CN110079149B - Printing ink, standard substance, preparation method and application thereof - Google Patents
Printing ink, standard substance, preparation method and application thereof Download PDFInfo
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- CN110079149B CN110079149B CN201910448320.6A CN201910448320A CN110079149B CN 110079149 B CN110079149 B CN 110079149B CN 201910448320 A CN201910448320 A CN 201910448320A CN 110079149 B CN110079149 B CN 110079149B
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- 239000000126 substance Substances 0.000 title claims abstract description 91
- 238000002360 preparation method Methods 0.000 title abstract description 7
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical group [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000000203 mixture Substances 0.000 claims abstract description 46
- 229910052793 cadmium Inorganic materials 0.000 claims abstract description 36
- 239000000463 material Substances 0.000 claims abstract description 25
- 239000012463 white pigment Substances 0.000 claims abstract description 22
- 238000001514 detection method Methods 0.000 claims abstract description 18
- 239000001054 red pigment Substances 0.000 claims abstract description 13
- 239000001052 yellow pigment Substances 0.000 claims abstract description 13
- 238000012544 monitoring process Methods 0.000 claims abstract description 12
- 239000000049 pigment Substances 0.000 claims abstract description 11
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000976 ink Substances 0.000 claims description 63
- 235000019504 cigarettes Nutrition 0.000 claims description 50
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 44
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 39
- 238000000034 method Methods 0.000 claims description 34
- 239000002904 solvent Substances 0.000 claims description 31
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 30
- 239000000945 filler Substances 0.000 claims description 30
- 238000002156 mixing Methods 0.000 claims description 27
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical group [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 22
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 16
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 16
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 15
- 239000012748 slip agent Substances 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 15
- 239000000454 talc Substances 0.000 claims description 14
- 229910052623 talc Inorganic materials 0.000 claims description 14
- 235000012222 talc Nutrition 0.000 claims description 14
- 239000004408 titanium dioxide Substances 0.000 claims description 14
- 239000011230 binding agent Substances 0.000 claims description 11
- 239000004200 microcrystalline wax Substances 0.000 claims description 11
- 235000019808 microcrystalline wax Nutrition 0.000 claims description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 8
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 8
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 8
- 239000006229 carbon black Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 5
- 229920005989 resin Polymers 0.000 claims description 5
- 239000011347 resin Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- 125000003158 alcohol group Chemical group 0.000 claims description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 4
- 238000005520 cutting process Methods 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 239000001993 wax Substances 0.000 claims description 3
- 229920000178 Acrylic resin Polymers 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- 150000001661 cadmium Chemical class 0.000 claims description 2
- VNTLIPZTSJSULJ-UHFFFAOYSA-N chromium molybdenum Chemical compound [Cr].[Mo] VNTLIPZTSJSULJ-UHFFFAOYSA-N 0.000 claims description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 2
- 239000001023 inorganic pigment Substances 0.000 claims description 2
- MOUPNEIJQCETIW-UHFFFAOYSA-N lead chromate Chemical compound [Pb+2].[O-][Cr]([O-])(=O)=O MOUPNEIJQCETIW-UHFFFAOYSA-N 0.000 claims description 2
- 229920006122 polyamide resin Polymers 0.000 claims description 2
- 229920000647 polyepoxide Polymers 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims description 2
- 229920005749 polyurethane resin Polymers 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- 238000004458 analytical method Methods 0.000 abstract description 4
- 239000003054 catalyst Substances 0.000 abstract 1
- 238000005259 measurement Methods 0.000 description 13
- 238000012360 testing method Methods 0.000 description 13
- 235000019441 ethanol Nutrition 0.000 description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 241000208125 Nicotiana Species 0.000 description 6
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 6
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 4
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 4
- 229910052785 arsenic Inorganic materials 0.000 description 4
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- 230000007774 longterm Effects 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 229910052711 selenium Inorganic materials 0.000 description 4
- 239000011669 selenium Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 238000013112 stability test Methods 0.000 description 3
- CBECDWUDYQOTSW-UHFFFAOYSA-N 2-ethylbut-3-enal Chemical group CCC(C=C)C=O CBECDWUDYQOTSW-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000000120 microwave digestion Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012353 t test Methods 0.000 description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Substances CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 2
- 241000304195 Salvia miltiorrhiza Species 0.000 description 1
- 235000011135 Salvia miltiorrhiza Nutrition 0.000 description 1
- 238000000692 Student's t-test Methods 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 244000269722 Thea sinensis Species 0.000 description 1
- CUPCBVUMRUSXIU-UHFFFAOYSA-N [Fe].OOO Chemical compound [Fe].OOO CUPCBVUMRUSXIU-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000540 analysis of variance Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000000673 graphite furnace atomic absorption spectrometry Methods 0.000 description 1
- 241000411851 herbal medicine Species 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910021519 iron(III) oxide-hydroxide Inorganic materials 0.000 description 1
- 238000011545 laboratory measurement Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- JTHNLKXLWOXOQK-UHFFFAOYSA-N n-propyl vinyl ketone Natural products CCCC(=O)C=C JTHNLKXLWOXOQK-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000000611 regression analysis Methods 0.000 description 1
- 239000010421 standard material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000010200 validation analysis Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
- C09D11/033—Printing inks characterised by features other than the chemical nature of the binder characterised by the solvent
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
- C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N11/00—Investigating flow properties of materials, e.g. viscosity, plasticity; Analysing materials by determining flow properties
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/3103—Atomic absorption analysis
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/62—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Biochemistry (AREA)
- Health & Medical Sciences (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Electrochemistry (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
The invention belongs to the field of detection and analysis, and particularly relates to ink which comprises a composition and a calibration object; wherein the calibration object is cadmium atom and/or cadmium ion, and the weight ratio of the composition to the calibration object is (0.1 × 10)6～8.0×106) 1, preparing a catalyst; and, the composition comprises the following components in parts by weight: 140-360 parts of white pigment, 1-20 parts of yellow pigment, 0.1-4 parts of red pigment, 0.01-0.5 part of black pigment and 30-160 parts of connecting material. The invention also relates to a standard substance, and also relates to the ink, a preparation method and application of the standard substance. The standard substance can be used for calibrating or monitoring the detection of cadmium residues in paper, and has high accuracy and good reliability.
Description
Technical Field
The invention belongs to the field of detection and analysis, and particularly relates to ink, a standard substance, a preparation method of the ink and the standard substance, and application of the ink and the standard substance in detection of paper cadmium residue.
Background
Generally, paper contains inorganic residues (such as cadmium residues), and the excessive inorganic residues can reduce the safety of the paper and damage the health of users, so that the inorganic residues in the paper need to be detected and controlled. Heretofore, detection of inorganic residues in paper requires complicated pretreatment, and the variety of detection instruments used is large, and both instrument variation and human operator error may affect the accuracy and reliability of detection, and therefore, it is necessary to calibrate or monitor the accuracy and reliability of detection by standard substances.
The standard substance (RM) is a substance or material that has been determined to have one or more sufficiently uniform and stable characteristic values, and is a "gauge" in the analytical measurement industry, which plays an indispensable role in calibrating a measuring instrument (device), evaluating a measurement analysis method, measuring a substance or material characteristic value, assessing an analyst's operation level, monitoring product quality, and the like. For example, the standard substances of tea industry GBW07604 and GBW07605, and the standard substances of Chinese herbal medicine industry radix Paeoniae Rubra (GBW (E)090066) and Salvia miltiorrhiza Bunge (GBW (E) 090066). However, no standard substance has been found for use in the detection of inorganic residues in paper so far.
There is a need to develop a standard substance for calibrating or monitoring the detection of inorganic residues, such as cadmium residues, in paper.
Disclosure of Invention
The invention provides ink, which is printed on the surface of base paper to prepare a standard substance, and the standard substance can be used for calibrating or monitoring the detection of cadmium residue in paper, and has high accuracy and good reliability. On the basis, the invention also provides a standard substance for detecting cadmium residues in calibration or monitoring paper, and a preparation method and application thereof.
The first aspect of the present invention relates to an ink comprising a composition and a taggant; wherein the calibration object is cadmium atom and/or cadmium ion, and the weight ratio of the composition to the calibration object is (0.1 × 10)6～8.0×106) 1, e.g. 0.2X 106:1、0.3×106:1、0.4×106:1、0.5×106:1、0.7×106:1、0.9×106:1、1.1×106:1、1.3×106:1、1.5×106:1、1.8×106:1、2.0×106:1、2.3×106:1、2.6×106:1、2.8×106:1、3.0×106:1、3.2×106:1、3.4×106:1、3.6×106:1、3.8×106:1、4.0×106:1、4.3×106:1、4.6×106:1、4.8×106:1、5.0×106:1、5.3×106:1、5.6×106:1、5.8×106:1、6.0×106:1、6.3×106:1、6.6×106:1、6.8×106:1、7.0×106:1、7.3×106:1、7.6×106:1、7.8×106:1；
And, the composition comprises the following components in parts by weight:
white pigments 140 to 360 (e.g., 160, 180, 200, 220, 240, 260, 280, 300, 320, 340, 350)
Yellow pigments 1 to 20 (e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 15, 17, 18, 19)
Red pigments 0.1 to 4 (e.g., 0.2, 0.4, 0.6, 0.8, 1, 1.2, 1.4, 1.6, 1.8, 2, 2.2, 2.4, 2.6, 2.8, 3, 3.2, 3.4, 3.6, 3.8, 4)
0.01 to 0.5 (e.g., 0.03, 0.05, 0.07, 0.09, 0.1, 0.12, 0.14, 0.16, 0.18, 0.2, 0.22, 0.24, 0.26, 0.28, 0.3, 0.32, 0.34, 0.36, 0.38, 0.4, 0.42, 0.44, 0.46, 0.48, 0.49)
A binder 30-160 (e.g., 32, 34, 36, 38, 40, 42, 44, 46, 48, 50, 52, 54, 56, 58, 60, 62, 64, 66, 68, 70, 72, 74, 76, 78, 80, 82, 84, 86, 88, 100, 103, 106, 108, 110, 112, 114, 116, 120, 123, 126, 130, 132, 136, 138, 140, 143, 146, 148, 150, 152, 155, 157, 159).
In some embodiments of the first aspect of the present invention, the cadmium ion is a divalent cadmium ion.
In some embodiments of the first aspect of the present invention, the composition further comprises a filler and/or a slip agent.
In certain embodiments of the first aspect of the present invention, the filler is selected from at least one of talc, calcium sulfate, calcium carbonate and aluminum hydroxide, preferably talc and calcium sulfate.
In some embodiments of the first aspect of the present invention, the filler comprises talc and calcium sulfate in a weight ratio of (12 to 100):1, e.g., 15:1, 18:1, 20:1, 23:1, 26:1, 28:1, 30:1, 32:1, 35:1, 38:1, 40:1, 42:1, 45:1, 47:1, 50:1, 53:1, 56:1, 58:1, 60:1, 62:1, 64:1, 66:1, 68:1, 70:1, 72:1, 74:1, 76:1, 78:1, 80:1, 82:1, 84:1, 86:1, 88:1, 90:1, 92:1, 94:1, 96:1, 98: 1.
In certain embodiments of the first aspect of the present invention, the filler is 10 to 100 parts by weight, for example 15, 20, 25, 30, 34, 36, 40, 42, 46, 48, 50, 53, 56, 58, 60, 63, 65, 67, 70, 73, 75, 77, 80, 84, 86, 89, 90, 92, 94, 96, 98 parts by weight.
In some embodiments of the first aspect of the present invention, the slip agent is a microcrystalline wax and/or a synthetic wax, preferably a microcrystalline wax.
In some embodiments of the first aspect of the present invention, the slip agent is 0.1 to 5 parts by weight, for example 0.3, 0.6, 0.9, 1.2, 1.4, 1.6, 1.8, 2, 2.2, 2.4, 2.6, 3, 3.2, 3.4, 3.6, 3.8, 4, 4.2, 4.4, 4.6, 4.8, 5 parts by weight.
In some embodiments of the first aspect of the present invention, the talc is talc commonly used in the ink field, and the mesh number of the talc is that of talc commonly used in the ink field.
In some embodiments of the first aspect of the present invention, the microcrystalline wax is a microcrystalline wax conventionally used in the ink art.
In some embodiments of the first aspect of the present invention, the ink comprises one or more of the following a to H:
A. at least one selected from the group consisting of a white pigment, a yellow pigment, a red pigment and a black pigment is an inorganic pigment;
B. the white pigment is selected from at least one of titanium dioxide, zinc oxide and lithopone, and is preferably titanium dioxide;
C. the yellow pigment is iron oxide yellow and/or lead chrome yellow, and preferably iron oxide yellow;
D. the red pigment is iron oxide red and/or molybdenum chromium red, preferably iron oxide red;
E. the black pigment is carbon black and/or iron oxide black, and is preferably carbon black;
F. the connecting material is a resin connecting material;
preferably, the resin binder is selected from at least one of polyvinyl butyral, polyurethane, epoxy, acrylic, and polyamide resins, more preferably polyvinyl butyral;
more preferably, the polyvinyl butyral has a viscosity of 7 to 50 mPas, such as 8 mPas, 10 mPas, 12 mPas, 14 mPas, 16 mPas, 18 mPas, 20 mPas, 22 mPas, 24 mPas, 26 mPas, 28 mPas, 30 mPas, 32 mPas, 34 mPas, 36 mPas, 38 mPas, 40 mPas, 42 mPas, 44 mPas, 46 mPas, 48 mPas, 50 mPas;
more preferably, the viscosity of a 10% (W/W) polyvinyl butyral-toluene/absolute ethanol solution is measured by a rotational viscometer method at 20 ℃. + -. 0.2 ℃;
further preferably, the polyvinyl butyral has a content of vinyl butyral groups of not less than 50% (m/m), preferably not less than 78% (m/m);
more preferably, the polyvinyl butyral has a volatiles content of less than or equal to 6% (m/m), preferably less than or equal to 3% (m/m);
more preferably, the polyvinyl butyral has a hydroxyl value of from 5% (m/m) to 27% (m/m), preferably from 11% (m/m) to 17% (m/m);
G. the weight percentage content of cadmium in the composition is less than or equal to 0.06mg/kg, preferably less than or equal to 0.05mg/kg, less than or equal to 0.04mg/kg and less than or equal to 0.03 mg/kg;
H. the calibrant is provided in the form of a solution containing the calibrant;
preferably, the calibrant-containing solution is a cadmium ion-containing solution, more preferably a cadmium salt solution.
In some embodiments of the first aspect of the present invention, the titanium dioxide is a titanium dioxide conventionally used in the ink field, such as rutile type titanium dioxide, anatase type titanium dioxide.
In some embodiments of the first aspect of the present invention, the mesh size of the titanium dioxide is the mesh size of titanium dioxide commonly used in the field of ink.
In some embodiments of the first aspect of the present invention, the composition further comprises a solvent.
In some embodiments of the first aspect of the present invention, the solvent is an alcohol, preferably at least one selected from the group consisting of ethanol, n-propanol and isopropanol, more preferably ethanol.
In some embodiments of the first aspect of the present invention, the solvent is 200 to 1000 parts by weight, for example 220, 240, 260, 280, 300, 320, 340, 360, 380, 400, 430, 460, 480, 500, 520, 540, 560, 580, 600, 620, 640, 660, 680, 700, 720, 740, 760, 780, 800, 820, 840, 860, 880, 900, 920, 940, 960, 980 parts by weight.
The second aspect of the present invention relates to a standard substance comprising a base paper and an ink layer printed on a surface of the base paper; wherein the ink layer comprises an ink according to some embodiments of the first aspect of the present invention.
In some embodiments of the second aspect of the present invention, the ink layer comprises a solvent, preferably ethanol.
In some embodiments of the second aspect of the present invention, the standard substance comprises one or more of the following a to d:
a. in the standard substance, the weight ratio of the base paper to the ink layer is (30-120): 1, such as 35:1, 40:1, 43:1, 46:1, 50:1, 52:1, 55:1, 57:1, 60:1, 63:1, 66:1, 68:1, 70:1, 73:1, 75:1, 77:1, 80:1, 82:1, 84:1, 86:1, 88:1, 90:1, 93:1, 96:1, 98:1, 100:1, 103:1, 106:1, 108:1, 110:1, 112:1, 114:1, 116:1 and 118: 1;
b. the base paper is base paper for cigarettes, preferably at least one selected from base paper for cigarette paper, base paper for lining paper for cigarettes, base paper for tipping paper for cigarettes, base paper for filter stick forming paper and base paper for trademark paper for cigarettes, and more preferably base paper for tipping paper for cigarettes;
c. the printing is full-page printing;
d. the base paper has a cadmium content of 0.043mg/kg or less, preferably 0.04mg/kg or less, 0.03mg/kg or less, for example 0.01, 0.02, 0.03, 0.04 mg/kg.
A third aspect of the present invention relates to a process for preparing the ink of the first aspect of the present invention, comprising the following steps (1), (2), (3) and optionally (3-1):
(1) mixing the components of the following combination 1 to obtain a first ink;
mixing the components of the following combination 2 to obtain a second ink;
mixing the components of the following combination 3 to obtain a third ink;
mixing the components of combination 4 below to obtain a fourth ink;
combination 1: white pigment, binder and solvent;
and (3) combination 2: yellow pigment, white pigment, binder, filler, slip agent and solvent;
and (3) combination: red pigment, white pigment, binder, filler, slip agent and solvent;
and (4) combination: black pigment, white pigment, connecting material, filler and solvent;
(2) mixing the four inks prepared in the step (1) to obtain a first mixture;
(3-1) mixing the first mixture with a solvent to obtain a second mixture;
(3) and mixing the first mixture or the second mixture with the calibration substance, or mixing the first mixture or the second mixture with the solution containing the calibration substance to obtain the ink.
In some embodiments of the third aspect of the invention, the method is one or more of the following 1) to 15):
1) in the step (1), in the combination 1, the weight ratio of the white pigment, the binder and the solvent is (1-7): 1 (5-12), preferably (2-6): 1 (5-10), such as 3:1:5, 3:1:6, 3:1:7, 4:1:5, 4:1:6, 4:1:7, 4:1:8, 4:1:9, 5:1:5, 5:1:6, 5:1:7, 5:1:8, 5:1:9
2) In the step (1), in the combination 2, the weight ratio of the yellow pigment, the white pigment, the connecting material, the filler, the slip agent and the solvent is 1 (10-40): 2-16): 1-13): 0.01-0.4): 30-110, preferably 1 (17-30): 5-12): 3-10): 0.04-0.18): 40-90, such as 1:24:9:6:0.09:63, 1:24:10:7:0.09:64, 1:22:8:5:0.07:58, 1:26:11:8:0.12: 65;
3) in the step (1), in the combination 2, the filler is selected from at least one of talcum powder, calcium sulfate, calcium carbonate and aluminum hydroxide, and preferably talcum powder and/or calcium sulfate;
more preferably, in the combination 2, the weight ratio of the talcum powder to the calcium sulfate is (30-70): 1, such as 35:1, 40:1, 45:1, 50:1, 55:1, 60:1, 65:1, 68: 1;
4) in the step (1), in the combination 3, the weight ratio of the red pigment, the white pigment, the connecting material, the filler, the slip agent and the solvent is 1 (17-65): 2-31): 2-30): 0.01-0.9): 60-150, preferably 1 (30-45): 7-18): 8-20): 0.07-0.2): 80-120, such as 1:35:12: 0.07:90, 1:38:13:13:0.1:100, 1:38:14: 0.1:100, 1:41:15:15:0.3: 120;
5) in the step (1), in the combination 3, the filler is selected from at least one of talc powder, calcium sulfate, calcium carbonate and aluminum hydroxide, and is preferably talc powder and/or calcium sulfate;
more preferably, in combination 3, the weight ratio of talc to calcium sulfate is (58-106): 1, e.g., 60:1, 62:1, 64:1, 66:1, 68:1, 70:1, 72:1, 4:1, 76:1, 78:1, 80:1, 82:1, 84:1, 86:1, 88:1, 90:1, 92:1, 94:1, 96:1, 98:1, 100:1, 102:1, 104:1, 105: 1;
6) in the step (1), in the combination 4, the weight ratio of the black pigment, the white pigment, the connecting material, the filler and the solvent is 1 (2-20): 1-12): 10-60, preferably 1 (5-14): 1-9): 20-50, such as 1:7:3:3:25, 1:9:5: 30, 1:12:7:7:35, 1:12:8:8: 40;
7) in the step (1), in the combination 4, the filler is at least one selected from talc powder, calcium sulfate, calcium carbonate and aluminum hydroxide, and is preferably talc powder;
8) in the step (2), the weight ratio of the first to fourth inks is (1-6): 2-10): 1: (0.003-0.09), preferably (1-4): 2-8): 1: (0.005-0.02), such as 1:4:1:0.006, 2:6:1:0.01, 3:8:1:0.02, 4:8:1: 0.03;
9) in step (2), the weight percentage of solids in the first mixture is 10% to 70%, for example 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%;
10) in the step (3-1), the weight ratio of the first mixture to the solvent is (0.8-5) to 1, for example, 1:1, 1.2:1, 1.4:1, 1.6:1, 1.8:1, 2:1, 2.2:1, 2.4:1, 2.6:1, 2.8:1, 3:1, 3.2:1, 3.4:1, 3.6:1, 3.8:1, 4:1, 4.2:1, 4.4:1, 4.6:1, 4.8: 1;
11) in the step (3-1), the mixing time is 0.5-5 hours, such as 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5 hours;
12) in the step (3-1), a TOYO3 # Zener cup is adopted to measure the flow speed of the second mixture to be 20-80 mm/s, such as 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75 and 80 mm/s;
13) in the step (3), the content of the calibrant in the solution containing the calibrant is 2-30 mg/mL, such as 4, 5, 6, 7, 9, 10, 12, 14, 16, 18, 20, 22, 24, 26, 27, 28, 29 mg/mL;
14) in the step (3), the weight ratio of the first mixture or the second mixture to the calibration material is (0.2X 10)6～8.0×106) 1, e.g. 0.3X 106:1、0.4×106:1、0.5×106:1、0.7×106:1、0.9×106:1、1.1×106:1、1.3×106:1、1.5×106:1、1.8×106:1、2.0×106:1、2.3×106:1、2.6×106:1、2.8×106:1、3.0×106:1、3.2×106:1、3.4×106:1、3.6×106:1、3.8×106:1、4.0×106:1、4.3×106:1、4.6×106:1、4.8×106:1、5.0×106:1、5.3×106:1、5.6×106:1、5.8×106:1、6.0×106:1、6.3×106:1、6.6×106:1、6.8×106:1、7.0×106:1、7.3×106:1、7.6×106:1、7.8×106:1；
15) In the step (3), the mixing time is 0.5 to 5 hours, such as 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5 hours.
In some embodiments of the third aspect of the present invention, in step (1), the solvent is an alcohol, preferably at least one selected from the group consisting of ethanol, n-propanol and isopropanol, and more preferably ethanol.
In some embodiments of the third aspect of the present invention, in the step (3-1), the solvent is an alcohol, preferably at least one selected from the group consisting of ethanol, n-propanol and isopropanol, and more preferably ethanol.
In some embodiments of the third aspect of the present invention, the first mixture has a weight percent cadmium content of 0.06mg/kg or less, preferably 0.05mg/kg or less, 0.04mg/kg or less, and 0.03mg/kg or less.
The fourth aspect of the present invention relates to a method for preparing the standard substance according to the second aspect of the present invention, comprising the steps of:
preparing ink according to the method of the third aspect of the invention;
and secondly, printing the ink on the surface of the base paper, and drying to obtain the standard substance.
In some embodiments of the fourth aspect of the invention, the method comprises one or more of the following i to vi:
step two, the printing is full-page printing;
in the second step, the printing speed is 80-150 m/min, such as 90, 95, 100, 110, 120, 130 and 140 m/min;
step III, printing by adopting an automatic ink stirring and circulating system;
IV, in the second step, the drying temperature is 70-130 ℃, such as 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃, 105 ℃, 110 ℃, 115 ℃, 120 ℃ and 125 ℃;
in the step (II), the weight ratio of the base paper to the printing ink is (40-80): 1, such as 42:1, 44:1, 46:1, 48:1, 50:1, 52:1, 54:1, 56:1, 58:1, 60:1, 62:1, 64:1, 66:1, 68:1, 70:1, 72:1, 74:1, 76:1 and 78: 1;
and the method also comprises the steps of cutting the standard substance, sealing and storing.
In a fifth aspect, the present invention relates to a method for detecting cadmium residues in paper, comprising calibrating or monitoring the detection of cadmium residues in paper using the standard substance according to the second aspect of the present invention.
A sixth aspect of the present invention relates to the use of an ink according to the first aspect of the present invention for the preparation of a standard substance.
In some embodiments of the sixth aspect of the present invention, the standard substance is a standard substance for calibrating or monitoring the detection of cadmium residue in paper.
In some embodiments of the sixth aspect of the present invention, the paper is a cigarette paper, preferably at least one selected from cigarette paper, cigarette inner liner paper, cigarette tipping paper, plug wrap paper and cigarette trademark paper, and more preferably cigarette tipping paper.
The seventh aspect of the present invention relates to the use of the standard substance according to the second aspect of the present invention for detecting cadmium residue in paper.
In some embodiments of the sixth aspect of the present invention, the use is for calibrating or monitoring a cadmium residue detection in paper.
In some embodiments of the sixth aspect of the present invention, the paper is a cigarette paper, preferably at least one selected from cigarette paper, cigarette inner liner paper, cigarette tipping paper, plug wrap paper and cigarette trademark paper, and more preferably cigarette tipping paper.
In the present invention, the TOYO3 # cup is a measuring instrument for viscosity by the flow rate of the liquid.
In some embodiments of the invention, the microcrystalline wax meets the petrochemical industry Standard SH/T0013-2008 "microcrystalline wax".
In one embodiment of the present invention, the microcrystalline wax is produced by the institute of chemical and physical research, Yingkou Tianyuan GmbH.
In the invention, the ethanol is absolute ethanol.
In the present invention, unless otherwise specified, wherein:
the term tipping paper for cigarettes refers to a paper product used in conjunction with cigarette paper to tipping a filter tip to a cigarette rod.
The term full-page printing refers to that all printing pages are uniformly printed, and the effect is uniform and uniform.
The term "yellow iron oxide", also known as yellow iron oxyhydroxide, is a chemically stable basic oxide with a chemical formula of Fe2O3·H2O, in the form of yellow powder.
The term "red iron oxide" has the molecular formula Fe2O3The molecular weight is 159.69, also called as iron oxide red and ferrite red, is red or dark brown red powder, the particle diameter is 0.5-2 μm, and the density is 5.24g/cm3。
The term "carbon black" is a black, powdery substance formed by incomplete combustion or pyrolysis of hydrocarbons in the gas phase under strictly controlled process conditions. The composition is mainly elemental carbon and contains a small amount of oxygen, hydrogen, sulfur and the like. The carbon black particles are approximately spherical and have a particle diameter of 10 to 500 μm.
The term "base paper" refers to the raw paper used to make various process papers.
The invention has the following beneficial effects:
the standard substance can be used for calibrating or monitoring the detection of cadmium residues in paper, and has high accuracy and good reliability.
Drawings
In order that the present disclosure may be more readily and clearly understood, reference is now made to the following detailed description of the embodiments of the present disclosure taken in conjunction with the accompanying drawings, in which
FIG. 1 is a graph showing a control of a mean value X in embodiment 6 of the present invention;
fig. 2 is a control diagram of the shift range R in embodiment 6 of the present invention.
Detailed Description
The following examples and comparative examples used the following materials:
polyvinyl butyral: the viscosity is 10-30 mPa.s (the viscosity of a 10% (W/W) sample-toluene/absolute ethanol solution is measured by adopting a rotational viscometer method at 20 +/-0.2 ℃), the content of vinyl butyral is more than or equal to 78% (m/m), the content of volatile is less than or equal to 3% (m/m), and the hydroxyl value is 11% (m/m) -17% (m/m).
White ink: mixing titanium dioxide, polyvinyl butyral and absolute ethyl alcohol in a weight ratio of 8:2:15 to prepare white ink;
yellow ink: mixing talcum powder, titanium dioxide, polyvinyl butyral, yellow pigment and absolute ethyl alcohol in a weight ratio of 6:23:9:3:59 to prepare yellow ink; wherein, the yellow pigment comprises the following components in percentage by weight: 32% of iron oxide yellow, 4% of calcium sulfate, 7% of polyvinyl butyral, 54% of absolute ethyl alcohol and 3% of microcrystalline wax (produced by yingkou Tianyu chemical research institute, Ltd.).
Red ink: mixing talcum powder, titanium dioxide, polyvinyl butyral, red pigment and absolute ethyl alcohol in a weight ratio of 8:23:8:2:59 to prepare red ink; wherein, the red pigment comprises the following components in percentage by weight: 30% iron oxide red, 5% calcium sulfate, 7% polyvinyl butyral, 55% absolute ethanol and 3% microcrystalline wax.
Black ink: mixing talcum powder, titanium dioxide, polyvinyl butyral, carbon black and absolute ethyl alcohol in a weight ratio of 5:9:5:1:30 to prepare black ink.
EXAMPLE 1 preparation of Standard substance
(1) Mixing white ink, yellow ink, red ink and black ink according to the weight ratio of 2:6:1:0.01 to obtain a mixture, wherein the solid content of the mixture is 30% (W/W), and the content of cadmium in the mixture is measured by ICP-MS to be less than or equal to 0.04 mg/kg.
(2) Mixing anhydrous ethanol and the mixture at a weight ratio of 1:1.1, stirring for 1.5-2 hr under the action of an electronic stirrer, and measuring the flow speed of TOYO3 # Zener cup to be 50mm/s to obtain 30kg of mixture.
(3) And (3) adding 2-3 mL of cadmium nitrate solution (the content of cadmium ions is 10mg/mL) into the mixture obtained in the step (2), and stirring for 0.5-1 hour under the action of an electronic stirrer to obtain the ink.
(4) The content of cadmium in the cigarette tipping base paper is 0.01-0.03 mg/kg and is lower than the quantitative limit of 0.043mg/kg specified in the tobacco industry standard YC/T316-2014, which is measured by adopting the method in the inductively coupled plasma mass spectrometry for measuring the residual amounts of chromium, nickel, arsenic, selenium, cadmium, mercury and lead in the cigarette material of the tobacco industry standard YC/T316-2014, and the cadmium in the cigarette tipping base paper can be considered not to be detected. Printing the ink obtained in the step (3) on the surface of the cigarette tipping base paper in a full-page mode, wherein the printing speed is 100-120 m/min, and an automatic ink stirring circulation system is started in the whole printing process; and then, drying in an oven at 85-115 ℃ to obtain the standard substance. In the standard substance, the weight ratio of the cigarette tipping base paper to the ink layer is 33: 0.5.
(5) Cutting the standard substance into 1cm × 1cm, subpackaging with brown glass bottle, each bottle about 20g, sealing with wax, and sealing at room temperature.
EXAMPLE 2 homogeneity test
16 vials of the standard material prepared in example 1 were randomly drawn for homogeneity testing. Weighing 0.2-0.3 g of sample from each bottle, adopting microwave digestion pretreatment in an inductively coupled plasma mass spectrometry method for measuring the residual quantity of chromium, nickel, arsenic, selenium, cadmium, mercury and lead in tobacco materials of YC/T316-.
TABLE 1
Carrying out homogeneity test by adopting an analysis of variance F test, and judging whether the standard substances of the bottles have obvious difference or not by using a ratio F of the mean square difference between the groups to the mean square difference in the groups; if the ratio F is less than the critical value F crit, the standard substances of each bottle are considered to be uniform; if the ratio F is greater than the threshold value Fcrit, the standard substances of the bottles are considered to have significant difference and nonuniformity. The results are shown in Table 2.
TABLE 2
F crit (critical value) obtained from table look-up according to the degree of freedom between groups and the degree of freedom in groups 1.880175
(significance level a ═ 0.05).
As shown in table 2, the ratio F of the mean square difference between groups to the mean square difference between groups was 1.684105, which is smaller than the critical value F crit, and therefore, the standard substance prepared in example 1 had good uniformity.
Example 3 short term stability test
From the standard substance prepared in example 1, 9 bottles were randomly extracted, 6 of them were opened and placed in a constant temperature oven at 60 ℃, and the remaining 3 bottles were left as they were under normal temperature conditions. Measuring the cadmium content of 3 bottles of samples at normal temperature on day 0; taking 3 bottles out of the oven on day 7, and measuring the cadmium content in the sample; taking out the rest 3 bottles from the oven on the 14 th day, and determining the cadmium content in the sample; the method for measuring the cadmium content is the same as that of example 2. Then, whether or not there was a significant difference between the results of the two subsequent measurements and the first measurement was compared by t-test (significance level a ═ 0.05), and the results are shown in table 3. Wherein, the calculation formula of t (test) is as follows:
in the formula:
is the average of the first measurement;
is the average of the results of the second or third measurement; s1Standard deviation of the first measurement; s2Standard deviation of the second or third measurement; n is1The number of samples measured for the first time; n is2The number of samples measured for the second or third time.
TABLE 3
As is clear from Table 3, the stability t of the standard substance prepared in example 1 stored at 60 ℃ for 7 days(test)Stability t of 1.87, storage at 60 ℃ for 14 days(test)The values of 2.74 were all less than the table-looked t 2.78 (obtained by table-looked at significance level a 0.05, intra-group degree of freedom 6 and inter-group degree of freedom 2), and thus the standard substance prepared in example 1 had good short-term stability.
Example 4 Long term stability test
At months 0, 1, 2, 4, 6, 8 and 11 after the standard substance is dispensed in the example 1, 5 bottles are randomly drawn every month, and the cadmium content in the sample is tested, and the average value is recorded as y. From the measurement time x and the average value y, a linear fitting equation y ═ ax + b is obtained by least squares regression analysis. Then, the standard deviation S and slope uncertainty S (a) of the residual are calculated according to the following formulas.
Wherein: n is the total number of months sampled, xiFor sampling month, yiThe average value of the cadmium content determined for the corresponding sampling month,
for the average of the sampling months, a is the slope of the linear fit equation and b is the intercept of the linear fit equation.
The test is carried out by slope comparison t test, the significance level a is 0.05, the test frequency n is 7, the degree of freedom f is n-2 is 5, and the table look-up t (0.05,5) is 2.57.
The results are shown in Table 4.
TABLE 4
As can be seen from table 4, the slope a of the linear fitting equation is smaller than s (a) × t (0.05,5), and therefore, the long-term stability at normal temperature of the standard substance prepared in example 1 is good.
EXAMPLE 5 quantitative determination
And (4) adopting a plurality of laboratories to collaborate and fix the value. Cadmium content was quantitatively determined in 9 laboratories for the standard substance prepared in example 1, wherein 5 laboratories were used for microwave digestion pretreatment-ICP-MS measurement, and 4 laboratories were used for graphite furnace atomic absorption spectrometry, and the results are shown in table 5.
TABLE 5
Note: measured by graphite furnace atomic absorption method.
In the data in table 5, validity test, normal distribution test, equal precision test and average value abnormity test are carried out, and no suspicious data are found, so that the total average value of 0.18mg/kg is taken as a fixed value of the cadmium content in the standard substance in the example 1.
Example 6 uncertainty assessment
The uncertainty of the fixed value result mainly comes from three uncertainty components of non-uniformity, instability and fixed value determination through cooperation of multiple laboratories, and the three uncertainty components are evaluated respectively.
a. Relative uncertainty u due to inhomogeneityUniformity：
The uncertainty S due to inhomogeneity is calculated as followsH：
Wherein, MSBetween groupsMean square error between groups, MS, of the results of the cadmium content determinationIn groupThe mean square difference in the group of the determination result of the cadmium content, and n is the parallel determination frequency of the cadmium content.
Then, the relative uncertainty caused by the heterogeneity is calculated according to the following formula:
wherein,
the average of all the cadmium content measurements in example 2.
b. Relative uncertainty u caused by stabilityStabilization：
Stability-induced uncertainty is mainly due to slope uncertainty S in the long-term stability test(a)Evaluation, long-term stability experiments were up to one year, time T was 12 months, and uncertainty was:
uT＝T×S(a)
then, the relative uncertainty u is calculated according to the following formulaStabilization：
Wherein,
the average of the results of all samples tested in example 4.
c. Relative uncertainty u caused by cooperative ratingCollaboration
The laboratory with the largest standard deviation of the fixed values has the largest influence on the uncertainty caused by the cooperation fixed values, so the relative uncertainty caused by the cooperation fixed values is calculated according to the following formula:
wherein S isMaximum ofFor the maximum standard deviation values in the laboratory data of example 5,
the average of the measurements from the laboratory with the largest standard deviation value.
Then, the synthesis uncertainty is calculated according to the following formula:
wherein,
the average of all the laboratory measurements of example 5.
Finally, the extended uncertainty is calculated according to the following formula, taking the inclusion factor k as 2 and the confidence level as 95%:
Uextension＝2×uSynthesis of
The calculation results show that the fixed value and the uncertain evaluation result of the cadmium content in the standard substance in the example 1 are as follows: 0.18. + -. 0.03 (mg/kg).
Example 7 validation of Standard substance monitoring detection method
32 standard substances prepared in example 1 are randomly sampled, the cadmium content in the sample is determined by the method in the inductively coupled plasma mass spectrometry method for determining the residual amounts of chromium, nickel, arsenic, selenium, cadmium, mercury and lead in the tobacco material in the tobacco industry standard YC/T316-2014, and the mean value is taken for the determination results
According to
(XnRepresenting the measurement result of the nth sample) to calculate the moving range average
The upper limit (UCL) of the single-value-moving range control chart is calculated according to the formula in ISO 8258-1991 Huohatt control chartX,UCLR) And lower limit (LCL)X,LCLR) The results are shown in Table 6. Wherein, the control factor E in the formula2、D4、D3As can be seen from tables 3 and 2 in ISO 8258-1991 Huhart control chart2＝2.660，D4＝3.267，D3＝0。
TABLE 6
According to Table 6, samples randomly obtained from the standard substance prepared in the rest of example 1 from 2016 to 2016 and 06 months were subjected to cadmium content determination by the method of inductively coupled plasma mass spectrometry for determining the residual amounts of chromium, nickel, arsenic, selenium, cadmium, mercury and lead in tobacco materials, YC/T316-. The solid line is a control limit, and the broken line is a constant value allowable range.
As can be seen from FIGS. 1-2: the determination results of the cadmium content all fall within the allowable range of the fixed value, so the accuracy of the determination result of the cadmium content in the tipping paper for the cigarette by adopting the standard substance is reliable. Cadmium content measurement result and moving extreme difference agent X measured continuously twicen-Xn-1All is between the upper limit and the lower limit of the X-R control diagram; the following does not occur: the continuous 9 points fall on the same side of the central line, the continuous 6 points are increased or decreased in number, and the adjacent points of the continuous 14 points alternate up and down; therefore, the process of detecting the cadmium content in the tipping paper for the cigarettes by adopting the standard substance is in a controlled state, and the stability is reliable.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (44)
1. A standard substance comprises base paper for cigarettes and an ink layer printed on the surface of the base paper for cigarettes, wherein the weight ratio of the base paper for cigarettes to the ink layer is (30-120): 1, and the cadmium content in the base paper for cigarettes is less than or equal to 0.043 mg/kg; wherein the ink layer comprises a composition and a taggant; wherein,the calibration substance is cadmium atom and/or cadmium ion, and the weight ratio of the composition to the calibration substance is (0.1 × 10)6～8.0×106) 1, the weight content of cadmium in the composition is less than or equal to 0.06 mg/kg;
and, the composition comprises the following components in parts by weight:
2. the standard substance of claim 1, wherein the composition further comprises a filler and/or a slip agent.
3. The standard substance of claim 2, wherein the filler is selected from at least one of talc, calcium sulfate, calcium carbonate, and aluminum hydroxide.
4. The standard substance of claim 2, wherein the filler is talc and calcium sulfate.
5. The standard substance according to claim 4, wherein the weight ratio of talc to calcium sulfate in the filler is (12-100): 1.
6. The standard substance according to claim 2, wherein the filler is 10 to 100 parts by weight.
7. The standard substance of claim 2, wherein the slip agent is a microcrystalline wax and/or a synthetic wax.
8. The standard substance of claim 2, wherein the slip agent is a microcrystalline wax.
9. The standard substance according to claim 2, wherein the slip agent is 0.1 to 5 parts by weight.
10. The standard substance of claim 1, characterized by one or more of the following:
A. at least one selected from the group consisting of a white pigment, a yellow pigment, a red pigment and a black pigment is an inorganic pigment;
B. the white pigment is at least one selected from titanium dioxide, zinc oxide and lithopone;
C. the yellow pigment is iron oxide yellow and/or lead chrome yellow;
D. the red pigment is iron oxide red and/or molybdenum chromium red;
E. the black pigment is carbon black and/or iron oxide black;
F. the connecting material is a resin connecting material;
G. the calibrant is provided in the form of a solution containing the calibrant.
11. The standard substance according to claim 10, wherein in item B, the white pigment is titanium dioxide.
12. The standard substance according to claim 10, wherein in item C, the yellow pigment is iron oxide yellow.
13. The standard substance according to claim 10, wherein in item D, the red pigment is red iron oxide.
14. The standard substance according to claim 10, wherein in item E, the black pigment is carbon black.
15. The standard substance of claim 10, wherein in item F, the resin binder is selected from at least one of polyvinyl butyral, polyurethane, epoxy, acrylic, and polyamide resins.
16. The standard of claim 10, wherein the resin binder is polyvinyl butyral, item F.
17. The standard substance according to claim 16, wherein in item F, the polyvinyl butyral has a viscosity of 7 to 50 mPa-s.
18. The standard substance according to claim 10, wherein in item G, the calibrant-containing solution is a cadmium ion-containing solution.
19. The standard substance of claim 10, wherein in item G, the calibrant-containing solution is a cadmium salt solution.
20. The standard substance of claim 1, wherein the composition further comprises a solvent.
21. The standard substance of claim 20, wherein the solvent is an alcohol.
22. The standard substance according to claim 20, wherein the solvent is at least one selected from the group consisting of ethanol, n-propanol and isopropanol.
23. The standard substance of claim 20, wherein the solvent is ethanol.
24. The standard substance according to claim 20, wherein the solvent is 200 to 1000 parts by weight.
25. The standard substance of any one of claims 1 to 24, characterized by one or more of the following:
a. the base paper for the cigarette is at least one selected from the group consisting of base paper of cigarette paper, base paper of lining paper for the cigarette, base paper of tipping paper for the cigarette, base paper of filter stick forming paper and base paper of trademark paper for the cigarette;
b. the printing is full-page printing;
c. the cadmium content in the base paper for the cigarette is less than or equal to 0.04 mg/kg.
26. The standard substance according to claim 25, wherein in item a, the base paper for cigarettes is a base paper for cigarette tipping paper.
27. A method of preparing a standard substance of any one of claims 1 to 26, comprising the steps of:
printing ink on the surface of base paper, and drying to obtain a standard substance;
wherein the step of preparing the ink comprises:
(1) mixing the components of the following combination 1 to obtain a first ink;
mixing the components of the following combination 2 to obtain a second ink;
mixing the components of the following combination 3 to obtain a third ink;
mixing the components of combination 4 below to obtain a fourth ink;
combination 1: white pigment, binder and solvent;
and (3) combination 2: yellow pigment, white pigment, binder, filler, slip agent and solvent;
and (3) combination: red pigment, white pigment, binder, filler, slip agent and solvent;
and (4) combination: black pigment, white pigment, connecting material, filler and solvent;
(2) mixing the four inks prepared in the step (1) to obtain a first mixture;
(3) and mixing the first mixture with the calibration substance or mixing the first mixture with a solution containing the calibration substance to obtain the ink.
28. The method of claim 27, wherein the step of preparing the ink further comprises:
(3-1) mixing the first mixture with a solvent to obtain a second mixture, wherein the second mixture is used for mixing with the calibration object or the solution containing the calibration object in the step (3).
29. The method of claim 27, the step of preparing an ink characterized by one or more of the following:
1) in the step (1), in the combination 1, the weight ratio of the white pigment to the connecting material to the solvent is (1-7) to (1-5-12);
2) in the step (1), in the combination 2, the weight ratio of the yellow pigment, the white pigment, the connecting material, the filler, the slip agent and the solvent is 1 (10-40): 2-16): 1-13): 0.01-0.4): 30-110;
3) in the step (1), in the combination 2, the filler is at least one selected from talcum powder, calcium sulfate, calcium carbonate and aluminum hydroxide;
4) in the step (1), in the combination 3, the weight ratio of the red pigment, the white pigment, the connecting material, the filler, the slip agent and the solvent is 1 (17-65): 2-31): 2-30): 0.01-0.9): 60-150;
5) in the step (1), in the combination 3, the filler is at least one selected from talc powder, calcium sulfate, calcium carbonate and aluminum hydroxide;
6) in the step (1), in the combination (4), the weight ratio of the black pigment, the white pigment, the connecting material, the filler and the solvent is 1 (2-20) to (1-12) to (10-60);
7) in the step (1), in the combination 4, the filler is at least one selected from talc powder, calcium sulfate, calcium carbonate and aluminum hydroxide;
8) in the step (2), the weight ratio of the first ink to the fourth ink is (1-6): 2-10): 1: (0.003-0.09);
9) in the step (2), the weight percentage of the solid in the first mixture is 10-70%;
10) in the step (3), the content of the calibration material in the solution containing the calibration material is 2-30 mg/mL;
11) in the step (3), the weight ratio of the first mixture to the calibration material is (0.2X 10)6～8.0×106):1；
12) In the step (3), the mixing time is 0.5-5 hours.
30. The method of claim 29, wherein in combination 2, the filler is talc and/or calcium sulfate.
31. The method according to claim 30, wherein in item 3), the weight ratio of talc powder to calcium sulfate in combination 2 is (30-70): 1.
32. The method of claim 29, wherein in combination 3, the filler is talc and/or calcium sulfate.
33. The method according to claim 32, wherein in item 5), the weight ratio of talc powder to calcium sulfate in combination 3 is (58-106): 1.
34. The method of claim 29, wherein in combination 4, the filler is talc.
35. The method according to claim 28, wherein in the step (3-1), the weight ratio of the first mixture to the solvent is (0.8-5): 1.
36. The method according to claim 28, wherein the mixing time in the step (3-1) is 0.5 to 5 hours.
37. The method as claimed in claim 28, wherein the flow rate of the second mixture in the step (3-1) is 20 to 80mm/s as measured by TOYO3 # Zener cup.
38. The method as claimed in claim 28, wherein the weight ratio of the second mixture to the calibrant in step (3) is (0.2 x 10)6～8.0×106):1。
39. The method according to any one of claims 27 to 38, characterized by one or more of the following:
the printing is full-page printing;
II, printing at a speed of 80-150 m/min;
printing by adopting an automatic ink stirring and circulating system;
IV, the drying temperature is 70-130 ℃;
v, the weight ratio of the base paper for the cigarettes to the printing ink is (20-120) to 1;
and the method also comprises the steps of cutting the standard substance, sealing and storing.
40. A method of detecting cadmium residue in paper comprising calibrating or monitoring the detection of cadmium residue in paper using the standard substance of any one of claims 1 to 26.
41. Use of the standard substance of any one of claims 1 to 26 for detecting cadmium residues in cigarette paper.
42. The use according to claim 41, wherein the use is for calibrating or monitoring cadmium residue detection in cigarette paper.
43. The use according to claim 41, wherein the paper for cigarettes is at least one selected from cigarette paper, cigarette inner liner paper, cigarette tipping paper, plug wrap paper and cigarette trademark paper.
44. The use according to claim 41, wherein the cigarette paper is cigarette tipping paper.
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| CN103396702A (en) * | 2013-08-16 | 2013-11-20 | 广东出入境检验检疫局检验检疫技术中心 | Preparation method of heavy metal-containing crayon standard sample for laboratory capability verification |
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| CN105181414A (en) * | 2015-09-30 | 2015-12-23 | 中国计量科学研究院 | Leather standard material containing arsenic and multiple metallic elements and preparation method of leather standard material |
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| US5541002A (en) * | 1993-12-27 | 1996-07-30 | Fuji Xerox Co., Ltd. | Ink jet printing paper |
| CN102732098A (en) * | 2012-07-23 | 2012-10-17 | 玉溪市星源油墨厂 | Ink for low-heavy metal tipping paper, and preparation method thereof |
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