CN1281017A - Starch ester paint - Google Patents
Starch ester paint Download PDFInfo
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- CN1281017A CN1281017A CN 99119229 CN99119229A CN1281017A CN 1281017 A CN1281017 A CN 1281017A CN 99119229 CN99119229 CN 99119229 CN 99119229 A CN99119229 A CN 99119229A CN 1281017 A CN1281017 A CN 1281017A
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- Prior art keywords
- starch
- composition
- ester
- coating
- starch ester
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- 229920002472 Starch Polymers 0.000 title claims abstract description 93
- 239000008107 starch Substances 0.000 title claims abstract description 93
- 235000019698 starch Nutrition 0.000 title claims abstract description 92
- 150000002148 esters Chemical class 0.000 title claims abstract description 60
- 239000003973 paint Substances 0.000 title abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000000203 mixture Substances 0.000 claims abstract description 37
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 11
- 239000004014 plasticizer Substances 0.000 claims abstract description 9
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 7
- 238000006467 substitution reaction Methods 0.000 claims abstract description 7
- 238000000576 coating method Methods 0.000 claims description 49
- 239000011248 coating agent Substances 0.000 claims description 46
- 239000008199 coating composition Substances 0.000 claims description 30
- 239000008186 active pharmaceutical agent Substances 0.000 claims description 25
- 239000004902 Softening Agent Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 13
- 230000008595 infiltration Effects 0.000 claims description 11
- 238000001764 infiltration Methods 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 239000004816 latex Substances 0.000 claims description 10
- 229920000126 latex Polymers 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 239000010410 layer Substances 0.000 claims description 5
- 125000004185 ester group Chemical group 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 3
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- 150000001408 amides Chemical class 0.000 claims description 3
- 239000011247 coating layer Substances 0.000 claims description 3
- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical compound NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 claims description 3
- 229940124530 sulfonamide Drugs 0.000 claims description 3
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 239000010409 thin film Substances 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims 2
- 239000005416 organic matter Substances 0.000 claims 1
- 239000000853 adhesive Substances 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 abstract 1
- 230000035515 penetration Effects 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- -1 aliphatic ester Chemical class 0.000 description 13
- 238000009835 boiling Methods 0.000 description 13
- 239000005357 flat glass Substances 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 229910001220 stainless steel Inorganic materials 0.000 description 11
- 239000010935 stainless steel Substances 0.000 description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 10
- 241000842962 Apoda limacodes Species 0.000 description 10
- 239000002390 adhesive tape Substances 0.000 description 10
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 10
- 239000001993 wax Substances 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 8
- 239000010408 film Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 229920001685 Amylomaize Polymers 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 238000010792 warming Methods 0.000 description 6
- 235000019439 ethyl acetate Nutrition 0.000 description 5
- 229920000728 polyester Polymers 0.000 description 5
- 235000019260 propionic acid Nutrition 0.000 description 5
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 5
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 description 4
- 229920002261 Corn starch Polymers 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 240000007594 Oryza sativa Species 0.000 description 4
- 235000007164 Oryza sativa Nutrition 0.000 description 4
- 240000008042 Zea mays Species 0.000 description 4
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000008120 corn starch Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 235000009566 rice Nutrition 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 4
- 239000008399 tap water Substances 0.000 description 4
- 235000020679 tap water Nutrition 0.000 description 4
- 241000239290 Araneae Species 0.000 description 3
- 230000001464 adherent effect Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229920000856 Amylose Polymers 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 2
- 235000016383 Zea mays subsp huehuetenangensis Nutrition 0.000 description 2
- 150000001242 acetic acid derivatives Chemical class 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 235000005822 corn Nutrition 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000007046 ethoxylation reaction Methods 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 235000009973 maize Nutrition 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 2
- 239000001384 succinic acid Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 229920001059 synthetic polymer Polymers 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- 239000011345 viscous material Substances 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- MEIRRNXMZYDVDW-MQQKCMAXSA-N (2E,4E)-2,4-hexadien-1-ol Chemical compound C\C=C\C=C\CO MEIRRNXMZYDVDW-MQQKCMAXSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 229920001353 Dextrin Polymers 0.000 description 1
- 239000004375 Dextrin Substances 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 240000003183 Manihot esculenta Species 0.000 description 1
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 description 1
- 244000061456 Solanum tuberosum Species 0.000 description 1
- 235000002595 Solanum tuberosum Nutrition 0.000 description 1
- 244000046109 Sorghum vulgare var. nervosum Species 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 244000098338 Triticum aestivum Species 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000012164 animal wax Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000012084 conversion product Substances 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 235000019425 dextrin Nutrition 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000002036 drum drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 230000002650 habitual effect Effects 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- TWNIBLMWSKIRAT-VFUOTHLCSA-N levoglucosan Chemical group O[C@@H]1[C@@H](O)[C@H](O)[C@H]2CO[C@@H]1O2 TWNIBLMWSKIRAT-VFUOTHLCSA-N 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 125000005375 organosiloxane group Chemical group 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000012169 petroleum derived wax Substances 0.000 description 1
- 235000019381 petroleum wax Nutrition 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000000452 restraining effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000004447 silicone coating Substances 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000012178 vegetable wax Substances 0.000 description 1
Landscapes
- Paper (AREA)
Abstract
A paint composition resisting against adhesive and water vapout penetration contains ester with 2-8 carbon atoms, starch ester with 1-2.2 degrees of substitution, hydrophobic plasticizer and water.
Description
The present invention relates to release coating and anti-steam infiltration coating, these coating are to use through the treated starch ester of selecting to make, and more particularly, are to make with the starch ester of the medium DS of ester moiety with 2-8 carbon atom and 1.0-2.2.
Release coating contains fusible composition and/or the auxiliary agent of controlling or eliminating between two surfaces usually.These coating generally have good anti-adhesion performance, and this performance is to allow to adhere to the ability (that is to say that this coating must provide low interfacial tension for the viscous substance that is in contact with it) that lip-deep viscous substance is easy to peel off.But good anti-adhesion performance is not the desired unique performance of this coating.Needed other performance of release coating comprise good cohesive strength, with the good binding property of backing ground and pollution-free or do not have composition to move in the viscous layer.
Silicone material for example organo-siloxane is well-known as the purposes of release agent and release coating.The U.S. Pat of issuing on January 8th, 1991 October 18 in 4983701,1994 U.S. Pat of issuing 5356706 and the U.S. Pat of issuing on December 27th, 1,994 5376420 all disclose uses silicone material as release agent in different application.The release agent of other type that has been used comprises synthetic polymer for example polyolefine and fluorocarbon, and long-chain alkyl derivative is aliphatic ester synthetic wax and lipid acid for example, and wax for example petroleum wax, vegetable wax and animal wax.
Though the material of giving an example above particularly silicone material has demonstrated the anti-adhesion performance that is suitable for various uses, when the paper product that needs pulp again, can reuse, they are unpractical.
In packing and other application, need anti-moisture pervious course to prevent that steam from passing through the infiltration of paper or other ground material sometimes.In many cases, used soft solid materials for example polyethylene form anti-moisture pervious course or water-proof coating.Though these materials are normally useful as protective coating,, for the application of the paper product of needs pulp again, the product that can reuse, they are unpractical.
In some application, used material based on starch.For example, the U.S. Pat 3746558 that was presented to people such as F.Berkhout on July 17th, 1973 discloses a kind of waterborne suspension of starch ester hydrophobic, low DS, and this suspension can be used to form water-proof coating.The U.S. Pat 4095992 that was presented to people such as S.Rudolph on June 20th, 1978 discloses the blended starch ester of monocarboxylic acid acid anhydride and polybasic acid anhydride, and this starch ester can provide water-repellancy as heat cured, hydrophobic coating.On June 9th, 1993, disclosed European patent application EP 0545228A1 disclosed the purposes of the mixture of treated starch and synthetic polymer, and this mixture is used as anti-moisture pervious course in the weather-proof dressing bag.On June 23rd, 1993 disclosed another piece European patent application EP 0547551A1 disclose contain treated starch, gelatin, softening agent, water and lipoid composition as edible film, these films provide water, lipoid, solute, gas, sealing coat physics or microorganism for food effectively.
Though above-mentioned starch substance provides anti-moisture perviousness and/or water-repellancy really in different application, they do not provide a kind of like this thermoplastic coating, and this coating is easy to form has the infiltrative successive film coating of excellent waterproof vapour.
Have now found that, have good non-stick property and anti-moisture perviousness with the coating composition of making through the treated starch ester of selecting, and this coating composition is biodegradable and favourable to environment, therefore makes in the application of this coating composition aspect the stationery that requires pulp again and can reuse particularly useful.
In more detail, the present invention relates to release coating compositions, this composition contains:
A) have the starch ester release agent of the ester moiety of 2-8 carbon atom and the substitution value of 1.0-2.2 (DS),
B) softening agent and
C) water.
The invention still further relates to the preparation method of the ground of antiseized coating, wherein, release coating compositions of the present invention is coated on the ground as latex, be heated to suitable temperature then, make the latex particle fusing and flow into the successive film.The invention still further relates to the pressure sensitive adhesion ground, this ground comprises ground, pressure sensitive adhesive layer and release coating layer, and release coating layer wherein contains starch ester release coating compositions of the present invention.
The invention still further relates to anti-steam infiltration coating composition, this coating composition contains:
A) have the starch ester of the ester moiety of 2-8 carbon atom and the substitution value of 1.1-2.2 (DS),
B) hydrophobic plasticizer and
C) water.
The invention still further relates to the preparation method of the ground of anti-steam pervious course coating, wherein, anti-steam infiltration coating composition of the present invention is coated on the ground as latex, be heated to suitable temperature then, make the present latex particulate fusing and flow into the successive film.
The invention provides release coating compositions and anti-steam infiltration coating composition, these compositions contain the starch esterification compound, and this compound has the substitution value that 2-8 carbon atom and this compound have 1.0-2.2 in ester moiety.These starch esters contain the ester cpds with following structural formula:
Wherein St is based on the material of starch, and R is alkyl, aryl, alkenyl, alkaryl or the aralkyl of 1-7 carbon atom, the alkyl or the alkenyl of preferred 1-4 carbon atom.More preferably, the R group that contains of this ester cpds is the alkyl of 1-2 carbon atom.Such starch ester comprises two or more mixture of amylcose acetate, propionic acid starch, butyric acid starch, caproic acid starch, phenylformic acid starch, these esters, for example amylcose acetate/propionic acid starch and starch wherein contain the substituent mixing starch ester of two or more different esters, acetate/propionic acid starch for example, that is, this ester has for example following structural formula:
Wherein R and the different substituting group of R ' as top defined R group.
In addition, these starch esters as defined above have the DS (substitution value) of 1.0-2.2, are preferably the DS of 1.2-1.9, more preferably the DS of 1.4-1.6.In other words, this starch ester has such DS, and this DS is high enough to prevent water-dispersion and is high enough to make starch is thermoplastic, that is to say, the Tg of anhydrous (the no moisture or do not have softening agent) that has is lower than about 200-220 ℃ decomposition temperature.Term used herein " substitution value " (DS) represents to have in each anhydroglucose unit of starch molecule the mean value of substituent point.
By for example making starch and organic acid anhydride reaction in the pyridine, can prepare the starch ester that the present invention uses with medium DS at solvent system.Recently, disclose the method that a kind of water established law prepares starch ester in being presented to people's such as R.Billmers U.S. Pat 5321132 on June 14th, 1994, it is for referencial use to quote this piece document in the present invention.This method relates to the single stage method that water becomes, and wherein makes the organic acid anhydride of starch and format high throughput and the alkaline reagents reaction of high density.
The raw starch material that is used for starch ester of the present invention can be those starch that obtain from any plant origin, these plant origins comprise corn, potato, wheat, rice, sago, cassava, waxy maize, Chinese sorghum and high amylose starch, promptly, starch with at least 45%, particularly at least 65% amylose content, for example amylomaize.Also can use starch powder.The above-mentioned raw materials starch substance also comprises the conversion product that obtains from any aforesaid raw material, for example the dextrin by acid and/or the preparation of hot hydrolytic action, the flowability by enzymatic conversion or weak acid hydrolysis preparation or rare boil starch, by with oxygenant for example clorox handle Sumstar 190 and the deutero-starch for preparing, for example positively charged ion, negatively charged ion, both sexes, nonionic and crosslinked starch.In other words, this starch substance can comprise particulate state or dispergated starch.Dispergated or non-granular starch is meant any starch that its structure is destroyed or decompose, that is, before deriving, destroy any starch of its structure by the method for hot (jet cooking, boiling water bath heating), machinery (dry drum drying, spraying drying, extruding) or chemistry (use liquid ammonia, dextrinizing, stand alkaline purification highly).
Release coating compositions and anti-steam infiltration coating composition also contain softening agent and water except starch ester.Softening agent is the nonvolatile organic substance compatible with starch ester.This softening agent should be non-water-soluble, promptly, solubleness in water is less than 5%, and this softening agent is hydrophobic, this softening agent absorbs the moisture of low amount under high humidity, that is to say that moisture content is less than 20% weight, preferably less than 15% weight under the situation of 23 ℃ and 90% relative humidity (RH).This softening agent is liquid under envrionment temperature or room temperature, and use this softening agent with such amount, this amount makes the Tg (second-order transition temperature) of starch ester be reduced to the scope of desired about 75-200 ℃ of processing, and preferably this scope is 80-135 ℃.This temperature is to be convenient to make the coating fusing necessary in the drying that for example adopts in the paper technology or the press polish step.The molecular weight of this softening agent generally is lower than about 10000.Can be with various plasticizer materials and the combination of the starch ester through selecting, to satisfy desired condition.Useful plasticizer materials comprises those compounds that contain polar group, these polar groups for example are sulphonamide, carboxylic acid and carboxylicesters, carboxylate salt, acid amides, phosphoric acid ester, alcohol (that is the compound of hydroxyl), epoxide, sulfone, ether, imide, amine, carbonic ether, urea and urethane groups.Preferred plasticizer is those softening agent that contain sulphonamide, alcohol, acid amides and ester group, they absorb the moisture of low amount under high humidity, that is to say that moisture content is less than about 20% weight, preferably less than about 15% weight under the situation of 90% relative humidity (RH) and 23 ℃.Preferred plasticizer does not comprise the compound of wetting ability type, other compound of glycerine or sorbyl alcohol and this type for example, the compound of this wetting ability type be hygroscopic and pick up easily and absorb moisture.Useful softening agent comprises low-molecular-weight the polyester for example polyester, the alcoxylates (for example ethoxylate of phenol and dihydroxyphenyl propane) and the fatty acid amide of poly-(hydroxybutyric acid-valerate), polycaprolactone, phenol and phenol derivatives of polyoxyethylene glycol and di-carboxylic acid (for example hexanodioic acid/Succinic Acid).Preferred plasticizer is the polyester of polyoxyethylene glycol and hexanodioic acid or Succinic Acid and the ethoxylate of dihydroxyphenyl propane.
This coating composition contains the softening agent of the starch ester of the 10-50% weight of having an appointment, about 0-30% weight and the water of about 20-90% weight usually.This composition preferably contains the softening agent of the starch ester of the 15-35% weight of having an appointment, about 5-25% weight and the water of about 35-80% weight.According to different purposes, can also in this composition, add other composition commonly used, for example filler, antioxidant, stablizer, tensio-active agent, wax and dyestuff or tinting material.
Starch ester of the present invention is hydrophobic and water-insoluble, and this starch ester even for example can not be dissolved or dispersed in the water under the temperature of room temperature to 150 ℃ in the temperature that raises, and therefore this starch ester can not be used or apply as the aqueous solution.Therefore, this starch ester composition is made latex, this latex contains discontinuous starch and the softening agent particulate that suspends in water.This latex is applied or is coated on the ground of wanting, the discontinuous film of dry then formation.Be heated to the Tg temperature of about starch ester or higher temperature, be generally about 100-200 ℃, make present latex particulate fusing and mobile, on ground, form continuous thin film.Because water can not dissolve polymer and is not film forming major cause, so can be heated to above the Tg temperature of starch ester the arbitrary time in drying process and/or after the moisture evaporation.Can or use baking oven, moisture eliminator or other conventional drying installation by dry air with the coating drying.Can for example press polish or thermal treatment be heated coating to form the successive film by certain methods.
Any habitual coating method may be used to this coating composition is applied on the ground, for example brushing, blade coating, dip-coating, roller coat, wire coating or scraper coating.Select coating method according to wanting coated ground.Anhydrate with being convenient to remove for the viscosity that reduces coating composition, can or be higher than under the temperature (preferably about 50-75 ℃) of room temperature, this composition is applied on the ground in room temperature.Also can or be higher than this mixture of preparation under the temperature of envrionment temperature in envrionment temperature.These components of heating help plasticizer absorption in the starch particulate in process for preparation, thereby form more uniform latex or dispersion.
This release coating compositions can be applied on any ground,, for example contain those products of pressure sensitive adhesive especially for paper product.These starch ester release coatings that are used for paper product provide good anti-adhesion performance, and because their biological degradability and other environmental performance make such product can be by pulp and recycling again.This anti-steam infiltration coating composition can be applied on any ground,, for example be used for those paper product of food product pack especially for paper product.These starch ester paints that are used for paper product provide excellent waterproof vapour perviousness, and because their biological degradability and other environmental performance make such product can be by pulp and recycling again.
Following embodiment will further specify embodiment of the present invention.Unless be illustrated in addition, in these embodiments, all umbers all are by weight, and all temperature all are meant centigradetemperature.
The embodiment I
Preparation contains the release coating compositions of starch ester of the present invention by the following method.
In the erlenmeyer flask of 250ml, add anhydrous granular amylcose acetate (70% the straight chain corn starch of 16.5 grams, the DS=1.3 of its acetic ester), 5.0 restrain the dihydroxyphenyl propane (Macol 206-EM, PPG Industries Inc.) of ethoxylations and make gross weight reach the tap water of 50.0 grams.Mix the content powerful mixing of spoon with stainless steel, till making this mixture form slurry with erlenmeyer flask.With plumbous weight be placed on this flask opening around and this flask is placed in the boiling water bath, make the liquid level of water be higher than the liquid level of flask contents.Under stirring state frequently,, from boiling water bath, take out flask and thorough mixing content then with this flask heating 1 hour.Adding water in flask makes weight reach initial gross weight.This mixture is put back in the boiling water bath, when preparing to be used for following application till.
The embodiment II
The body paper (9 " * 11 ") of one page paper label (quantitatively: 4#, high pressure Gurley Gas permeability is 270 seconds) is placed on the big sheet glass, the face end margin of this paper is bonded on the sheet glass with adhesive tape.This piece sheet glass is placed on the smooth horizontal surface, with #9 wire wound rod (wire round) be placed on this paper ground above.From boiling water bath, take out the coating for preparing in the embodiment I, this coating is dripped to sidewards with 1/2 inch pearl on the face of paper ground (just below wire wound rod).When applying light pressure, wire wound rod terminal and pulled down the end of this paper ground promptly.Take off the paper that this has coating from sheet glass, and this paper down is placed on the festoon drier (drying ring) with coated side.Spider is placed on the festoon drier and places a weight in the above, make coating carry out dry air.
Take off the paper ground dry from festoon drier.Make a coated side to warming mill, with of the ground press polish of stainless steel warming mill with this coating.Processing conditions is 5000psi (roll gap pressure), 90 ℃ (temperature of top stainless steel rider) and 2 press polish (paper is by twice).
Estimate anti-adhesion performance and guarantor's viscosity energy of the label body paper of this coating by the following method:
1. one section 8 inches long Scotch Magic tape #810 adhesive tape layer is pressed onto on the paper of above-mentioned coating.
2. guarantee between adhesive tape and Detackified compositions, to form excellent contact.
3. at room temperature make adhesive tape remain on the adherent surfaces 3 weeks when being.
4. measure the required power of from the adherent surfaces stripping tape (being to peel off with the angles of 180 degree under the situation of 10.0 inch per minute clocks at test speed) with the Instron tester.
5. remove the second adhesive tape with hand from adherent surfaces.
6. the adhesive tape in above-mentioned 5 is adhered to cleaning, smooth stainless steel plate (Chem Instruments, cat#TP-39) on.With the sample roll-in, (Chem Instruments cat#WR-100) by 2 times, left standstill sample 20 minutes before test to the pressure roller that covers with 2 kilograms rubber.
7. in above-mentioned 4, measure stripping strength.
8. as measuring stripping strength (restraining/0.75 inch) in above-mentioned 7, write down antiseized value.
9. adhere on the stainless steel plate resembling a new adhesive tape (not contacted) in above-mentioned 6, remove adhesive tape and as in above-mentioned 4, measure with separate paper.
10. protect the per-cent of viscosity=derive from binding property * 100/ in above-mentioned 7 and derive from binding property in above-mentioned 9.
Below table 1 expression be the label body paper that applied with starch ester of the present invention and with the physicals of the siloxanes separate paper contrast test of commodity.This embodiment explanation is keeping the excellent fusible while, has same antiseized ability based on the coating of starch.
Table 1
| Sample | Non-stick property (gram/inch) | Protect viscosity % |
| Amylcose acetate (DS=1.3) | ????255 | ????98 |
| Rhinelander Tight Release (siloxanes, #402-8437) | ????52 | ????88 |
| Body paper (uncoated) | Fiber tearing | ????- |
The embodiment III
Use the anhydrous granular starch of 30 grams (70% straight chain corn starch, its acetic ester DS=1.3), 10.0 gram succinate polyester (Resoflex R-804, U.S. Cambridge industrial) and make total amount reach 133.3 the gram tap water, according to preparing release coating compositions in the embodiment I like that.Be coated on the label body paper resembling this coating composition in the embodiment II, test various physicalies, and expression in following table 2, compare with the commercial siloxanes separate paper of two kinds of trades mark.This sample shows, forms the smooth continuous coated of the paper character that is similar to silicone coating.
Table 2
| Sample | High pressure Gurley Gas permeability (second) | Parker?Print | Hercules Size test |
| Body paper (uncoated) | ????800 | ????5．10 | ????27 |
| Amylcose acetate ester (DS=1.3) on body paper | ????4950 | ????3．7 | ????185 |
| Rhinelander Premium Release (siloxanes, #442-8354) | ????2670 | ????3．86 | ????960 |
| Rhinelander Tight Release (siloxanes, #402-8437) | ????3152 | ????3．86 | ????2580 |
The embodiment IV
A kind of content of wax starch of acid degradation is pre-dispersed, then with the DS of this starch acetylize to 1.0.Come this acetylizad product of purifying by the decantation aqueous medium with distilled water development.According to the such coating composition for preparing that illustrates in the embodiment I.With different starch esters, that is, based on the starch ester of waxy maize or amylomaize (70% amylose starch), they are dispergated or granulous, prepare other similar coating.Be coated in like that on the paper label body paper in the combination image embodiment II with preparation, test various physicalies, will the results are shown in the following table 3.These presentation of results under the situation with gratifying coating result, can use starch ester with granular or dispergated form, and can operate under different temperature.All samples all have the Gas permeability greater than 100000 high pressure Gurley seconds.
Table 3
| Specimen coding | Starch structure | Starch type | Softening agent % | The preparation temperature (℃) | Parker?Print | Antiseized ability (gram/inch) |
| ????1 | Dispersed | The content of wax | 25 | Room temperature | ????2．3 | ????572 |
| ????2 | Dispersed | The content of wax | 25 | ????65 | ????2．5 | ????561 |
| ????3 | Granular | The content of wax | 25 | Room temperature | ????3．9 | ????295 |
| ????4 | Granular | The content of wax | 25 | ????65 | ????3．3 | ????289 |
| ????5 | Granular | High amylose starch | 25 | Room temperature | ????3．1 | ????255 |
| ????6 | Granular | High amylose starch | 25 | ????65 | ????2．2 | ????230 |
| ????7 | Dispersed | The content of wax | 50 | ????65 | ????2．9 | ????225 |
The embodiment V
Preparation contains the anti-steam infiltration coating composition of starch ester of the present invention by the following method.
In the erlenmeyer flask of a 250ml, add anhydrous granular amylcose acetate (70% the straight chain corn starch of 30 grams, its acetic ester DS=1.3), 10.0 gram succinate polyester (Resoflex R-804, U.S. Cambridge industrial) and tap water, make gross weight reach 133.3 grams.Mix the content powerful mixing of spoon with stainless steel, till making this mixture form slurry with erlenmeyer flask.With plumbous weight be placed on this flask opening around and this flask is placed in the boiling water bath, make the liquid level of water be higher than the liquid level of flask contents.Under the condition of stirring this flask was being heated 1 hour frequently, from boiling water bath, taking out flask and thorough mixing content then.Adding water in flask makes weight reach initial gross weight.This mixture is put back in the boiling water bath, when preparing to be used for following application till.
The embodiment VI
With the body paper (9 " * 11 ") of one page paper label (quantitatively: 42#) be placed on the big sheet glass, the face end margin of this paper is bonded on the sheet glass with adhesive tape.This piece sheet glass is placed on the smooth horizontal surface, with the #15 wire wound rod be placed on this paper ground above.From boiling water bath, take out the coating for preparing in the example I, this coating is dripped to sidewards top go up (just below the wire wound rod) of this paper ground with 1/2 inch pearl.When applying light pressure, wire wound rod terminal and pulled down the end of this paper ground promptly.Take off the paper that this has coating from sheet glass, and this paper down is placed on the festoon drier with coated side.Spider is placed on the festoon drier and places a weight in the above, make coating carry out dry air.
Take off the paper ground dry from festoon drier.Make coated one side towards warming mill, with of the ground press polish of stainless steel warming mill with this coating.Processing conditions is 5000psi (roll gap pressure), 90 ℃ (temperature of top stainless steel rider) and 2 press polish (paper is by twice).
Estimate the water vapor permeable rate (MVTR) of the label body paper that applied by the following method with TAPPI T448 om-89: 1. siccative is encased in test chamber (No.68-1, Thwing Albert Instrument Co.) in, be loaded into from top 5mm place, 2. from wanting underproof sample scraps of paper to cut the circular paper of 3 inch diameters, 3. will test facing down and be placed on the test chamber of coating of the scraps of paper, 4. decorative cover is put on the test chamber and with it and tightens, 5. test chamber being placed on relative humidity is 50%, temperature is in 23 ℃ the moistening case, 6. take out sample and write down weight in designated time intervals (24 hours), 7. calculate water vapor permeable rate: MVTR=gram/(rice by the following method
2) (my god)=x/Ay x=increasing y=through the weight of certain hour and increase the area (rice that the elapsed time A=of institute sample is exposed wherein in gram in the weight in sky
2).
Following table 4 explanation, use the coating composition (amylcose acetate DS=1.3) of embodiment I preparation and, all improved the water vapor permeable rate with the similar coating composition that the starch (acetic ester DS=1.5) of mobile high amylose starch (70%) corn of acid degradation prepares.
Table 4
At 50%RH, the water vapor permeable rate sample MVTR (gram/rice under 23 ℃
2/ day) body paper (uncoated) 170.5 amylcose acetates (DS=1.3) 97.19 mobile amylcose acetates (DS=1.5) 85.10
The embodiment VII
Preparation contains the anti-steam infiltration coating composition of starch ester of the present invention in accordance with the following methods.In the erlenmeyer flask of 250ml, add anhydrous granular amylcose acetate (70% the straight chain corn starch of 50.0 grams, its acetic ester DS=1.3), 16.7 restrain the dihydroxyphenyl propane (Macol 206-EM, PPG Industries Inc.) of ethoxylations and make gross weight reach the tap water of 150.7 grams.Mix the content powerful mixing of spoon with stainless steel, till making this mixture form slurry with erlenmeyer flask.With plumbous weight be placed on this flask opening around and this flask is placed in the boiling water bath, make the liquid level of water be higher than the liquid level of flask contents.Under the condition of stirring this flask was being heated 2 hours frequently, from boiling water bath, taking out flask and thorough mixing content then.Adding water in flask makes weight reach initial gross weight.This mixture is put back in the boiling water bath, when preparing to be used for following application till.
The body paper (9 " * 11 ") of one page Rhinelander paper label is placed on the big sheet glass, the face end margin of this paper is bonded on the sheet glass with adhesive tape.This piece sheet glass is placed on the smooth horizontal surface, with the #9 wire wound rod be placed on this paper ground above.The coating for preparing above taking out from boiling water bath drips to this coating with 1/2 inch pearl by top (just below the festoon drier) of this paper ground sidewards.When applying light pressure, wire wound rod terminal and pulled down the end of this paper ground promptly.Take off the paper that this has coating from sheet glass, and this paper down is placed on the festoon drier with coated side.Spider is placed on the festoon drier and places a weight in the above, make the coating drying.Take off the paper ground dry from festoon drier.Make coated one side towards warming mill, with of the ground press polish of this stainless steel warming mill with this coating.Processing conditions is 5000psi (roll gap pressure), 90 ℃ (temperature of top stainless steel rider) and 2 press polish (paper is by twice).
Estimate the label body paper that applies with above-mentioned amylcose acetate composition and with the physicals of the copy paper of same coating coating, that is, high pressure (HP) Gurley and Hercules Size test (HST).Use the same method and estimate the paper that applies with propionic acid starch (DS=1.3) composition, provided the result in the following table 5.
Table 5 label body paper copy paper sample HP Gurley HST HP Gurley HST amylcose acetate＞100000 seconds 82 seconds 42 seconds 22 seconds propionic acid starch＞100000 seconds 92 seconds 65 seconds 40 seconds uncoated 800 seconds 27 seconds 11.1 seconds 10 seconds
Claims (11)
1. the coating composition of an antiseized or anti-steam infiltration, said composition contains: a) have the starch ester of the ester moiety of 2-8 carbon atom and the substitution value of 1.0-2.2 (DS), b) hydrophobic plasticizer, and c) water.
2. the composition of claim 1, starch ester wherein has the DS of 1.2-1.9.
3. the composition of above-mentioned any one claim, starch ester wherein has 2-5 carbon atom in ester moiety.
4. the composition of above-mentioned any one claim, said composition contains the softening agent of the starch ester of the 10-50% weight of having an appointment, about 0-30% weight and the water of about 20-90% weight.
5. the composition of above-mentioned any one claim, starch ester wherein has following structural formula:
Wherein St is based on the material of starch, and R is alkyl, aryl, alkenyl, alkaryl or the aralkyl of 1-7 carbon atom.
6. the composition of above-mentioned any one claim, softening agent wherein is the nonvolatile polar organic matter matter compatible with starch ester, and exists with the amount that the Tg that is enough to make starch ester is reduced to about 75-200 ℃ temperature.
7. the composition of above-mentioned any one claim, softening agent wherein contains sulphonamide, alcohol, acid amides or ester group.
8. the method for preparing the coated substrate of antiseized or anti-steam infiltration, this method comprises: a kind of coating composition that contains starch ester latex a) is provided, this coating composition contains the composition of above-mentioned any one claim, b) this coating composition is coated on the ground, and c) ground that will apply is heated to the Tg temperature of starch ester or is higher than the temperature of this temperature, makes particles fuse and forms continuous thin film.
9. the method for claim 8, wherein the ground drying that before heating, will apply.
10. the method for claim 9, ground wherein is a paper.
11. a pressure sensitive adhesion member, this member comprise substrate layer, pressure sensitive adhesive layer and release coating layer, release coating wherein contains any one the composition of claim 1-7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99119229 CN1281017A (en) | 1999-07-20 | 1999-07-20 | Starch ester paint |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99119229 CN1281017A (en) | 1999-07-20 | 1999-07-20 | Starch ester paint |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1281017A true CN1281017A (en) | 2001-01-24 |
Family
ID=5280778
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 99119229 Pending CN1281017A (en) | 1999-07-20 | 1999-07-20 | Starch ester paint |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1281017A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106274120A (en) * | 2016-08-17 | 2017-01-04 | 安徽文峰特种纸业有限公司 | A kind of preferable printing paper of solid color and preparation method thereof |
-
1999
- 1999-07-20 CN CN 99119229 patent/CN1281017A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106274120A (en) * | 2016-08-17 | 2017-01-04 | 安徽文峰特种纸业有限公司 | A kind of preferable printing paper of solid color and preparation method thereof |
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