CN102020893B - Erasable ball-pen ink composite and preparation method thereof - Google Patents
Erasable ball-pen ink composite and preparation method thereof Download PDFInfo
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- CN102020893B CN102020893B CN 201010611792 CN201010611792A CN102020893B CN 102020893 B CN102020893 B CN 102020893B CN 201010611792 CN201010611792 CN 201010611792 CN 201010611792 A CN201010611792 A CN 201010611792A CN 102020893 B CN102020893 B CN 102020893B
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- 238000002360 preparation method Methods 0.000 title claims description 15
- 239000002131 composite material Substances 0.000 title abstract description 5
- 238000009835 boiling Methods 0.000 claims abstract description 95
- 239000003960 organic solvent Substances 0.000 claims abstract description 68
- 229920005989 resin Polymers 0.000 claims abstract description 48
- 239000011347 resin Substances 0.000 claims abstract description 48
- 239000000049 pigment Substances 0.000 claims abstract description 46
- 229920001971 elastomer Polymers 0.000 claims abstract description 35
- 239000000806 elastomer Substances 0.000 claims abstract description 34
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 27
- 239000000976 ink Substances 0.000 claims description 81
- 239000000203 mixture Substances 0.000 claims description 38
- 239000004902 Softening Agent Substances 0.000 claims description 26
- 239000002904 solvent Substances 0.000 claims description 22
- 239000011118 polyvinyl acetate Substances 0.000 claims description 16
- 229940075065 polyvinyl acetate Drugs 0.000 claims description 12
- 229920002689 polyvinyl acetate Polymers 0.000 claims description 12
- 239000008187 granular material Substances 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 8
- 229920003023 plastic Polymers 0.000 claims description 4
- 239000004033 plastic Substances 0.000 claims description 4
- 239000002671 adjuvant Substances 0.000 claims description 3
- 238000000518 rheometry Methods 0.000 claims description 3
- 239000004014 plasticizer Substances 0.000 abstract description 3
- 239000003921 oil Substances 0.000 description 24
- 235000019198 oils Nutrition 0.000 description 24
- 229930195733 hydrocarbon Natural products 0.000 description 10
- 150000002430 hydrocarbons Chemical class 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 229920003052 natural elastomer Polymers 0.000 description 8
- 229920001194 natural rubber Polymers 0.000 description 8
- 229910002012 Aerosil® Inorganic materials 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 238000009736 wetting Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 244000043261 Hevea brasiliensis Species 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000012188 paraffin wax Substances 0.000 description 6
- PGMYKACGEOXYJE-UHFFFAOYSA-N pentyl acetate Chemical compound CCCCCOC(C)=O PGMYKACGEOXYJE-UHFFFAOYSA-N 0.000 description 6
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 6
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000005038 ethylene vinyl acetate Substances 0.000 description 5
- HNRMPXKDFBEGFZ-UHFFFAOYSA-N 2,2-dimethylbutane Chemical compound CCC(C)(C)C HNRMPXKDFBEGFZ-UHFFFAOYSA-N 0.000 description 4
- FLTJDUOFAQWHDF-UHFFFAOYSA-N 2,2-dimethylhexane Chemical compound CCCCC(C)(C)C FLTJDUOFAQWHDF-UHFFFAOYSA-N 0.000 description 4
- ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 2,3-dimethylbutane Chemical compound CC(C)C(C)C ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 0.000 description 4
- JVSWJIKNEAIKJW-UHFFFAOYSA-N 2-Methylheptane Chemical compound CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 4
- AFABGHUZZDYHJO-UHFFFAOYSA-N 2-Methylpentane Chemical compound CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 4
- LAIUFBWHERIJIH-UHFFFAOYSA-N 3-Methylheptane Chemical compound CCCCC(C)CC LAIUFBWHERIJIH-UHFFFAOYSA-N 0.000 description 4
- SFRKSDZMZHIISH-UHFFFAOYSA-N 3-ethylhexane Chemical compound CCCC(CC)CC SFRKSDZMZHIISH-UHFFFAOYSA-N 0.000 description 4
- PFEOZHBOMNWTJB-UHFFFAOYSA-N 3-methylpentane Chemical compound CCC(C)CC PFEOZHBOMNWTJB-UHFFFAOYSA-N 0.000 description 4
- CHBAWFGIXDBEBT-UHFFFAOYSA-N 4-methylheptane Chemical compound CCCC(C)CCC CHBAWFGIXDBEBT-UHFFFAOYSA-N 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 4
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 4
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- QZCLKYGREBVARF-UHFFFAOYSA-N Acetyl tributyl citrate Chemical compound CCCCOC(=O)CC(C(=O)OCCCC)(OC(C)=O)CC(=O)OCCCC QZCLKYGREBVARF-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
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- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 3
- 235000012424 soybean oil Nutrition 0.000 description 3
- 239000003549 soybean oil Substances 0.000 description 3
- JEVGKYBUANQAKG-UHFFFAOYSA-N victoria blue R Chemical compound [Cl-].C12=CC=CC=C2C(=[NH+]CC)C=CC1=C(C=1C=CC(=CC=1)N(C)C)C1=CC=C(N(C)C)C=C1 JEVGKYBUANQAKG-UHFFFAOYSA-N 0.000 description 3
- UIWORXHEVNIOJG-UHFFFAOYSA-N 1,1,4-trimethylcyclohexane Chemical compound CC1CCC(C)(C)CC1 UIWORXHEVNIOJG-UHFFFAOYSA-N 0.000 description 2
- OSNILPMOSNGHLC-UHFFFAOYSA-N 1-[4-methoxy-3-(piperidin-1-ylmethyl)phenyl]ethanone Chemical compound COC1=CC=C(C(C)=O)C=C1CN1CCCCC1 OSNILPMOSNGHLC-UHFFFAOYSA-N 0.000 description 2
- OKVWYBALHQFVFP-UHFFFAOYSA-N 2,3,3-trimethylpentane Chemical compound CCC(C)(C)C(C)C OKVWYBALHQFVFP-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- ZFOZVQLOBQUTQQ-UHFFFAOYSA-N Tributyl citrate Chemical compound CCCCOC(=O)CC(O)(C(=O)OCCCC)CC(=O)OCCCC ZFOZVQLOBQUTQQ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 150000005690 diesters Chemical class 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
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- 239000007965 rubber solvent Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229920003051 synthetic elastomer Polymers 0.000 description 2
- 239000005061 synthetic rubber Substances 0.000 description 2
- MFYSUUPKMDJYPF-UHFFFAOYSA-N 2-[(4-methyl-2-nitrophenyl)diazenyl]-3-oxo-n-phenylbutanamide Chemical compound C=1C=CC=CC=1NC(=O)C(C(=O)C)N=NC1=CC=C(C)C=C1[N+]([O-])=O MFYSUUPKMDJYPF-UHFFFAOYSA-N 0.000 description 1
- LVOJOIBIVGEQBP-UHFFFAOYSA-N 4-[[2-chloro-4-[3-chloro-4-[(5-hydroxy-3-methyl-1-phenylpyrazol-4-yl)diazenyl]phenyl]phenyl]diazenyl]-5-methyl-2-phenylpyrazol-3-ol Chemical compound CC1=NN(C(O)=C1N=NC1=CC=C(C=C1Cl)C1=CC(Cl)=C(C=C1)N=NC1=C(O)N(N=C1C)C1=CC=CC=C1)C1=CC=CC=C1 LVOJOIBIVGEQBP-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 229920002396 Polyurea Polymers 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- AOADSHDCARXSGL-ZMIIQOOPSA-M alkali blue 4B Chemical compound CC1=CC(/C(\C(C=C2)=CC=C2NC2=CC=CC=C2S([O-])(=O)=O)=C(\C=C2)/C=C/C\2=N\C2=CC=CC=C2)=CC=C1N.[Na+] AOADSHDCARXSGL-ZMIIQOOPSA-M 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- QFFVPLLCYGOFPU-UHFFFAOYSA-N barium chromate Chemical compound [Ba+2].[O-][Cr]([O-])(=O)=O QFFVPLLCYGOFPU-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 239000001055 blue pigment Substances 0.000 description 1
- RFAFBXGYHBOUMV-UHFFFAOYSA-N calcium chromate Chemical compound [Ca+2].[O-][Cr]([O-])(=O)=O RFAFBXGYHBOUMV-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- HBHZKFOUIUMKHV-UHFFFAOYSA-N chembl1982121 Chemical compound OC1=CC=C2C=CC=CC2=C1N=NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O HBHZKFOUIUMKHV-UHFFFAOYSA-N 0.000 description 1
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- PLYDMIIYRWUYBP-UHFFFAOYSA-N ethyl 4-[[2-chloro-4-[3-chloro-4-[(3-ethoxycarbonyl-5-oxo-1-phenyl-4h-pyrazol-4-yl)diazenyl]phenyl]phenyl]diazenyl]-5-oxo-1-phenyl-4h-pyrazole-3-carboxylate Chemical compound CCOC(=O)C1=NN(C=2C=CC=CC=2)C(=O)C1N=NC(C(=C1)Cl)=CC=C1C(C=C1Cl)=CC=C1N=NC(C(=N1)C(=O)OCC)C(=O)N1C1=CC=CC=C1 PLYDMIIYRWUYBP-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000001056 green pigment Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- JMXROTHPANUTOJ-UHFFFAOYSA-H naphthol green b Chemical compound [Na+].[Na+].[Na+].[Fe+3].C1=C(S([O-])(=O)=O)C=CC2=C(N=O)C([O-])=CC=C21.C1=C(S([O-])(=O)=O)C=CC2=C(N=O)C([O-])=CC=C21.C1=C(S([O-])(=O)=O)C=CC2=C(N=O)C([O-])=CC=C21 JMXROTHPANUTOJ-UHFFFAOYSA-H 0.000 description 1
- CTIQLGJVGNGFEW-UHFFFAOYSA-L naphthol yellow S Chemical compound [Na+].[Na+].C1=C(S([O-])(=O)=O)C=C2C([O-])=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 CTIQLGJVGNGFEW-UHFFFAOYSA-L 0.000 description 1
- 239000001053 orange pigment Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000001054 red pigment Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 230000008698 shear stress Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- VVNRQZDDMYBBJY-UHFFFAOYSA-M sodium 1-[(1-sulfonaphthalen-2-yl)diazenyl]naphthalen-2-olate Chemical compound [Na+].C1=CC=CC2=C(S([O-])(=O)=O)C(N=NC3=C4C=CC=CC4=CC=C3O)=CC=C21 VVNRQZDDMYBBJY-UHFFFAOYSA-M 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
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- UGCDBQWJXSAYIL-UHFFFAOYSA-N vat blue 6 Chemical compound O=C1C2=CC=CC=C2C(=O)C(C=C2Cl)=C1C1=C2NC2=C(C(=O)C=3C(=CC=CC=3)C3=O)C3=CC(Cl)=C2N1 UGCDBQWJXSAYIL-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
The invention provides an erasable ball-pen ink composite, comprising the following components in parts by weight: 10-40 parts of low boiling point organic solvent, 5-10 parts of intermediate boiling point organic solvent, 5-20 parts of plasticizer, 30-75 parts of elastomer resin, 10-30 parts of pigment and 0-2 parts of ink rheological agent. The erasable ball-pen ink composite can be used for solving the problems of discontinuous strokes, ink leakage at the joint of a pen point and an ink tube, and serious discontinuous strokes and pocking of ink after the a ball pen is placed for a long time in the prior art.
Description
Technical field
The present invention relates to a kind of ink composite and preparation method thereof, particularly a kind of Erasable ink composition for ball pen and preparation method thereof.
Background technology
Ballpoint pen erasable printing ink has come out 20 years left and right time, from writing in the past serious broken string pit, write feel and be poor to present write line roadbed originally normally, feel is still weaker than common ball pen ink, but because it has the rubber of using wiped clean, function with modification, still ceaselessly developing.At present on the market the erasable ball pen ink exist write, the problem of the aspects such as preservation, outward appearance and steady quality, erasable ball pen ink is in the past used natural or synthetic rubber substantially fully, basic for natural rubber, rubber solvent naphtha (being generally gasoline, benzene or dimethylbenzene) they are solvent, can play to natural rubber that the softening agent of some softening plasticization effects and pigment produced adding.Because use the gasoline equal solvent, make and write the petrolic solvent volatilization that volatility is very high, smell is very serious, so have a strong impact on health, it is all filling in the stainless steel oil pipe of certain air pressure is arranged letting alone general erasable ball pen ink, uses danger very high.And the current softening agent to good this large class of phthalic ester of natural rubber plasticization effect is all because the Environmental Safety problem is inhibited in the stationery industry and uses; In addition, also there is first stroke of a Chinese character broken string in the printing ink of producing at present on writing, nib writes with the leakage of oil of oil pipe junction, the rear printing ink of long-time placement the problem that the broken string pit is serious, and in the different shortcoming of different paper surface writing effect, in addition after existing ballpoint pen erasable Printing ink producing between product batches difference also very large.
In sum, this area lacks can solve the first stroke of a Chinese character broken string that prior art exists, and after nib and the leakage of oil of oil pipe junction, the long-time placement, printing ink is write the printing ink of the problem that the broken string pit is serious.
Summary of the invention
The first purpose of the present invention is to obtain and can solves the first stroke of a Chinese character broken string that prior art exists, and after nib and the leakage of oil of oil pipe junction, the long-time placement, printing ink is write the ink composite of the problem that the broken string pit is serious.
The second purpose of the present invention is to obtain and can solves the first stroke of a Chinese character broken string that prior art exists, and after nib and the leakage of oil of oil pipe junction, the long-time placement, printing ink is write the printing ink of the problem that the broken string pit is serious.
The 3rd purpose of the present invention is to obtain and can solves the first stroke of a Chinese character broken string that prior art exists, the preparation method that after nib and the leakage of oil of oil pipe junction, the long-time placement, printing ink is write the printing ink of the problem that the broken string pit is serious.
The 4th purpose of the present invention is to obtain and can solves the first stroke of a Chinese character broken string that prior art exists, and after nib and the leakage of oil of oil pipe junction, the long-time placement, printing ink is write the goods of the problem that the broken string pit is serious.
In a first aspect of the present invention, a kind of Erasable ink composition for ball pen is provided, it comprises following components by weight percent:
Low boiling point organic solvent 10～40 weight parts;
Mid-boiling point organic solvent 5～10 weight parts;
Softening agent 5～20 weight parts;
Elastomer resin 30～75 weight parts;
Pigment 10～30 weight parts; And
Printing ink auxiliary rheological agents 0～2 weight part.
In a specific embodiment of the present invention,
The boiling point of described low boiling point organic solvent is lower than 120 ℃; With
The boiling point of described mid-boiling point organic solvent is lower than 200 ℃, higher than 120 ℃.3. composition as claimed in claim 2, is characterized in that,
The boiling point of described low boiling point organic solvent is 70～120 ℃; The boiling point of described mid-boiling point organic solvent is 120～180 ℃; And the weight ratio of low boiling point organic solvent and mid-boiling point organic solvent is 4: 1～8: 1.
In a preference, described low boiling point organic solvent is: rudimentary (C5～C10) alkane of straight chain or alkene, side chain lower paraffin hydrocarbons or alkene, rudimentary naphthenic hydrocarbon or alkene, as long as the scope that boiling point is requiring.Be for example commercially available (Skellysolve A, normal hexane, 2-methylbutane, 2-methylpentane, 3-methylpentane, 2,2-dimethylbutane, 2,3-dimethylbutane, normal heptane, 2-methylheptane, 3-methylheptane, 4-methylheptane, 3-ethyl hexane, 2,2-dimethylhexane, 2,3,3-trimethylpentane, commercially available oil extract solvent etc.
In a preference, described mid-boiling point organic solvent is: straight chain lower paraffin hydrocarbons (C9～C17), side chain lower paraffin hydrocarbons, rudimentary naphthenic hydrocarbon, ether, alcohol, alcohol ether, as long as boiling point in the scope required, can the solvent necessarily mixed be arranged in above-mentioned low boiling point organic solvent.Be for example (positive nonane, 2,2,5-trimethyl cyclohexane, n-decane, amylalcohol, pimelinketone, pentyl acetate and the commercially available oil extraction solvent that meets described boiling point requirement.
Particularly, low boiling point organic solvent is 70～120 ℃.
In a specific embodiment of the present invention, described elastomer resin is polyvinyl acetate (PVA), plastic of poly vinyl acetate or the two mixture, and this elastomer resin number-average molecular weight is 200,000～700,000; Both can mix and use with arbitrary proportion.
In a specific embodiment of the present invention, described pigment is that oil-proofness, light permanency and solvent resistance are not less than the pigment of three grades.
The rank of described pigment is by the GB detection assay.
In a specific embodiment of the present invention, the weight summation of described low boiling point organic solvent, mid-boiling point organic solvent, softening agent, elastomer resin, pigment and printing ink rheology adjuvant component accounts for 95～100% of composition total weight.
In a specific embodiment of the present invention, also comprise rust-preventive agent, antiskinning agent or its combination.
The ballpoint pen erasable printing ink printing ink that a second aspect of the present invention provides a kind of composition of the present invention to prepare.
A third aspect of the present invention provides a kind of preparation method of ballpoint pen erasable printing ink of the present invention,
The pigment of 30～75 weight part elastomer resins, 10～30 weight parts, 0～2 weight part printing ink auxiliary rheological agents are soaked and to be dissolved in 10～40 weight part low boiling point organic solvents, 5～10 weight part mid-boiling point organic solvents and 5～20 parts of softening agent liquid, obtain mixture;
After described mixture is ground to required viscosity and granules of pigments particle diameter and reaches required scope, by filtration, obtain described ballpoint pen erasable printing ink.
In a preference, treat that elastomer resin dissolves fully, the pigment complete wetting is disperseed, after being uniformly dissolved, auxiliary rheological agents obtains described mixture.
In a preference, on three-roll grinder, repeatedly be ground to required viscosity and granules of pigments particle diameter five below micron after, obtain described ballpoint pen erasable printing ink by press filtration.
A fourth aspect of the present invention provides a kind of ballpoint pen goods of ballpoint pen erasable printing ink of the present invention.
Embodiment
The inventor, through extensive and deep research, by improving preparation technology, has obtained the first stroke of a Chinese character that solves the prior art existence and has broken, and nib is write the formula of the problem that the broken string pit is serious with the leakage of oil of oil pipe junction, the rear printing ink of long-time placement.Completed on this basis the present invention.
Below described in detail to various aspects of the present invention:
Erasable ink composition for ball pen and the printing ink prepared thereof
A kind of Erasable ink composition for ball pen of the present invention, is characterized in that, comprises following components by weight percent:
Low boiling point organic solvent 10～40 weight parts;
Mid-boiling point organic solvent 5～10 weight parts;
Softening agent 5～20 weight parts;
Elastomer resin 30～75 weight parts;
Pigment 10～30 weight parts; And
Printing ink auxiliary rheological agents 0～2 weight part.
Preferably, the weight summation of described low boiling point organic solvent, mid-boiling point organic solvent, softening agent, elastomer resin, pigment and printing ink rheology adjuvant component accounts for 95～100% of composition total weight.
Described composition can also comprise rust-preventive agent, antiskinning agent or its combination.
low boiling point organic solvent and mid-boiling point organic solvent
Preferably, the boiling point of described low boiling point organic solvent is lower than 120 ℃; With
The boiling point of described mid-boiling point organic solvent is lower than 200 ℃, higher than 120 ℃.
Preferably, the boiling point of described low boiling point organic solvent is 70～120 ℃; The boiling point of described mid-boiling point organic solvent is 120～180 ℃; And the weight ratio of low boiling point organic solvent and mid-boiling point organic solvent is 4: 1～8: 1.
As the present invention, further improve, described low boiling point organic solvent is: boiling point is lower than 120 ℃ (volatilize fast in order to reach solvent, do not carry pigment and resin penetration in the paper space, preferably 70～100 ℃ of boiling points), the solvent that rate of volatilization is 3～8, consumption is 10～40 weight parts.
In a preference, described low boiling point organic solvent is: rudimentary (C5～C10) alkane of straight chain or alkene, side chain lower paraffin hydrocarbons or alkene, rudimentary naphthenic hydrocarbon or alkene, as long as the scope that boiling point is requiring.Be for example commercially available Skellysolve A, normal hexane, 2-methylbutane, 2-methylpentane, 3-methylpentane, 2,2-dimethylbutane, 2,3-dimethylbutane, normal heptane, 2-methylheptane, 3-methylheptane, 4-methylheptane, 3-ethyl hexane, 2,2-dimethylhexane, 2,3,3-trimethylpentane, commercially available oil extract solvent etc.
As the present invention, further improve, the mid-boiling point organic solvent is that boiling point is 120～200 ℃ and (in order to reach ink, is arranged certain volatilization time at the nib place, make printing ink there is writing quality at better intermittence, boiling point is chosen in 120～180 ℃), the solvent that rate of volatilization is 8～15, consumption is 5～10 weight parts, and described mid-boiling point organic solvent needs the complete mixing of elastomer resin that can dissolve with low boiling point organic solvent, not stratified separating out.
In a preference, described mid-boiling point organic solvent is: straight chain lower paraffin hydrocarbons (C9～C17), side chain lower paraffin hydrocarbons, rudimentary naphthenic hydrocarbon, ether, alcohol, alcohol ether, as long as boiling point in the scope required, can the solvent necessarily mixed be arranged in above-mentioned low boiling point organic solvent.Be for example positive nonane, 2,2,5-trimethyl cyclohexane, n-decane, amylalcohol, pimelinketone, pentyl acetate and the commercially available oil extraction solvent that meets described boiling point requirement.
At present on the market the erasable ball pen ink exist write, the problem of the aspects such as preservation, outward appearance and steady quality, erasable ball pen ink is in the past used natural or synthetic rubber substantially fully, basic for natural rubber, rubber solvent naphtha (being generally gasoline, benzene or dimethylbenzene) they are solvent, can play to natural rubber that the softening agent of some softening plasticization effects and pigment produced adding.Because use the gasoline equal solvent, make and write the petrolic solvent volatilization that volatility is very high, smell is very serious, so have a strong impact on health, it is all filling in the stainless steel oil pipe of certain air pressure is arranged letting alone general erasable ball pen ink, uses danger very high.And the current softening agent to good this large class of phthalic ester of natural rubber plasticization effect is all because the Environmental Safety problem is inhibited in the stationery industry and uses; In addition, also there is first stroke of a Chinese character broken string in the printing ink of producing at present on writing, nib writes with the leakage of oil of oil pipe junction, the rear printing ink of long-time placement the problem that the broken string pit is serious, and in the different shortcoming of different paper surface writing effect, after existing ballpoint pen erasable Printing ink producing between product batches difference also very large.Adopt solvent combination of the present invention to address the above problem.
elastomer resin
Particularly, described elastomer resin is polyvinyl acetate (PVA), plastic of poly vinyl acetate or the two mixture, and this elastomer resin number-average molecular weight is 200,000～700,000; Both can mix and use with arbitrary proportion.
The elastomer resin consumption is 30～75 weight parts.
pigment
Described pigment is that oil-proofness, light permanency and solvent resistance are not less than the pigment of three grades.
As the present invention, further improve, described pigment oil-proofness, light permanency and solvent resistance be all more than 3 grades, its easy grinding distribution to 5 below micron can, as: as carbon black, acetylene black, ivory black and the nigrosine etc. of black pigment; Organic yellow, permanent yellow, naphthol yellow S, hansa yellow G, organic yellow 10G, benzidine yellow G and benzidine yellow G R etc. as yellow ultramarine; As the permanent orange GTR of orange pigments and Benzidine orange G etc.; Permanent bordeaux, lithol red and pyrazolone red etc. as red pigment; Alkali blue lake, victoria blue color lake, phthalocyanine blue and indanthrene blue BC etc. as blue pigments; As the pigment green B of veridian, phthalocyanine green, naphthol green etc.; Above-mentioned pigment can be used separately, also can two or more be used in combination, and optimum consumption is 10～30 weight parts, and amount of pigment is on the low side, writes color and luster partially light, affects use properties; Amount of pigment is higher, and granules of pigments is easily assembled and made and write circuit and produce pit and erasable degradation.
softening agent
As the present invention, further improve, as long as described softening agent can be by the good plasticising of elastomer resin, high and low temperature resistance is good to be got final product, as: epoxy soybean oil, fatty silicon ester, tributyl citrate, ATBC, hexanodioic acid certain herbaceous plants with big flowers diester, alkyl sulfonic ester, alkyl sulfonic ester etc., in order to make ink stability higher, select the softening agent higher with the elastomer resin coordination, as: alkyl sulfonic ester and alkyl sulfonic ester etc., optimum consumption is 5～20; Plasticizer consumption is low, resin can not be plastified fully, writes feel unfluent; Plasticizer consumption is higher, can cause again excessively plasticizing and can't obtain and write normally circuit of resin.
the printing ink auxiliary rheological agents
As the present invention, further improve, described printing ink auxiliary rheological agents improves system rheological performance for printing ink, commonly used as polyurea modified auxiliary rheological agents, inorganic bentonite, aerosil, urethane etc., add certain auxiliary rheological agents, making printing ink the time is high viscosity state in storage, and brings printing ink some shear-stresses when the ball of nib rolls, the viscosity of printing ink will descend, make and write the feel smoothness, circuit is full, and its optimum consumption is 0.1～1 weight part.
the preparation method
A kind of preparation method of described ballpoint pen erasable printing ink comprises the steps:
The pigment of 30～75 weight part elastomer resins, 10～30 weight parts, 0～2 weight part printing ink auxiliary rheological agents are soaked and to be dissolved in 10～40 weight part low boiling point organic solvents, 5～10 weight part mid-boiling point organic solvents and 5～20 parts of softening agent liquid, obtain mixture;
After described mixture is ground to required viscosity and granules of pigments particle diameter and reaches required scope, by filtration, obtain described ballpoint pen erasable printing ink.
In a preference, treat that elastomer resin dissolves fully, the pigment complete wetting is disperseed, after being uniformly dissolved, auxiliary rheological agents obtains described mixture.
In a preference, on three-roll grinder, repeatedly be ground to required viscosity and granules of pigments particle diameter five below micron after, obtain described ballpoint pen erasable printing ink by press filtration.
The invention has the advantages that:
Between gained ballpoint pen erasable ink product of the present invention batch, difference is little, writing quality good, and film-forming polymer content is high, solvent evaporates less environment-friendly type erasable printing ink; And have simultaneously leakproof oiliness and keeping quality good advantage, environmental protection, to healthy harmless.
Further beneficial effect of the present invention is: between the Erasable ink composition for ball pen product batches of using this preparation method to produce, difference is little, writing quality good, and film-forming polymer content is high, the less environment-friendly type erasable printing ink that obtains of solvent evaporates; And have simultaneously leakproof oiliness and keeping quality good advantage.The present invention adopts environment-friendly materials to make, and to healthy harmless, environmentally safe, used safe, durable.
As no specific instructions, various raw material of the present invention all can obtain by commercially available; Or prepare according to the ordinary method of this area.Unless otherwise defined or described herein, the familiar same meaning of all specialties used herein and scientific words and those skilled in the art.Any method similar or impartial to described content and material all can be applicable in the inventive method in addition.
Other aspects of the present invention, due to the disclosure of this paper, are apparent to those skilled in the art.
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only are not used in and limit the scope of the invention for the present invention is described.The experimental technique of unreceipted actual conditions in the following example, measure according to national standard usually.If there is no corresponding national standard, according to general international standard, normal condition or the condition of advising according to manufacturer, carry out.Unless otherwise indicated, otherwise all umbers are weight part, and all per-cents are weight percentage, and described polymericular weight is number-average molecular weight.
Unless otherwise defined or described herein, the familiar same meaning of all specialties used herein and scientific words and those skilled in the art.Any method similar or impartial to described content and material all can be applicable in the inventive method in addition.
Embodiment 1
Composition of the present invention and component concentration following (unit is gram):
Low boiling point organic solvent (normal hexane) 19.5 grams;
Mid-boiling point organic solvent (amylalcohol) 5 grams;
Softening agent (epoxy soybean oil) 10 grams;
Polyvinyl acetate resin (400,000 molecular weight) 45 grams;
Carbon black 20 grams;
Aerosil 0.5 gram.
Preparation method of the present invention is as follows:
The charcoal blacks of 45 weight part polyvinyl acetate resin elastomer resins, 20 weight parts, 0.5 weight part aerosil printing ink auxiliary rheological agents are soaked and to be dissolved in 19.5 weight part lower boilings, 5 weight part mid-boiling point organic solvents and 10 parts of softening agent liquid, treat that elastomer resin dissolves fully, the pigment complete wetting is disperseed, after auxiliary rheological agents is uniformly dissolved, on three-roll grinder, repeatedly be ground to required viscosity and granules of pigments particle diameter five below micron after, obtain erasable ball pen ink of the present invention by press filtration.
Described erasable ball pen ink reaches industry standard.
Embodiment 2
Composition of the present invention and component concentration following (unit is gram):
Low boiling point organic solvent (Skellysolve A) 19.5 grams;
Mid-boiling point organic solvent (pimelinketone) 6 grams;
Softening agent (ATBC) 12 grams;
Ethylene vinyl acetate (500,000 molecular weight) 40 grams;
Carbon black 22 grams;
Aerosil 0.5 gram.
Preparation method of the present invention is as follows:
The charcoal blacks of 40 parts by weight of ethylene vinyl acetate elastomer resins, 22 weight parts, 0.5 weight part aerosil printing ink auxiliary rheological agents are soaked and to be dissolved in 19.5 weight part lower boilings, 6 weight part mid-boiling point organic solvents and 12 parts of softening agent liquid, treat that elastomer resin dissolves fully, the pigment complete wetting is disperseed, after auxiliary rheological agents is uniformly dissolved, on three-roll grinder, repeatedly be ground to required viscosity and granules of pigments particle diameter five below micron after, obtain erasable ball pen ink of the present invention by press filtration.
Described erasable ball pen ink reaches industry standard.
Embodiment 3:
Composition of the present invention and component concentration following (unit is gram):
Low boiling point organic solvent (normal heptane) 16 grams;
Mid-boiling point organic solvent (pentyl acetate) 8 grams;
Softening agent (hexanodioic acid certain herbaceous plants with big flowers diester) 8 grams;
Polyvinyl acetate resin and ethylene vinyl acetate hybrid resin (weight ratio is 1: 1) 50 grams;
Permanent bordeaux 18 grams;
Preparation method of the present invention is as follows:
By the permanent bordeaux pigment of 50 weight part polyvinyl acetate resins and ethylene vinyl acetate mixed elastomer resin, 18 weight parts, soak and be dissolved in 16 weight part lower boilings, 8 weight part mid-boiling point organic solvents and 8 parts of softening agent liquid, treat that elastomer resin dissolves fully, the pigment complete wetting is disperseed, after auxiliary rheological agents is uniformly dissolved, on three-roll grinder, repeatedly be ground to required viscosity and granules of pigments particle diameter five below micron after, obtain erasable ball pen ink of the present invention by press filtration.
Described erasable ball pen ink reaches industry standard.
Embodiment 4:
Composition of the present invention and component concentration following (unit is gram):
Low boiling point organic solvent (normal hexane) 23 grams;
Mid-boiling point organic solvent (amylalcohol) 6 grams;
Softening agent (epoxy soybean oil) 6 grams;
Polyvinyl acetate resin and ethylene vinyl acetate hybrid resin (weight ratio is 1: 1) 40 grams;
Victoria blue color lake 25 grams;
Preparation method of the present invention is as follows:
By the victoria blue color lake of 40 weight part polyvinyl acetate resins and ethylene vinyl acetate mixed elastomer resin, 25 weight parts, soak and be dissolved in 23 weight part lower boilings, 6 weight part mid-boiling point organic solvents and 6 parts of softening agent liquid, treat that elastomer resin dissolves fully, the pigment complete wetting is disperseed, after auxiliary rheological agents is uniformly dissolved, on three-roll grinder, repeatedly be ground to required viscosity and granules of pigments particle diameter five below micron after, obtain erasable ball pen ink of the present invention by press filtration.
Described erasable ball pen ink reaches industry standard.
Embodiment 5:
Composition of the present invention and component concentration following (unit is gram):
Low boiling point organic solvent (Skellysolve A) 23.5 grams;
Mid-boiling point organic solvent (pimelinketone) 6 grams;
Softening agent (ATBC) 10 grams;
Polyvinyl acetate resin (molecular weight is 500,000) 38 grams;
Phthalocyanine green 22 grams;
Aerosil 0.5 gram.
Preparation method of the present invention is as follows:
The phthalocyanine green pigment of 38 weight part polyvinyl acetate resin elastomer resins, 22 weight parts, 0.5 weight part aerosil printing ink auxiliary rheological agents are soaked and to be dissolved in 23.5 weight part lower boilings, 6 weight part mid-boiling point organic solvents and 10 parts of softening agent liquid, treat that elastomer resin dissolves fully, the pigment complete wetting is disperseed, after auxiliary rheological agents is uniformly dissolved, on three-roll grinder, repeatedly be ground to required viscosity and granules of pigments particle diameter five below micron after, obtain erasable ball pen ink of the present invention by press filtration.
Described erasable ball pen ink reaches industry standard.
Performance embodiment
Embodiment 1～5 is carried out to the test of writing quality (pit) by adopting picture circle instrument to carry out, adopt picture circle instrument to draw at least three circles that diameter is 3.1cm, all nibs all adopt unified hourglass head, if three circles all do not find that leakage of oil, pit, discontinuous phenomenon are for qualified.
After tested, the printing ink that above-described embodiment obtains is not all found leakage of oil, pit, discontinuous phenomenon after making pen.
The foregoing is only preferred embodiment of the present invention, not in order to limit essence technology contents scope of the present invention, essence technology contents of the present invention is broadly to be defined in the claim scope of application, any technology entity or method that other people complete, if defined identical with the claim scope of application, also or a kind of change of equivalence, all will be regarded as being covered by among this claim scope.
All documents of mentioning in the present invention are all quoted as a reference in this application, just as each piece of document quoted separately as a reference.Should be understood that in addition, after having read foregoing of the present invention, those skilled in the art can make various changes or modifications the present invention, these equivalent form of values fall within the application's appended claims limited range equally.
Claims (7)
1. an Erasable ink composition for ball pen, is characterized in that, comprises following components by weight percent:
Low boiling point organic solvent 10～40 weight parts; The boiling point of wherein said low boiling point organic solvent is 70～120 ℃;
Mid-boiling point organic solvent 5～10 weight parts; The boiling point of wherein said mid-boiling point organic solvent is 120～180 ℃; The weight ratio of described low boiling point organic solvent and mid-boiling point organic solvent is 4:1～8:1;
Softening agent 5～20 weight parts;
Elastomer resin 30～75 weight parts; Wherein said elastomer resin is polyvinyl acetate (PVA), plastic of poly vinyl acetate or the two mixture, and this elastomer resin number-average molecular weight is 200,000～700,000; Both can mix and use with arbitrary proportion;
Pigment 10～30 weight parts; And
Printing ink auxiliary rheological agents 0～2 weight part.
2. composition as claimed in claim 1, is characterized in that, described pigment is the pigment that oil-proofness, light permanency and solvent resistance are not less than three grades of GBs.
3. composition as claimed in claim 1, is characterized in that, the weight summation of described low boiling point organic solvent, mid-boiling point organic solvent, softening agent, elastomer resin, pigment and printing ink rheology adjuvant component accounts for 95～100% of composition total weight.
4. composition as claimed in claim 1, is characterized in that, also comprises rust-preventive agent, antiskinning agent or its combination.
5. the ballpoint pen erasable printing ink that composition as claimed in claim 1 prepares.
6. the preparation method of a ballpoint pen erasable printing ink claimed in claim 5, is characterized in that,
The pigment of 30～75 weight part elastomer resins, 10～30 weight parts, 0～2 weight part printing ink auxiliary rheological agents are soaked and to be dissolved in 10～40 weight part low boiling point organic solvents, 5～10 weight part mid-boiling point organic solvents and 5～20 parts of softening agent liquid, obtain mixture;
Wherein, the boiling point of described low boiling point organic solvent is 70～120 ℃; The boiling point of described mid-boiling point organic solvent is 120～180 ℃; The weight ratio of described low boiling point organic solvent and mid-boiling point organic solvent is 4:1～8:1; Described elastomer resin is polyvinyl acetate (PVA), plastic of poly vinyl acetate or the two mixture, and this elastomer resin number-average molecular weight is 200,000～700,000; Both can mix and use with arbitrary proportion;
After described mixture is ground to required viscosity and granules of pigments particle diameter and reaches required scope, by filtration, obtain described ballpoint pen erasable printing ink.
7. ballpoint pen goods that contain ballpoint pen erasable printing ink as claimed in claim 5.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010611792 CN102020893B (en) | 2010-12-29 | 2010-12-29 | Erasable ball-pen ink composite and preparation method thereof |
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| CN 201010611792 CN102020893B (en) | 2010-12-29 | 2010-12-29 | Erasable ball-pen ink composite and preparation method thereof |
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| CN102020893B true CN102020893B (en) | 2013-12-18 |
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| US9486368B2 (en) | 2013-12-05 | 2016-11-08 | Medline Industries, Inc. | Disposable hygienic article with means for diagnostic testing |
| CN103911036B (en) * | 2014-04-30 | 2016-01-20 | 苏州安洁科技股份有限公司 | Silk screen printing bright black ink |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4407985A (en) * | 1982-05-05 | 1983-10-04 | Scripto, Inc. | Method of making and improved compositions for an initially erasable ink for a ball point writing instrument |
| CN1125243A (en) * | 1995-09-21 | 1996-06-26 | 郝培志 | Erasable writing ink |
| US6503965B1 (en) * | 2000-08-24 | 2003-01-07 | Bic Corporation | Solvent-based non-fluorescent ink for writing instruments based upon pigment dispersions in non-aqueous solvents |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8524802B2 (en) * | 2008-11-07 | 2013-09-03 | Manish Babulal Shah | Ink composition and a ball point pen comprising the same |
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2010
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4407985A (en) * | 1982-05-05 | 1983-10-04 | Scripto, Inc. | Method of making and improved compositions for an initially erasable ink for a ball point writing instrument |
| CN1125243A (en) * | 1995-09-21 | 1996-06-26 | 郝培志 | Erasable writing ink |
| US6503965B1 (en) * | 2000-08-24 | 2003-01-07 | Bic Corporation | Solvent-based non-fluorescent ink for writing instruments based upon pigment dispersions in non-aqueous solvents |
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