CN104710875A - Novel soya-bean oil-type newsprint rotary ink formula - Google Patents
Novel soya-bean oil-type newsprint rotary ink formula Download PDFInfo
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- CN104710875A CN104710875A CN201310679342.6A CN201310679342A CN104710875A CN 104710875 A CN104710875 A CN 104710875A CN 201310679342 A CN201310679342 A CN 201310679342A CN 104710875 A CN104710875 A CN 104710875A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21F—PAPER-MAKING MACHINES; METHODS OF PRODUCING PAPER THEREON
- D21F9/00—Complete machines for making continuous webs of paper
- D21F9/02—Complete machines for making continuous webs of paper of the Fourdrinier type
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
- D21H11/14—Secondary fibres
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
- D21H23/02—Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
- D21H23/22—Addition to the formed paper
- D21H23/32—Addition to the formed paper by contacting paper with an excess of material, e.g. from a reservoir or in a manner necessitating removal of applied excess material from the paper
- D21H23/34—Knife or blade type coaters
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
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- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to a novel soya-bean oil-type newsprint rotary ink formula, which is characterized in that a glass transition peak is generated in a 20-100 DEG C scope, another type is a conversion peak at -65 DEG C, and the glass-transition temperature of a sample is CB75N>RFE>MDI>RMDI>IPDI>TDI>N100>N3330>HDI; wherein the glass-transition temperature of two polyurethane samples synthesized by aromatic isocyanate is highest, the glass-transition temperature of aromatic and alicyclic diisocyanate (two rings) is secondary highest, then glass-transition temperature of a sample synthesized by aromatic and aromatic and alicyclic diisocyanate (one ring) is third highest; and the p conversion peak of the polyurethane sample synthesized by RMDI is -30 DEG C, conversion is relative to molecular movement, impending molecular chain in the other polyurethane sample is cut by double decomposition effect, and conversion of polyurethane synthesized by RMDI is caused due to conformation change of cyclohexyl of diiso fluoric acid ester.
Description
One, field
The novel soya-bean oil type news offset rotary ink formula of the present invention belongs to chemical field.
Two, brief introduction
Since the eighties in 20th century, external printing technology development rapidly, heat-set offset technology is used widely with its practicality, high efficiency, require higher to newsprinting paper printing performance, surface property, anti-hair and powder dropping performance, glossiness, smoothness and the adaptive faculty to ink, common newsprint difficult quality meets this requirement.
For this reason, external paper manufacturers undergoes technological transformation to existing newspaper machine, develops a series of dab newsprinting paper machine finished coated newsprint being one by one applicable to the technical requirements of heat-set offset newsprinting paper.
Supercalendered paper (sc) and light basis weight painting is reached in order to make the surface property of newsprinting paper
Cloth paper (LW C) level, meets four-color process requirement, and external paper manufacturers have developed another kind of main dab newsprinting paper---cold-set offset coated newsprint paper in phase late 1990s.
In order to the condition of production helping newsprinting paper manufacturing enterprise of China to understand external dab newsprinting paper, improving international competition strength, herein to two paper kinds of external dab newsprinting paper---machine finished coated newsprint and the cold-set offset coated newsprint paper condition of production are briefly introduced.
Since the eighties in 20th century, due to fibrous material shortage, the newsprinting paper manufacturer of Japan and U.S.West Coast extensively adopts pulp from decoloured waste paper to make raw material production newsprinting paper.
Because pulp from decoloured waste paper fiber fines too much makes newsprint quality decline, in offset printing process, there is serious hair and powder dropping phenomenon.
In order to address this problem, manufacturer utilizes a roll coater to adopt starch to carry out top sizing to newsprinting paper.In order to improve printing effect further, paper manufacturers adds again the Gao Ling-h of some amount in starch or calcium carbonate pigment has produced machine finished coated newsprint.
This paper is called as " BiToKoShi or " trace hydrocarbons paper " in Japan.Press polish still adopts the interior hard press polish of the machine used when producing newsprinting paper.
Because this production technique makes ornamenting ditch in the fields cloth paper glue spread in the machine produced high, often produce spot, present most manufacturer has used two nip soft press-polishing machines in film sizer and machine instead and has produced.
This paper main raw material is pulp from decoloured waste paper, the quantitative 49-54g/m of paper, every face glue spread <6g/m2, glossiness 25% one 45%, whiteness 75% ~ 80% (example consumption).
Europe machine finished coated newsprint is produced slightly early than Japan and the U.S., has powerful competitive power, particularly Finland in the international market.
Slurry therewith: mechanical pulp 65%, bleached sulphate softwood pulp 30%, pearl filler 5%; Stock freeness 60 ~ 70CSF (~: when producing newsprint, slurry dissociates 100CSF) cloth equipment mainly short delay knife coater of holding withg both hands, calendering equipment is more complicated, both organic interior hard rolling press, also organic interior soft press-polishing machine or the outer supercalender of machine.
Quantitative 52 ~ the 70g/m of the paper produced ~, every face glue spread 7 ~ 1lg/m, whiteness 75% ~ 80%, glossiness 20% ~ 30%.
Before transformation, paper machine copies wide 5.5m, speed of a motor vehicle lO00m/min, and throughput is low, does not possess and large-scale newspaper machine competitive strength.
Net wide 5 9m, copy wide 5.4m, speed of a motor vehicle 1250m/min, throughput l4 ten thousand tons/year.
After transformation, paper machine primarily of SymFlo head box, SymFormer former, SymPress I/ unipress .SDTA Dynamtc ~ lJ] hasty and careless cloth machine, Valmet two nip soft press-polishing machine, standard winder and Wh ~ Roll-Wari ~ ep rewinding machine composition.
Whole White Board in two nip soft press-polishing machines transformation newspaper machine production machine in film sizer and machine.
Before transformation, throughput is low, and unable and large-scale newspaper machine is competed.
The wide 5.6m of paper machine net after transformation, copies wide 5.2m, speed of a motor vehicle 1260m/min, throughput 13 5 ten thousand tons/year.
After transformation, paper machine is primarily of Sym ~ o}ls head box, sp day 9d FormerHs former, band the 4th separate press nips fgTfiwa ~ t unipress, Symsizer film sizer, Valmet two nip Opti concept of optimization soft press-polishing machine, standard winder and JagFloat rewinding machine composition.
Slurry therewith: mechanical pulp 65% ~ 70*/0, bleached sulphate softwood pulp 25% one 30%, pearl filler 5%, quantitative 45 ~ the 54g/m 2 of the paper produced, every face glue spread <6g/m2, whiteness 75% ~ 8 [Y/b, glossiness >45%.Machine finished coated newsprint is produced after transformation in 1988.
Improved paper machine speed 1 500ill/illin, nets wide 6.0ill, copies wide by 5.4111, throughput 140,000 tons/year.
After transformation, paper machine is by TaillFlo head box, TamFormer Hs former, 11amP1% II unipress of band the 4th separate press nips, the hasty and careless cloth machine of SDTA Beloit scraper, Kleinew two nip soft press-polishing machine, standard winder and Vail-Top rewinding machine composition.
These two paper machines represent 8O age in 20th century advanced level of the hasty and careless cloth paper of ornamenting in production machine in the world.
But owing to adopting knife coater to produce, make chemical pulp proportioning higher, become paper glue spread higher, page surface often produces the paper defects such as thin spot.
External paper manufacturers just adopts advanced selling price second quarter in 1998 to be 5600 ~ 5950 yuan/ton successively.
Before transformation, throughput is low, cannot compete with large-scale newspaper machine.
After nineteen ninety-five transformation, paper 6 2m after production machine transformation, copies wide 5.7m, speed of a motor vehicle 1000m/rain, throughput 110,000 tons/year.
After transformation, paper machine is primarily of H yd ranli C head box, SYm sizerNit film sizing applicator, Valmet two nip ∞ concept of optimization soft press-polishing machine, standard winder and twin-roll rewinding machine composition.
Slurry therewith: mechanical pulp 65% ~ 70%, bleached sulphate softwood pulp 25% ~ 30%, pearl filler 5%, quantitative 45 ~ the 54g/m of the paper produced, every face glue spread <6g/nl, whiteness 75% ~ 80%, glossiness >45%.
{ ~ f//~ r1999 is 5600-5950 yuan/ton the second quarter in sale.
Copy wide 7.6m before transformation, speed of a motor vehicle l200m/ II blood, produce traditional featherweight coated paper (LW C), main employing scraper for coating and the outer supercalendering of machine.
Production cost is high, quality product is low, competitive power is weak.
After transformation, the wide 8.3m of paper machine net, copies wide 7.6m, speed of a motor vehicle l220m/min, throughput 200,000 tons/year.
After transformation, paper machine is primarily of SymFlo head box, SymFormer former, the Twinver unipress of band the 3rd separate press nips, Symsizer ~ film sizing applicator, Valmet two nip Opti concept of optimization soft press-polishing machine, Opd concept of optimization winder and Winbelt rewinding machine composition.
After this paper machine rebuilding, become the world's most nineties in 20th century representational machine finished coated newsprint machine because-ft is beautiful and Europe is large to low gloss coating machinery slurry paper demand, featherweight coated paper (LWC) cost ratio machine finished coated newsprint is high, does not produce machine finished coated newsprint and direct production featherweight coated paper (LW C) after No. 5 machines transformation of Port Albemi paper plant.
Raw materials used: mechanical pulp (CTMP) 50% ~ 80%, bleached sulphate softwood pulp 2O% ~ 25%. high ridge f: or pearl filler 5%.
Produce featherweight coated paper (Lw c) quantitative 47 ~ 66g, m (average 59g/m), every face glue spread 7-9.5g/m, glossiness 50% ~ 55%, whiteness 65% one 75%.Selling price is 6000-6500 yuan/ton the second quarter in 1999.
Cold solid amine print coated newsprint paper is the new paper kind that external paper manufacturers is developed by cold-set offset technical requirements, be mainly used in newpapers and periodicals inset and advertisement insert is rich because current heat-set offset technology accounts for leads status, this cold-set offset coated newsprint paper is not yet used widely, and demand is only 1,000,000 tons/year.
After entering for eight 21 centurys, along with a large amount of the popularizing of cold solid chamber print technology, this cold-set offset newsprinting paper demand will increase sharply, and progressively in newpapers and periodicals inset and advertisement insert, replaces featherweight coated paper, machine finished coated newsprint and supercalendered paper.
The manufacturer of current this paper is only limitted to Europe, and wherein German Hah ~ dl Augsburg ~ department's annual production reaches 400,000 tons, German SchwedthPa ~ er company, t ~ ' qorsk Skog ~ department and UPM-Kymmene company of Finland produce 6o ten thousand tons/year altogether.After entering 2000, North America also starts to produce this paper, ~ BASF AG.
These companies produce cold-set offset coated newsprint paper paper making equipment used and provide primarily of Valmet company, particularly Vahnet company Opti concept of optimization series product, as OptiFlo head box, OptiFormer ~ shape device, OotiPrn ~ squeezing, Optisizer ~ film sizing applicator, Optiload rolling press, OptiReel winder and wiT1Belt rewinding machine etc., the speed of a motor vehicle can surpass the restriction of i ~ 2000in/min.
Slurry therewith: pulp from decoloured waste paper 60% one 70%, mechanical pulp l5% ~ 25%, bleached sulphate softwood pulp 1 (P/o mono-15%, calcium carbonate or kaolin clay filler 5%.The cold-set offset coated newsprint paper produced: quantitative 45-5Og/m, every face glue spread <6g/m, whiteness 75% 1 80%, glossiness >50%.
Selling price 1999 ~ the second quarter is 54OO ~ 5500 yuan/ton.Page characteristic has met or exceeded supercalendered paper (SC) and featherweight coated paper, and (LW CPR puts down, and meets the needs that four-color process technical requirements eyefidelity is high completely.
After entering 2l century, the print media publishers such as newspaper will be subject to the larger pressure of electronic medium.In order to help the print media publishers such as newspaper to stand firm in the market competition of fierceness, paper manufacturers must improve production efficiency and product quality significantly, reduces production cost.Produce cost ratio machine finished coated newsprint and featherweight coated paper lower, quality particularly surface property meets or exceeds supercalendered paper and featherweight coated paper, meets the cold-set offset coated newsprint paper of four-color process requirement.
In order to protection of the environment, the production of this paper is except selecting part bleached sulphate softwood pulp and mechanical pulp, and major part can select pulp from decoloured waste paper to be raw material, adds and fills out and will select calcium carbonate and kaolin.Slave unit is selected, and main selection Valmet company Opti conception-optimized paper machine, the speed of a motor vehicle is generally more than 2000m/min.
As a kind of raw material of novel synthesis of polyurethane, soya-bean oil type polyvalent alcohol extracts from vegetables oil, is a kind of reproducible resource.
Compare favourably with the urethane that the performance of the urethane of soya-bean oil type polyvalent alcohol synthesis can be synthesized with the polyvalent alcohol extracted from oil in many aspects.
The thermo-oxidative stability of soya-bean oil type polyurethane is higher than poly(propylene oxide) based polyurethanes.Soybean oil has very strong hydrophobicity, therefore will have good weathering resistance with the urethane of soybean oil synthesis.
The soya-bean oil type polyurethane of synthesis can be used for polyurethane foam, elastomerics, coating etc.
Its structure of soya-bean oil polyvalent alcohol used in this research is similar to furans.On the 9th or the 10th carbon atom that its hydroxyl is positioned at lipid acid and on the 12nd or the 13rd carbon atom.
Therefore, when completely crosslinked, the part of molecular chain (as from the 10th carbon atom to
Between 18th carbon atom) be not connected in cross-linked network, but unsettled, in system, serve the effect of softening agent.
The performance of polymer network depends on their chemical structure and hands over density.Experiment shows, polyvalent alcohol and 4, and the urethane crosslinks density that 4 one phenylbenzene alkane vulcabond (MDI) synthesize is not
High.
Second-order transition temperature (Tg is 5O ~ 7O DEG C) and modulus not high yet.
By changing the functionality of a 0H quantity or isocyanic ester in polyvalent alcohol.Cross-linking density can be changed.
Chemical structure due to isocyanic ester also affects the performance of urethane network, and we discuss isocyanide ester functionality (two functionality and three-functionality-degree) and chemical structure (fat under study for action
Fat race, alicyclic and aromatic series) impact on urethane performance.
In this research, the polyvalent alcohol of synthesis of polyurethane is soya-bean oil type polyvalent alcohol.
Have various isocyanic ester to can be used for the synthesis of urethane, they impart the different performance of urethane.Compared with the urethane that wherein urethane and the aliphatics isocyanic acid of aromatic isocyanate synthesis synthesizes, there is higher rigidity, but it is oxidized and ultraviolet (uV) less stable.
Employ two kinds of aromatic diisocyanates (MDI and tolylene diisocyanate (TDI)); Two kinds of alicyclic diisocyanates (hexamethylene-diisocyanate (HDI)) and four kinds of triisocyanates (two kinds be aromatic series, two kinds be aliphatics).
The chemical structure of urethane is made up of polyvalent alcohol and isocyanic ester two kinds of structural units.The soya-bean oil type polyvalent alcohol that we use has four functionality, and irregular structure, thus avoid the crystallization of urethane, be obtained by reacting single-phase random thermosetting resin with vulcabond or triisocyanate.
The chemical structure of isocyanic ester affects rigidity and the cross-linking density of urethane network.Along with the change of isocyanic ester kind, the rigidity order of urethane network is as follows: the alicyclic < aromatic series of aliphatics <.
The cross-linking density of the urethane that triisocyanate synthesizes is higher compared with two isocyanide ester fat, so affect sample density, 71g, mechanical property, swelling property.If know the interaction parameter of solvent and polymkeric substance, then cross-linking density enters by polymkeric substance swelling property in a solvent
Row is estimated.
Usually, degree of swelling is higher, and cross-linking density is lower, and the solvent as polymkeric substance is better.The degree of swelling of urethane in toluene of aliphatics, alicyclic diisocyanate resin synthesis is maximum, aromatic diisocyanate and the different urethane of trembling vinegar synthesis of aliphatics three take second place, the urethane degree of swelling of two kinds of aromatic tri-isocyanates synthesis is minimum, and the degree of swelling of the urethane wherein synthesized than Desmodru RFE with the degree of swelling of the urethane of CB75N synthesis is low.
Suppose that cross-linking density is identical, then the degree of swelling of urethane of aliphatics triisocyanate synthesis is greater than the urethane of aromatic tri-isocyanates synthesis, for the two, and the good solvent of the toluene urethane of aliphatics triisocyanate synthesis especially.
Also same rule is had for aliphatics and alicyclic triisocyanate.Different isocyanic ester is on the impact of density.
Can find out, the urethane synthesized by aromatic tri-isocyanates RFE, CB75 N has the highest density.
The high-density of phosphoric wherein in DesmodurRFE to polymkeric substance has significant contribution, and the urethane that its density is synthesized compared with CB75N is also high.
The density of the urethane of aromatic series dicyanate MDI, TDI and aliphatics triisocyanate N100, N3300 synthesis is taken second place.
The density of the urethane of aliphatics and alicyclic diisocyanate synthesis is minimum.
Obviously, the benzene ring structure of isocyanic ester is on the impact of density polymer than cross-linking density
Impact is large.
The Young's modulus of all samples sharply increases along with the increase of temperature.This phenomenon is demonstrated by the test of bend specimen and tension specimen.The rubber elasticity theory that prediction modulus increases with the increase of temperature: E=3 R T=3 P R T/M C (1) are wherein the concentration of living chain; R is gas law constant; T is absolute temperature; P is density; Me is the equal molecular mass of number of network medium chain.
The molecular chain group that modulus increases is because its molecular chain convergent force increases, entropy increase, and forms the molecular chain ball of string shunk.
Sample can be observed the convergent force of thermo-elasticity or increase when being in rubbery state, but only has sample
Product, higher than thermo-elasticity transition point, are in when drawing secondary state and just can observe.
General elongation is about 7%.Comparatively large to system contribution lower than this thermal expansion, shrink system contribution large higher than this scope entropy.
By the dynamic experiments in linear elastic region. demonstrate as Zhongchang rate <l% (thermal expansion should be occupied an leading position on the impact of system), polyol molecule chain is in cross-linked state and the prevailing hypothesis of the impact of convergent force on system is rational in a stretched state.
The Young's modulus of sample does not change with the change of frequency, and this may be because reach equilibrium state.Cross-linking density between sample is different, but its order of magnitude is accurately.The urethane Mc=662 of N3300 type triisocyanate synthesis; The urethane Mc=929 of N100 type triisocyanate synthesis; The urethane Mc:l 427 of HDI synthesis; Polyurethane and MC=2 229 of TDI synthesis.The MC value of the polyurethane samples of wherein being synthesized by TDI is 149 DEG C of mensuration, and the Mc value of other samples is 100 DEG C of mensuration.The theoretical value Me=874 of the soya-bean oil type polyvalent alcohol of three-functionality-degree and the Mc of HDI synthesis of polyurethane is worth as reference.
Observed value and the calculated value of Mc there are differences, cause the reason of this species diversity: a part be due to the theory of computation defect (this theory by hypothesis network model be that affine model calculates Mc, but actual molecules chain possibility length is inadequate, end-to-end distance does not reach the requirement of Gaussian distribution, and hypothesis is false.); Another part causes due to experimental error, but observed value is consistent with the order of magnitude of calculated value.
The chemical structure of isocyanic ester and experiment parameter (as stepping up power) may have certain influence to the modulus of sample, but the cross-linking density of polyurethane samples that the cross-linking density of the polyurethane samples of two kinds of triisocyanates synthesis synthesizes than two kinds of vulcabond is high.The urethane of aromatic series and alicyclic synthesis its modulus can not be measured higher than during rg, this is because more than 150 DEG C, sample decomposes.
Be the glass transition peak occurred within the scope of 20 ~ 100 DEG C, another kind is the transformation peaks that one 65 o[=occur.The second-order transition temperature of sample is: CB75N>RFE > MDI> RM DI> IPDI> TDI> N100 > N3330>HDI.Wherein the second-order transition temperature of the polyurethane samples of two kinds of aromatic tri-isocyanates synthesis is the highest, aromatic series and alicyclic diisocyanate (having two rings) take second place, and are then the samples that aromatic series and alicyclic diisocyanate (having a ring) synthesize.
The urethane of aliphatics three carbimide synthesis can be used for manufacturing leather, gathering of HDI synthesis
Ammonia ester can be used as rubber elastomer.8 of polyurethane samples transits out of a present 8O ~ mono-4O oI=; But except the polyurethane samples of RMDI synthesis, the transformation peaks of other polyurethane samples is all at one 65 DEG C.
The p transformation peaks of the polyurethane samples of RMDI synthesis is at one 30 cI=, this is because change relevant with molecular motion, molecular chain unsettled in other polyurethane samples is cut off by metathesis, and Lu's transformation is what to be caused by the conformational change of the cyclohexyl of two different fluoric acid esters in the urethane of RMDI synthesis.
Respectively by DSC, ' TMA and DMA measure Tg value there is identical trend.
Three, definition and application
Ink is the important materials for wrapping material printing, and pattern, the present stock curing ink of literal table are comprised main component and ancillary component by printing by it, and they mix equably and form the gluey fluid of a kind of viscosity through repeat-rolling.Be made up of pigment, low-melting ink vehicle and auxiliary agent and solvent etc.For various printings such as books and periodicals, packing and decorating, building decorations.Along with social demand increases, ink kind and output is respective extension and growth also.
Along with the develop rapidly of Chinese national economy, the prosperity of press-packaging industry has driven the manufacturing Fast Growth of ink, China is emerged rapidly between the nearest more than ten years and becomes one of ink manufacture big country of the world, current domestic ink industry size just maintains sustained and rapid growth with the speed of more than 10%.
The ink feature of environmental protection that current domestic production goes out is not strong, and even some is below standard, and high-grade ink is under-supply in addition.The development history of overall ink industry is positive, but some shortcomings existed and weak tendency, we also will improve and strengthen the market competitiveness of oneself, strengthen the input in science and technology of industry, strengthen the exploitation of environment-friendly ink, the development of ink should take autonomous innovation as main direction; Strengthen cultivation of ink theoretical investigation and skilled personnel etc.The enforcement of these measures, will push peak to the development of ink.
Four, composition and composition
The chemical structure of isocyanic ester and experiment parameter (as stepping up power) may have certain influence to the modulus of sample, but the cross-linking density of polyurethane samples that the cross-linking density of the polyurethane samples of two kinds of triisocyanates synthesis synthesizes than two kinds of vulcabond is high.The urethane of aromatic series and alicyclic synthesis its modulus can not be measured higher than during rg, this is because more than 150 DEG C, sample decomposes.
Be the glass transition peak occurred within the scope of 20 ~ 100 DEG C, another kind is the transformation peaks that one 65 o[=occur.The second-order transition temperature of sample is: CB75N>RFE > MDI> RM DI> IPDI> TDI> N100 > N3330>HDI.Wherein the second-order transition temperature of the polyurethane samples of two kinds of aromatic tri-isocyanates synthesis is the highest, aromatic series and alicyclic diisocyanate (having two rings) take second place, and are then the samples that aromatic series and alicyclic diisocyanate (having a ring) synthesize.
The urethane of aliphatics three carbimide synthesis can be used for manufacturing leather, gathering of HDI synthesis
Ammonia ester can be used as rubber elastomer.8 of polyurethane samples transits out of a present 8O ~ mono-4O oI=; But except the polyurethane samples of RMDI synthesis, the transformation peaks of other polyurethane samples is all at one 65 DEG C.
The p transformation peaks of the polyurethane samples of RMDI synthesis is at one 30 cI=, this is because change relevant with molecular motion, molecular chain unsettled in other polyurethane samples is cut off by metathesis, and Lu's transformation is what to be caused by the conformational change of the cyclohexyl of two different fluoric acid esters in the urethane of RMDI synthesis.
Respectively by DSC, ' TMA and DMA measure Tg value there is identical trend.
Its composition is substantially as follows: pigment (dyestuff) ... 10-15%
Solid resin (binder component) ... 25-35%
Auxiliary ... 0.5-4% stopping composition ... 0-15%
Organic solvent (volatile components) ... 40-60%.
Claims (8)
1. the soya-bean oil type news offset rotary ink formula main raw material that the present invention is novel is pulp from decoloured waste paper, quantitative 49-the 54g/m of paper, every face glue spread <6g/m2, glossiness 25% one 45%, whiteness 75% ~ 80% (example consumption);
Slurry therewith: mechanical pulp 65%, bleached sulphate softwood pulp 30%, pearl filler 5%; Stock freeness 60 ~ 70CSF (~: when producing newsprint, slurry dissociates 100CSF) cloth equipment mainly short delay knife coater of holding withg both hands, calendering equipment is more complicated, both organic interior hard rolling press, also organic interior soft press-polishing machine or the outer supercalender of machine;
Quantitative 52 ~ the 70g/m of the paper produced ~, every face glue spread 7 ~ 1lg/m, whiteness 75% ~ 80%, glossiness 20% ~ 30%;
Front paper machine copies wide 5.5m, speed of a motor vehicle lO00m/min, and throughput is low, does not possess and large-scale newspaper machine competitive strength.
2. net wide 5 9m, copy wide 5.4m, speed of a motor vehicle 1250m/min, throughput l4 ten thousand tons/year;
The wide 5.6m of paper machine net after transformation, copies wide 5.2m, speed of a motor vehicle 1260m/min, throughput 13 5 ten thousand tons/year;
The present invention novel soya-bean oil type news offset rotary ink formula primarily of Sym ~ o}ls head box, sp day 9d FormerHs former, be with the 4th separate press nips fgTfiwa ~ t unipress, Symsizer film sizer, Valmet two nip Opti concept of optimization soft press-polishing machine, standard winder and JagFloat rewinding machine composition;
Slurry therewith: mechanical pulp 65% ~ 70*/0, bleached sulphate softwood pulp 25% one 30%, pearl filler 5%, quantitative 45 ~ the 54g/m 2 of the paper produced, every face glue spread <6g/m2, whiteness 75% ~ 8 [Y/b, glossiness >45%; Machine finished coated newsprint is produced after transformation in 1988;
Improved paper machine speed 1 500ill/illin, nets wide 6.0ill, copies wide by 5.4111.
3. after transformation, paper machine is by TaillFlo head box, and TamFormer Hs former, is with 11amP1% II unipress of the 4th separate press nips, the hasty and careless cloth machine of SDTA Beloit scraper, Kleinew two nip soft press-polishing machine, standard winder and Vail-Top rewinding machine composition;
Mechanical pulp 65% ~ 70%, bleached sulphate softwood pulp 25% ~ 30%, pearl filler 5%, quantitative 45 ~ the 54g/m of the paper produced, every face glue spread <6g/nl, whiteness 75% ~ 80%, glossiness >45%;
Copy wide 7.6m before transformation, speed of a motor vehicle l200m/ II blood, produce traditional featherweight coated paper (LW C), main employing scraper for coating and the outer supercalendering of machine.
4. produced featherweight coated paper (Lw c) quantitative 47 ~ 66g, m (average 59g/m), every face glue spread 7-9.5g/m, glossiness 50% ~ 55%, whiteness 65% one 75%;
The soya-bean oil type news offset rotary ink formula slurry therewith that the present invention is novel: pulp from decoloured waste paper 60% one 70%, mechanical pulp l5% ~ 25%, bleached sulphate softwood pulp 1 (P/o mono-15%, calcium carbonate or kaolin clay filler 5%; The cold-set offset coated newsprint paper produced: quantitative 45-5Og/m, every face glue spread <6g/m, whiteness 75% 1 80%, glossiness >50%;
The thermo-oxidative stability of the soya-bean oil type news offset rotary ink formula soya-bean oil type polyurethane that the present invention is novel is higher than poly(propylene oxide) based polyurethanes; Soybean oil has very strong hydrophobicity, therefore will have good weathering resistance with the urethane of soybean oil synthesis;
The soya-bean oil type polyurethane of synthesis can be used for polyurethane foam, elastomerics, coating etc.;
Therefore, when completely crosslinked, a part (as from the 10th carbon atom to the 18th carbon atom) for molecular chain is not connected in cross-linked network, but unsettled, serves the effect of softening agent in system;
The performance of polymer network depends on their chemical structure and hands over density; Experiment shows, polyvalent alcohol and 4, and the urethane crosslinks density that 4 one phenylbenzene alkane vulcabond (MDI) synthesize is not high;
Second-order transition temperature (Tg is 5O ~ 7O DEG C) and modulus not high yet;
By changing the functionality of a 0H quantity or isocyanic ester in polyvalent alcohol; Cross-linking density can be changed.
5., because the chemical structure of isocyanic ester also affects the performance of urethane network, we discuss isocyanide ester functionality (two functionality and three-functionality-degree) and chemical structure (aliphatics, the alicyclic and aromatic series) impact on urethane performance under study for action;
Have various isocyanic ester to can be used for the synthesis of urethane, they impart the different performance of urethane; Compared with the urethane that wherein urethane and the aliphatics isocyanic acid of aromatic isocyanate synthesis synthesizes, there is higher rigidity, but it is oxidized and ultraviolet (uV) less stable;
Employ two kinds of aromatic diisocyanates (MDI and tolylene diisocyanate (TDI)); Two kinds of alicyclic diisocyanates (hexamethylene-diisocyanate (HDI)) and four kinds of triisocyanates (two kinds be aromatic series, two kinds be aliphatics);
The chemical structure of urethane is made up of polyvalent alcohol and isocyanic ester two kinds of structural units; The soya-bean oil type polyvalent alcohol that we use has four functionality, and irregular structure, thus avoid the crystallization of urethane, be obtained by reacting single-phase random thermosetting resin with vulcabond or triisocyanate;
The chemical structure of isocyanic ester affects rigidity and the cross-linking density of urethane network; Along with the change of isocyanic ester kind, the rigidity order of urethane network is as follows: the alicyclic < aromatic series of aliphatics <;
The cross-linking density of the urethane that triisocyanate synthesizes is higher compared with two isocyanide ester fat, so affect sample density, 71g, mechanical property, swelling property; If know the interaction parameter of solvent and polymkeric substance, then cross-linking density is estimated by polymkeric substance swelling property in a solvent;
Usually, degree of swelling is higher, and cross-linking density is lower, and the solvent as polymkeric substance is better; The degree of swelling of urethane in toluene of aliphatics, alicyclic diisocyanate resin synthesis is maximum, aromatic diisocyanate and the different urethane of trembling vinegar synthesis of aliphatics three take second place, the urethane degree of swelling of two kinds of aromatic tri-isocyanates synthesis is minimum, and the degree of swelling of the urethane wherein synthesized than Desmodru RFE with the degree of swelling of the urethane of CB75N synthesis is low.
6. suppose that cross-linking density is identical, then the degree of swelling of urethane of aliphatics triisocyanate synthesis is greater than the urethane of aromatic tri-isocyanates synthesis, for the two, and the good solvent of the toluene urethane of aliphatics triisocyanate synthesis especially;
Also same rule is had for aliphatics and alicyclic triisocyanate; Different isocyanic ester is on the impact of density;
Can find out, the urethane synthesized by aromatic tri-isocyanates RFE, CB75 N has the highest density;
The density of the urethane of aromatic series dicyanate MDI, TDI and aliphatics triisocyanate N100, N3300 synthesis is taken second place;
The density of the urethane of aliphatics and alicyclic diisocyanate synthesis is minimum;
Obviously, the benzene ring structure of isocyanic ester is larger than the impact of cross-linking density on the impact of density polymer;
The Young's modulus of all samples sharply increases along with the increase of temperature; This phenomenon is demonstrated by the test of bend specimen and tension specimen; The rubber elasticity theory that prediction modulus increases with the increase of temperature: E=3 R T=3 P R T/M C (1) are wherein the concentration of living chain; R is gas law constant; T is absolute temperature; P is density; Me is the equal molecular mass of number of network medium chain;
The molecular chain group that modulus increases is because its molecular chain convergent force increases, entropy increase, and forms the molecular chain ball of string shunk;
Sample can be observed the convergent force of thermo-elasticity or increase when being in rubbery state, but only has sample higher than thermo-elasticity transition point, is in when drawing secondary state and just can observes;
General elongation is about 7%; Comparatively large to system contribution lower than this thermal expansion, shrink system contribution large higher than this scope entropy.
7. demonstrate as Zhongchang rate <l% (thermal expansion should be occupied an leading position on the impact of system), polyol molecule chain is in cross-linked state and the prevailing hypothesis of the impact of convergent force on system is rational in a stretched state;
The urethane Mc=662 of N3300 type triisocyanate synthesis; The urethane Mc=929 of N100 type triisocyanate synthesis; The urethane Mc:l 427 of HDI synthesis; Polyurethane and MC=2 229 of TDI synthesis; The MC value of the polyurethane samples of wherein being synthesized by TDI is 149 DEG C of mensuration, and the Mc value of other samples is 100 DEG C of mensuration; The theoretical value Me=874 of the soya-bean oil type polyvalent alcohol of three-functionality-degree and the Mc of HDI synthesis of polyurethane is worth as reference;
Observed value and the calculated value of Mc there are differences, cause the reason of this species diversity: a part be due to the theory of computation defect (this theory by hypothesis network model be that affine model calculates Mc, but actual molecules chain possibility length is inadequate, end-to-end distance does not reach the requirement of Gaussian distribution, and hypothesis is false; ); Another part causes due to experimental error, but observed value is consistent with the order of magnitude of calculated value;
The chemical structure of isocyanic ester and experiment parameter (as stepping up power) may have certain influence to the modulus of sample, but the cross-linking density of polyurethane samples that the cross-linking density of the polyurethane samples of two kinds of triisocyanates synthesis synthesizes than two kinds of vulcabond is high; The urethane of aromatic series and alicyclic synthesis its modulus can not be measured higher than during rg, this is because more than 150 DEG C, sample decomposes;
Be the glass transition peak occurred within the scope of 20 ~ 100 DEG C, another kind is the transformation peaks that one 65 o=occur; The second-order transition temperature of sample is: CB75N>RFE > MDI> RM DI> IPDI> TDI> N100 > N3330>HDI; Wherein the second-order transition temperature of the polyurethane samples of two kinds of aromatic tri-isocyanates synthesis is the highest, aromatic series and alicyclic diisocyanate (having two rings) take second place, and are then the samples that aromatic series and alicyclic diisocyanate (having a ring) synthesize;
The urethane of aliphatics three carbimide synthesis can be used for manufacturing leather, and the urethane of HDI synthesis can be used as rubber elastomer; 8 of polyurethane samples transits out of a present 8O ~ mono-4O oI=; But except the polyurethane samples of RMDI synthesis, the transformation peaks of other polyurethane samples is all at one 65 DEG C;
The p transformation peaks of the polyurethane samples of RMDI synthesis is at one 30 cI=, this is because change relevant with molecular motion, molecular chain unsettled in other polyurethane samples is cut off by metathesis, and Lu's transformation is what to be caused by the conformational change of the cyclohexyl of two different fluoric acid esters in the urethane of RMDI synthesis;
The Tg value measured respectively by DSCTMA and DMA has identical trend;
The present invention novel soya-bean oil type news offset rotary ink formula ink be for wrapping material printing important materials, pattern, the present stock curing ink of literal table are comprised main component and ancillary component by printing by it, and they mix equably and form the gluey fluid of a kind of viscosity through repeat-rolling; Be made up of pigment, low-melting ink vehicle and auxiliary agent and solvent etc.; For various printings such as books and periodicals, packing and decorating, building decorations; Along with social demand increases, ink kind and output is respective extension and growth also;
The chemical structure of isocyanic ester and experiment parameter (as stepping up power) may have certain influence to the modulus of sample, but the cross-linking density of polyurethane samples that the cross-linking density of the polyurethane samples of two kinds of triisocyanates synthesis synthesizes than two kinds of vulcabond is high; The urethane of aromatic series and alicyclic synthesis its modulus can not be measured higher than during rg, this is because more than 150 DEG C, sample decomposes;
Be the glass transition peak occurred within the scope of 20 ~ 100 DEG C, another kind is the transformation peaks that one 65 o=occur; The second-order transition temperature of sample is: CB75N>RFE > MDI> RM DI> IPDI> TDI> N100 > N3330>HDI; Wherein the second-order transition temperature of the polyurethane samples of two kinds of aromatic tri-isocyanates synthesis is the highest, aromatic series and alicyclic diisocyanate (having two rings) take second place, and are then the samples that aromatic series and alicyclic diisocyanate (having a ring) synthesize;
The urethane of aliphatics three carbimide synthesis can be used for manufacturing leather, and the urethane of HDI synthesis can be used as rubber elastomer; 8 of polyurethane samples transits out of a present 8O ~ mono-4O oI=; But except the polyurethane samples of RMDI synthesis, the transformation peaks of other polyurethane samples is all at one 65 DEG C;
The p transformation peaks of the polyurethane samples of RMDI synthesis is at one 30 cI=, this is because change relevant with molecular motion, molecular chain unsettled in other polyurethane samples is cut off by metathesis, and Lu's transformation is what to be caused by the conformational change of the cyclohexyl of two different fluoric acid esters in the urethane of RMDI synthesis.
8. respectively by DSC, ' TMA and DMA measure Tg value there is identical trend;
The novel soya-bean oil type news offset rotary ink of the present invention its composition of filling a prescription is substantially as follows: pigment (dyestuff) ... 10-15%
Solid resin (binder component) ... 25-35%
Auxiliary ... 0.5-4% stopping composition ... 0-15%
Organic solvent (volatile components) ... 40-60%.
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