oxides, barium sulfate, and calcium carbonate. Examples of the metal oxide include titanium oxide, zinc oxide, alumina, magnesium oxide and the like. From the viewpoint of high hiding power and the like, the white pigment used in combination with the filler of the present invention is preferably titanium oxide or zinc oxide, and titanium oxide is most suitable.
本発明の填剤、例えば本発明の填剤を含む顔料組成物が配合される油性インクは、特に制限されず、光硬化型、熱硬化型、紫外線硬化型等の公知の油性インクに適用することができる。
また、本発明の填剤が配合されたインクにより塗膜を形成する方法としては、特に限定されず、通常の塗工方式を適用することができる。具体的には、スクリーン印刷等の孔版印刷、グラビア印刷等の凹版印刷、又はロールコーティング等の各種コーティング法を適用することができる。
The filler of the present invention, for example, an oil-based ink containing a pigment composition containing the filler of the present invention is not particularly limited, and is applied to known oil-based inks such as a photocurable type, a thermosetting type, and an ultraviolet curable type. be able to.
Further, the method of forming the coating film with the ink containing the filler of the present invention is not particularly limited, and a normal coating method can be applied. Specifically, various coating methods such as stencil printing such as screen printing, intaglio printing such as gravure printing, and roll coating can be applied.
本発明の填剤が配合されたインクの用途は特に限定されないが、例えば、優れた隠蔽性を活かして、モバイルデバイス用のディスプレイの額縁の塗膜に利用することができる。
通常、このようなディスプレイの基材はガラス製であり、遮光性を満足するためには何層もの重ね塗りが必要であるが、本発明の填剤が配合されたインクは遮光性に優れるため、重ね塗りの回数を低減させることができる。
The use of the ink containing the filler of the present invention is not particularly limited, but for example, it can be used as a coating film on a frame of a display for a mobile device by taking advantage of its excellent hiding power.
Normally, the base material of such a display is made of glass, and multiple layers are required to satisfy the light-shielding property. However, the ink containing the filler of the present invention has excellent light-shielding property. , The number of recoating can be reduced.
本発明の優れた効果を、次の実験例により説明する。
なお、以下の実験において、各種測定は、以下の方法により行った。
The excellent effect of the present invention will be described with reference to the following experimental examples.
In the following experiments, various measurements were performed by the following methods.
（１）体積基準平均粒径（Ｄ５０）
Ｍａｌｖｅｒｎ社製Ｍａｓｔｅｒｓｉｚｅｒ ３０００を用いてレーザ回折散乱法により測定した。
(1) Volume-based average particle size (D 50 )
It was measured by a laser diffraction / scattering method using a Mastersizer 3000 manufactured by Malvern.
（２）ＢＥＴ比表面積及び一次粒子径
（株）島津製作所製トライスターII ３０２０を用いて窒素吸着法により測定を行ない、ＢＥＴ法により比表面積を測定した。尚、前処理は減圧条件下にて１５０℃で２時間行った。
また、ＢＥＴ比表面積から、下記式により、一次粒子径ｄを算出した。
ｄ＝６／ρＳ
ρ：シリカの密度
Ｓ：ＢＥＴ比表面積
(2) BET specific surface area and primary particle size The measurement was carried out by the nitrogen adsorption method using Tristar II 3020 manufactured by Shimadzu Corporation, and the specific surface area was measured by the BET method. The pretreatment was carried out at 150 ° C. for 2 hours under reduced pressure conditions.
Further, the primary particle diameter d was calculated from the BET specific surface area by the following formula.
d = 6 / ρS
ρ: Silica density S: BET specific surface area
（３）嵩密度（見かけ比重）：鉄シリンダー法
ＪＩＳ Ｋ ６２２０−１ ７．８．２：２０１５に準拠して測定した。
(3) Bulk density (apparent specific weight): Measured according to the iron cylinder method JIS K 6220-1 7.8.2: 2015.
（４）強熱減量
強熱減量は、１１０℃で２時間乾燥した試料を１０５０℃で１時間強熱後、放冷した後に残量から定量した。
(4) Ignition loss The ignition loss was quantified from the remaining amount after the sample dried at 110 ° C. for 2 hours was ignited at 1050 ° C. for 1 hour, allowed to cool, and then allowed to cool.
（５）吸油量
ＪＩＳ Ｋ ５１０１−１３−１：２００４に準拠して測定した。
(5) Oil absorption The amount was measured according to JIS K 5101-13-1: 2004.
（６）塩素有含量の測定
試料３ｇを９０ｇの水に分散させて１時間煮沸し、液を遠心分離した後に上澄みを濾過後、（株）島津製作所製高速液体クロマトグラフＰｒｏｍｉｎｅｎｃｅを用いて濾液の塩素含有量を定量した。
(6) Measurement of chlorine content 3 g of the sample is dispersed in 90 g of water, boiled for 1 hour, the liquid is centrifuged, the supernatant is filtered, and then the filtrate is prepared using a high performance liquid chromatograph Promindes manufactured by Shimadzu Corporation. The chlorine content was quantified.
（７）隠蔽性
ＪＩＳ Ｋ ５１０１−４（顔料試験方法―第４部）に準拠して、粉末試料をクリアウレタン塗料に分散させ、隠蔽率試験紙に塗布し、日本電色工業（株）製分光白色時計・色差計カラーメーターＰＦ−７０００を用いて試験紙の白色部と黒色部の三刺激値のＹ値から隠蔽率を算出した。
(7) Concealment property According to JIS K 5101-4 (Pigment test method-Part 4), the powder sample is dispersed in clear urethane paint, applied to the concealment rate test paper, and manufactured by Nippon Denshoku Kogyo Co., Ltd. The concealment rate was calculated from the Y value of the tristimulus values of the white part and the black part of the test paper using a spectral white clock / color difference meter color meter PF-7000.
（８）濡れ性
ＪＩＳ Ｋ ６７６８：１９９９（プラスチックフィルム及びシート−ぬれ張力試験方法)に準拠して、ダインレベル（表面エネルギー値)が３２ｍＮ／ｍ、３５ｍＮ／ｍであるダインペンを用いて評価した。
具体的には、ダインレベルが３２ｍＮ／ｍ、３５ｍＮ／ｍのペンを使用して，同時に塗膜に線を引き、５秒後及び６０秒後において、引いた線の状態を観察し、次の三段階で評価した。
〇：引いた線が水滴にならずに安定に保持されている。
△：引いた線がわずかに水滴になっていることが観察されるが、線としての形態は保持されている。
×：引いた線が水滴になっていることが明確に観察され、線が細くなり、一部は欠けてしまっている。
ダインレベルが高い程，接着性(濡れ性)が高くなる。
(8) Wetness According to JIS K 6768: 1999 (Plastic film and sheet-wetting tension test method), evaluation was performed using a dyne pen having a dyne level (surface energy value) of 32 mN / m and 35 mN / m.
Specifically, using a pen with a dyne level of 32 mN / m and 35 mN / m, a line is drawn on the coating film at the same time, and after 5 seconds and 60 seconds, the state of the drawn line is observed, and the following It was evaluated on a three-point scale.
〇: The drawn line is held stably without becoming water droplets.
Δ: It is observed that the drawn line is slightly water droplets, but the morphology as a line is maintained.
X: It is clearly observed that the drawn line is a water droplet, the line becomes thin, and a part is missing.
The higher the dyne level, the higher the adhesiveness (wetting property).
＜実施例１＞
以下の方法により沈降法非晶質シリカＡを製造した。
８０乃至９０℃に加熱した１５質量％塩化ナトリウム溶液中に、ケイ酸ソーダ溶液（Ｎａ２Ｏ ７質量％、ＳｉＯ２ ２２質量％）と１４質量％塩酸を反応液のｐＨを４乃至６に保持しながら６時間同時注加した。次いで塩酸にて反応液のｐＨを３乃至５に調整し、熟成した後、濾過をし５０℃の温水で洗浄して得られたケーキを１２０℃乃至１４０℃で乾燥した後、粉砕し沈降法非晶質シリカＡを得た。
<Example 1>
Sedimentation method Amorphous silica A was produced by the following method.
80 to 15 wt% sodium chloride solution was heated to 90 ° C. retention, sodium silicate solution (Na 2 O 7 wt%, SiO 2 22 wt%) and 14 wt% hydrochloric acid the pH of the reaction solution 4 to 6 At the same time, it was added simultaneously for 6 hours. Next, the pH of the reaction solution was adjusted to 3 to 5 with hydrochloric acid, and after aging, the cake was filtered and washed with warm water at 50 ° C., dried at 120 ° C. to 140 ° C., and then pulverized and settled. Amorphous silica A was obtained.
＜比較例１＞
以下の方法により沈降法非晶質シリカＢを製造した。
７０乃至８０℃に加熱した水中に、ケイ酸ソーダ溶液（Ｎａ２Ｏ ７質量％、ＳｉＯ２ ２２質量％）と１４質量％硫酸を反応液のｐＨを７乃至９に保持しながら９時間同時注加した。次いで硫酸にて反応液のｐＨを２乃至４に調整し、熟成した後、濾過をし５０℃の温水で洗浄して得られたケーキを１２０℃乃至１４０℃で乾燥した後、粉砕し沈降法非晶質シリカＢを得た。
<Comparative example 1>
Sedimentation method Amorphous silica B was produced by the following method.
In water heated to 70 to 80 ° C., sodium silicate solution (Na 2 O 7 wt%, SiO 2 22 wt%) 9 hours simultaneously Note while maintaining the pH to 7-9 with 14% by weight of the reaction liquid sulfuric acid Added. Next, the pH of the reaction solution was adjusted to 2 to 4 with sulfuric acid, and after aging, the cake was filtered and washed with warm water at 50 ° C., dried at 120 ° C. to 140 ° C., and then pulverized and settled. Amorphous silica B was obtained.
上記で製造された非晶質シリカＡおよび非晶質シリカＢについて、各種物性を測定し、その結果を表１に示した。 Various physical properties of the amorphous silica A and the amorphous silica B produced above were measured, and the results are shown in Table 1.
＜隠蔽率評価試験＞
実施例１で製造された非晶質シリカＡ及び比較例１で製造された非晶質シリカＢについて、隠蔽率の評価試験を行った。
具体的には、試料の非晶質シリカＡ或いはＢを、塗料１００質量部に対してそれぞれ、２０質量部、３０質量部をクリアウレタン塗料に分散させて隠蔽率を測定し、その結果を表２、表３に示した。
なお、２０質量部配合の時は、４５０μｍアプリケータを使用し、３０質量部配合の時は、２５０μｍアプリケータを使用した。
また、非晶質シリカＢ（比較例１で製造された非晶質シリカ）を３０質量部配合したときは、塗料が著しく増粘してしまい、塗布することができず、隠蔽率を測定することができなかった。
<Concealment rate evaluation test>
An evaluation test of the concealment rate was carried out on the amorphous silica A produced in Example 1 and the amorphous silica B produced in Comparative Example 1.
Specifically, 20 parts by mass and 30 parts by mass of the amorphous silica A or B of the sample were dispersed in the clear urethane paint with respect to 100 parts by mass of the paint, and the hiding ratio was measured, and the results are shown in the table. 2. It is shown in Table 3.
When 20 parts by mass was blended, a 450 μm applicator was used, and when 30 parts by mass was blended, a 250 μm applicator was used.
Further, when 30 parts by mass of amorphous silica B (amorphous silica produced in Comparative Example 1) is blended, the paint becomes extremely thickened and cannot be applied, and the hiding ratio is measured. I couldn't.
また、白色顔料である酸化チタン３０質量部をクリアウレタン塗料に配合したときの塗膜の６０°グロス及び隠蔽率を測定し、さらに、酸化チタンの一部を６０°グロスが同等となるように、非晶質シリカＡ（実施例１）、非晶質シリカＢ（比較例１）でそれぞれ置き換え、そのときの６０°グロス及び隠蔽率を表４に示した。 In addition, the 60 ° gloss and concealment rate of the coating film when 30 parts by mass of titanium oxide, which is a white pigment, is blended with the clear urethane paint are measured, and a part of titanium oxide is adjusted to have the same 60 ° gloss. , Amorphous silica A (Example 1) and amorphous silica B (Comparative Example 1), respectively, and the 60 ° gloss and concealment rate at that time are shown in Table 4.
表４に示されているように、同等グロス値となる場合においては，実施例１の非晶質シリカＡは、酸化チタンの３分の１（１０質量部）を置き換えても９６％という高い隠蔽率を示したのに対し，比較例１の非晶質シリカＢは、３０質量部のうち２．５質量部置き換えただけで実施例１の隠蔽率を下回った。 As shown in Table 4, when the equivalent gloss value is obtained, the amorphous silica A of Example 1 is as high as 96% even if one third (10 parts by mass) of titanium oxide is replaced. While the concealment rate was shown, the amorphous silica B of Comparative Example 1 was lower than the concealment rate of Example 1 only by replacing 2.5 parts by mass out of 30 parts by mass.
＜濡れ性評価試験＞
表４に示されているグロス測定に用いた塗料のそれぞれについて、３２ｍＮ／ｍ、３５ｍＮ／ｍのダインペンでの塗膜の５秒後及び６０秒後の濡れ性を評価した。その結果を以下に示す。
また、５秒後、６０秒後での各塗膜の写真を図１〜図６に示した。
<Wetability evaluation test>
For each of the paints used for the gloss measurement shown in Table 4, the wettability of the coating film with a Dyne pen of 32 mN / m and 35 mN / m after 5 seconds and 60 seconds was evaluated. The results are shown below.
Further, photographs of each coating film after 5 seconds and 60 seconds are shown in FIGS. 1 to 6.
酸化チタン３０質量部配合のウレタン塗料；
３５ｍＮ／ｍのペンでの塗膜
５秒後評価：×
６０秒後評価：×
３２ｍＮ／ｍのペンでの塗膜
５秒後評価：〇
６０秒後評価：〇
Urethane paint containing 30 parts by mass of titanium oxide;
Coating film with a 35mN / m pen
Evaluation after 5 seconds: ×
Evaluation after 60 seconds: ×
Coating film with a 32mN / m pen
Evaluation after 5 seconds: 〇
Evaluation after 60 seconds: 〇
酸化チタン２０質量部と非晶質シリカＡ（実施例１）１０質量部を混合した顔料組成物を配合したウレタン塗料；
３５ｍＮ／ｍのペンでの塗膜
５秒後評価：〇
６０秒後評価：〇
３２ｍＮ／ｍのペンでの塗膜
５秒後評価：〇
６０秒後評価：〇
Urethane paint containing a pigment composition in which 20 parts by mass of titanium oxide and 10 parts by mass of amorphous silica A (Example 1) are mixed;
Coating film with a 35mN / m pen
Evaluation after 5 seconds: 〇
Evaluation after 60 seconds: 〇 Coating film with a pen of 32 mN / m
Evaluation after 5 seconds: 〇
Evaluation after 60 seconds: 〇
酸化チタン２７．５質量部と非晶質シリカＢ（比較例１）２．５質量部を混合した顔料組成物を配合したウレタン塗料；
３５ｍＮ／ｍのペンでの塗膜
５秒後評価：△
６０秒後評価：×
３２ｍＮ／ｍのペンでの塗膜
５秒後評価：〇
６０秒後評価：〇
Urethane paint containing a pigment composition in which 27.5 parts by mass of titanium oxide and 2.5 parts by mass of amorphous silica B (Comparative Example 1) are mixed;
Coating film with a 35mN / m pen
Evaluation after 5 seconds: △
Evaluation after 60 seconds: ×
Coating film with a 32mN / m pen
Evaluation after 5 seconds: 〇
Evaluation after 60 seconds: 〇
上記の結果から、濡れ性は、酸化チタン＜比較例１＜実施例１の順で高くなっており、経時によって、この差はより顕著になっていることが判る。即ち、本発明の非晶質シリカおよび白色顔料を含む油性インク用組成物は、隠蔽率が高いだけではなく、濡れ性も高い。
また、比較例１においては非晶質シリカＢの添加量を増やせば濡れ性の向上が期待できるが、この場合には、隠蔽率の低下や粘度上昇などの問題が生じてしまう。
From the above results, it can be seen that the wettability increases in the order of titanium oxide <Comparative Example 1 <Example 1, and this difference becomes more remarkable with time. That is, the composition for oil-based ink containing the amorphous silica and the white pigment of the present invention not only has a high hiding rate but also a high wettability.
Further, in Comparative Example 1, if the amount of amorphous silica B added is increased, the wettability can be expected to be improved, but in this case, problems such as a decrease in the hiding rate and an increase in viscosity occur.
Claims (8)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2019194531 | 2019-10-25 | ||
| JP2019194531 | 2019-10-25 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2021070822A true JP2021070822A (en) | 2021-05-06 |
Family
ID=75712629
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2020177530A Pending JP2021070822A (en) | 2019-10-25 | 2020-10-22 | Filler for oil-based ink and pigment composition for oil-based ink |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2021070822A (en) |
-
2020
- 2020-10-22 JP JP2020177530A patent/JP2021070822A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4090405B2 (en) | Method for producing titanium dioxide pigment | |
| ES2204789T3 (en) | DCIATED PRECIPITATED SILICONE ACID. | |
| KR101790553B1 (en) | Process for production of hollow silica particles, hollow silica particles, and composition and insulation sheet which contain same | |
| CA2453936C (en) | High surface area aggregated pigments | |
| KR102403301B1 (en) | Titanium dioxide composite pigments containing calcium phosphate and method for the production thereof | |
| US20050228112A1 (en) | Titanium dioxide pigment and method for producing the same and resin composition using the same | |
| FI115212B (en) | A process for preparing silica hydrate | |
| WO1997024289A1 (en) | Titanium dioxide reduced in volatile water content, process for producing the same, and masterbatch containing the same | |
| US9605155B2 (en) | Gold pigment | |
| JP6031175B2 (en) | Titanium dioxide pigment, method for producing the same, and printing ink composition | |
| ES2879438T3 (en) | Nanoparticulate mineral pigment | |
| JP4764558B2 (en) | Amorphous silica particles with increased oil absorption, production method and use thereof | |
| DE10297614T5 (en) | Inorganic porous fine particles | |
| JP2021070822A (en) | Filler for oil-based ink and pigment composition for oil-based ink | |
| JP6176421B1 (en) | Low α-dose barium sulfate particles, their use and production method | |
| JP6732781B2 (en) | Aluminum hydroxide-containing composite pigment and method for producing the same | |
| JP3046060B2 (en) | Fine powdery alumina-based composite oxide, method for producing the same, and filler for inkjet recording paper | |
| ES2851498T3 (en) | Process for removing ink from cardboard or coated paper | |
| JP5702590B2 (en) | Composite particles, composite particle internal paper and coated paper | |
| JP4407789B2 (en) | Modified carbon black particle powder and method for producing the same, paint and resin composition containing the modified carbon black particle powder | |
| JP6457228B2 (en) | Complex pigment | |
| JP3719688B2 (en) | Method for producing fine powder precipitated silicic acid having abrasiveness | |
| JP2018053127A (en) | White pigment aqueous dispersion and coated film body using the same | |
| JP2013129575A (en) | Alumina fine particle, alumina hydrate fine particle and coating material composition | |
| JPH0416404B2 (en) |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20230720 |
|
| RD03 | Notification of appointment of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7423 Effective date: 20230720 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20240318 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20240416 |