CN1746038A - Recording sheets and image forming method using the recording sheets - Google Patents
Recording sheets and image forming method using the recording sheets Download PDFInfo
- Publication number
- CN1746038A CN1746038A CN 200510051147 CN200510051147A CN1746038A CN 1746038 A CN1746038 A CN 1746038A CN 200510051147 CN200510051147 CN 200510051147 CN 200510051147 A CN200510051147 A CN 200510051147A CN 1746038 A CN1746038 A CN 1746038A
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- Prior art keywords
- paper
- record
- starch
- amidin
- pulp
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- Granted
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Images
Landscapes
- Paper (AREA)
- Ink Jet Recording Methods And Recording Media Thereof (AREA)
- Ink Jet (AREA)
Abstract
The invention discloses a recording sheet whcih is obtained by coating a base paper including pulp with a surface sizing agent including a starch as a main component, wherein the recording sheet exhibits a reflection density in a specific range when provided with a povidone-iodine liquid. Also disclosed is a recording sheet prepared by coating the surface of a base paper including a pulp fiber and a filler as main components with a processing liquid including a starch, wherein when 0.06 m<2>of the recording sheet is subjected to hot water extraction, a solid amount of an extract is 0.01 to 0.4 g and a carboxyl group content in the solid is 0 to 5 meq/100 g.
Description
Technical field
The ink-jet imaging method that the present invention relates to record-paper, uses the electrophotographic image forming method of this record-paper and use this record-paper.
Background technology
Utilizing the duplicator of electrophotographic method and laser printer is essential tool in the office.Use common paper in this class machine.This common paper is the record-paper with the coating that comprises pigment.
It is universal that ink jet recording method has become in office, because this method can be easily painted, used energy is less, and the recording noise that is produced is less, and reduced the producing cost of printer.Therefore, the feature that the so-called common paper of using in the office must have is, this class common paper can be used for electrophotographic recording method and ink jet recording method and not have problems.
Yet in the electrophotographic recording method, when when being transferred to toner image on the paper and carrying out heat fixation, paper takes place to curl.This be because when heat fixation the single face of heating paper only, and only remove the moisture of paper from heating surface.Therefore, for example exist in paper delivery and paperboard partly takes place and problem such as defective on collection tray, occurs piling up.
In order to solve the problem of curling the printing back a lot of suggestions have been proposed.An one example (being disclosed in Japanese kokai publication hei 5-341554) is conceived to the tension force of paper inherence, and the method for its proposition is included in when copying paper and dry paper the transfer paper dry method that stretches.Humidity when its another example comprises control packing paper with the moisture of reduction paper, thereby reduces the percentage elongation of paper when suction.For example the flat 7-219262 of Japanese kokai publication hei 5-241366 and Te Kai has proposed to limit immediately the method for the moisture of coated paper after press polish is handled.
Other method has been proposed among the Japanese kokai publication hei 6-138688, that is, and the method for the moisture when fiber orientation difference and qualification packing are opened between two surfaces of reduction paper.It is believed that by reducing the difference of fiber orientation between two surfaces, can reduce the difference of percentage elongation characteristic between two surfaces.Yet, in the heat fixation of the electrophotographic method part fixedly the most common way of toner be with paper clamp between heater block and extruder member.Because heater block and extruder member have different temperatures, the percentage elongation between two surfaces produces difference.Therefore, be difficult to curling behind this method inhibition heat fixation.Even the moisture of paper is reduced when unpacking, paper also can be opened the back in packing and absorb moisture.Therefore, the low moisture content in the packing is very little to the curling action that suppresses behind the heat fixation.
Japanese kokai publication hei 8-123066 discloses another kind of method, and this method defines the moisture of paper when unpacking by the coating of porous pigment layer.Yet although for coat of colo(u)r provides hole improving picture quality, the existence of hole curling after to heat fixation do not exert an influence.In addition, as mentioned above, even the moisture of paper has obtained reduction when unpacking, but the back paper of unpacking still can absorb moisture.Therefore, the inhibitory action of curling of the low moisture content in the packing after to heat fixation is very little.
Another method is disclosed among the Japanese kokai publication hei 11-282193, the moisture of paper when promptly limiting the elongation of paper in water and unpacking.Yet curling behind the heat fixation is the change in size of the paper under the drying regime.Therefore, because elongation is the change in size of the paper in the dampness extremely in the water, so can not suppress curling behind the heat fixation by elongation in the control water.As mentioned above, even reduced moisture when unpacking, the back paper of unpacking still can absorb moisture.Therefore, the inhibitory action of curling of the low moisture content in the packing after to heat fixation is very little.
Disclose a kind of method among the Japanese kokai publication hei 6-202371, the moisture of this method in limiting packing, also defined the moisture that is under 28 ℃, 85%RH (relative humidity) condition.This method define equilibrium moisture content in the high humidity environment and the moisture when unpacking between difference.This method also is conceived to the easy degree that paper absorbs moisture.Therefore, this method can not suppress fully effectively by curling behind the heat fixation of dehydration generation.Also have some other methods to be disclosed in Japanese kokai publication hei 6-295087 and the flat 11-338181 of Te Kai.Yet these methods can not suppress curling behind the heat fixation fully effectively.
Japanese kokai publication hei 3-287894 discloses the method that limits the paper that the comprises reuse paper moisture under 20 ℃, 65%RH condition.Yet this method is conceived to the easy degree that paper absorbs moisture.Therefore, this method can not suppress fully effectively by curling behind the heat fixation of dehydration generation.
The development of duplicator and printer makes their miniaturizations and for example have automatic double face copying and multiple function such as bookbinding automatically.Along with the development of duplicator and printer, it is complicated that the frame for movement of equipment and paper path become, and the diameter of heat-fixing roll diminishes, and heat-fixing roll becomes complicated.Therefore, even by the change in size difference between the above-mentioned technology reduction paper two sides, when using this paper under high humidity, serious curling still can take place in paper.When this paper was used for the printing of little printer of the one side of heating paper only, this curled obvious especially.Owing to take place to curl, the end of paper is the parts in the contact arrangement probably, thereby are easy to cause paperboard.Therefore, suppress curling behind the heat fixation unsatisfactorily with aforesaid conventional method.
Also have problems when adopting ink jet recording method on common paper, to print.For example, colouring agent can not remain on the paper, makes colour development performance deficiency thus.In addition, because used water-soluble colorant, the image resistance to water deficiency that is write down.Above-mentioned conventional art does not address these problems.
In order to address this problem, a kind of method is proposed in No. 296368 communique of Japan Patent.In this method, the printing ink that will comprise water-soluble dye is used to comprise the record on the paper of ionic substance, and this ionic substance has and the opposite ion polarity of water-soluble dye in the printing ink.Yet if this method uses the paper of hydrophobicity deficiency to print, and use rapid draing printing ink for example is used for the printing ink of high-speed printer, colour development mis-behave.This is because of the very fast infiltration paper of printing ink, and the colouring agent in the printing ink arrives paper inside, thereby reduces the colouring agent relative quantity that remains on the paper surface.
In the said method, because paper comprises a large amount of highly ionized materials, paper can be subjected to the excessive influence of environmental change, so that the resistance of paper reduces.Therefore, this paper may be to the transfer printing generation ill-effect of toner in electrophotographic printer or the electrophotographic copier.Thereby, also there is not to solve the shared paper (referring to Japanese kokai publication hei 10-166713 and the flat 7-257017 of Te Kai) of electrophotographic recording and ink mist recording problem.In addition, can not suppress curling behind the paper heat fixation with conventional method.
In the conventional ink jet printers, usually, black ink comprises pigment and infiltrates record-paper at leisure, and colored ink comprises dyestuff and infiltrates record-paper soon, thereby can improve the quality of black literal, and the paper (intercolor bleed) that can suppress to spread and sink between look.Yet, be used to print image if can infiltrate the colored ink of record-paper soon with high record density, print the back paper serious curling can be taken place at once, occur in the printer scratch occurring in paperboard or the image-region thereby make.
In addition, want spended time or make ink setting want spended time because the record-paper that curls at once after the printing is unfolded, so printing effect is extremely low under the duplex printing situation.When printing the high record density image, curling that air-dry back produces is very serious.Therefore, can not satisfy simultaneously high-quality fully and to the requirement of the inhibition aspect of curling.
As mentioned above, being crimped onto in electrophotographic system and the ink-jet system of record-paper is a big problem.
Except that said method, proposed multiple other method and suppressed curling of record-paper in the electrophotographic system.The example comprises: the method for the remnant curvature of disclosed control transfer paper among the Japanese kokai publication hei 3-243953; The method of disclosed control content of ashes difference among the flat 7-295280 of Japanese kokai publication hei 7-202897 and Te Kai, this method is conceived to the property difference between the transfer paper two sides; The method of disclosed control percentage elongation difference among the Japanese kokai publication hei 3-236062; The method of disclosed control paper density variation among the Japanese kokai publication sho 58-176641; The method of disclosed control freedom difference among the Japanese kokai publication hei 6-110243.
Yet even if reduced change in size difference between the paper two sides with above-mentioned technology, but when using this paper under high humidity, serious curling still can take place in paper.When the printing of the little printer that this paper is used for the one side of heating paper only, this curls obvious especially.Owing to take place to curl, the end of paper is the parts in the contact arrangement probably, thereby cause paperboard easily.
For curling of suppressing to take place in the ink-jet system, proposed to use formaldehyde resin to wait the percentage elongation when suppressing to absorb water among Japanese kokai publication hei 10-046498 and the Te Kai 2002-201597 so that the method that suppresses to curl.Yet, mixes with paper material with material if copy will suppress before the paper to curl, because the curling high response of using material of inhibition, the cellulose fibre in the paper can flocculate, thereby makes the surface quality severe exacerbation.
Even providing suppress to curl by size press use material, suppress curling also can initiation reaction before applied with material, surface size become sticky and flocculate.Therefore, reduced the inhibition that touches the cellulose fibre in the paper and curled, thereby can not obtain enough curling inhibition effects with the amount of material.
Carry out image when record with ink jet recording method, with multiple starch for example enzymically modified starch and cationic starch as the Cypres of the paper that is intended to prevent to spread and sink in.
As enzymically modified starch, reported the multiple starch of handling through amylase (for example Japanese kokai publication hei 1-156595, spy open flat 1-162894, spy open flat 2-3000, spy and open in 2000-307813 and the flat 10-219596 of Te Kai and No. 3237104 communique of Japan Patent and No. 2936996 communique).Using enzymically modified starch in the record-paper is effectively for the paper that prevents to spread and sink in, but can not suppress curling fully effectively.
TOHKEMY 2004-143612 proposes a kind of record-paper, and this record-paper uses cationic starch as the Cypres that is used to suppress to curl.Yet when cationic starch infiltrated paper inside, cationic starch had strengthened the formation of hydrogen bond between cellulose fibre.Therefore, when this paper is used for electrophotographic image when record under the high humidity, use cationic starch can make behind the heat fixation curl more serious.When unusable paper in the ink-jet recording system of the big water gaging of use, also can curl, and the parts in the paper edge contact machine, thereby be easy to generate paperboard etc.
As mentioned above, be not enough to prevent to curl as the Cypres in the record-paper by using starch according to conventional method.
Summary of the invention
In view of the problems referred to above of conventional art, finished the present invention.
One aspect of the present invention provides a kind of record-paper.The basic paper that the Cypres coating that described record-paper employing is main component with starch comprises paper pulp obtains.With this record-paper after leaving standstill 5 hours under 23 ℃, the condition of 50%RH, on the surface of this recording medium with 10ml/m
2Amount PVP-I concentration is provided is that 70mg/ml and available iodine content are the PVP-I liquid of 7mg/ml, then this record-paper was left standstill 5 hours under 23 ℃, the condition of 50%RH, the reflection density on surface with described PVP-I liquid is for smaller or equal to 0.60.
Another aspect of the present invention provides a kind of image recording process.This image recording process comprises: uniform charging is carried out on the surface to the electrostatic latent image holding member; The face exposure that makes this electrostatic latent image holding member is to form electrostatic latent image; Make this latent electrostatic image developing to form toner image with electrostatic developer; This toner image is transferred to the record-paper surface; This toner image is fixed on this record-paper surface.In this method, the basic paper that the Cypres coating that described record-paper employing is main component with starch comprises paper pulp makes.Described record-paper is such paper: with this record-paper after leaving standstill 5 hours under 23 ℃, the condition of 50%RH, on the surface of this recording medium with 10ml/m
2Amount PVP-I concentration is provided is that 70mg/ml and available iodine content are the PVP-I liquid of 7mg/ml, then this record-paper was left standstill 5 hours under 23 ℃, the condition of 50%RH, the reflection density on surface with described PVP-I liquid is for smaller or equal to 0.60.
Another aspect of the present invention provides a kind of ink jet recording method.This recording method comprises to record-paper provides droplet of ink, thus on this record-paper surface document image.In this method, the basic paper that the Cypres coating that described record-paper employing is main component with starch comprises paper pulp makes.Described record-paper is such paper: with this record-paper after leaving standstill 5 hours under 23 ℃, the condition of 50%RH, on the surface of this recording medium with 10ml/m
2Amount PVP-I concentration is provided is that 70mg/ml and available iodine content are the Betagen Solution of 7mg/ml, then this record-paper was left standstill 5 hours under 23 ℃, the condition of 50%RH, the reflection density on surface with described Betagen Solution is for smaller or equal to 0.60.
Further investigate the result of crimping mechanism behind the heat fixation as the present inventor, have been found that: if be coated with the record-paper surface with the treatment fluid that comprises starch, the feasible solid that is obtained by the hot water extracting of this record-paper has the carboxyl-content of 0～5meq/100g (mM/100 grams), then can in the electrophotographic recording method, suppress to curl behind the heat fixation, and can in ink jet recording method, improve color rendition.
The record-paper that is used for the electrophotographic recording method comprises conductive agent.The inventor also finds, by with multivalent metal salt as conductive agent with the record-paper surface treatment to predetermined extent, both can keep the transfer printing in the electrophotographic recording, also can obtain the high color repeatability in the ink mist recording simultaneously.Specifically:
Another aspect of the present invention provides a kind of record-paper, and this record-paper is by being that the surface of the basic paper of main component prepares with the treatment fluid coating that comprises starch with paper pulp fiber and filler.This record-paper is such record-paper: when to 0.06m
2Record-paper when carrying out hot water extracting, the amount of solid of this extract is 0.01g～0.4g, and carboxyl-content is 0～5 mM/100 grams in this solid.
In one embodiment, described treatment fluid comprises the salt of the above metal of divalence or divalence, and under 23 ℃, the condition of 50%RH, the surface resistivity of this record-paper and the ratio of specific insulation are 0.1～1, and its surface resistivity is 1.0 * 10
9Ω/sq～1.0 * 10
11Ω/sq, and specific insulation is 5.0 * 10
9Ω cm～5.0 * 10
11Ω cm.
The carboxyl amount of the starch in the described treatment fluid can be 0～5 mM/100 grams.
Another aspect of the present invention provides a kind of image recording process.This image recording process comprises: uniform charging is carried out on the surface to the electrostatic latent image holding member; The face exposure that makes this electrostatic latent image holding member is to form electrostatic latent image; Make this latent electrostatic image developing to form toner image with electrostatic developer; Toner image is transferred to the record-paper surface; This toner image is fixed on this record-paper surface.In this method, described record-paper is selected from above-mentioned record-paper.
Another aspect of the present invention provides a kind of image recording process.This image recording process comprises to the record-paper surface provides droplet of ink, and this droplet of ink comprises colouring agent and is selected from water and at least a material of water-miscible organic solvent.In this method, described record-paper is selected from above-mentioned record-paper.
Another aspect of the present invention provides a kind of record-paper, the basic paper that the Cypres coating that described record-paper employing is main component with starch comprises paper pulp obtains, wherein, with this record-paper after leaving standstill 5 hours under 23 ℃, the condition of 50%RH, on the surface of this recording medium with 10ml/m
2Amount PVP-I concentration is provided is that 70mg/ml and available iodine content are the PVP-I liquid of 7mg/ml, then with this record-paper after leaving standstill 5 hours under 23 ℃, the condition of 50%RH, the reflection density on surface with described PVP-I liquid is for smaller or equal to 0.60; And work as 0.06m
2Record-paper when carrying out hot water extracting, the amount of solid of this extract is 0.01g～0.4g, and carboxyl-content is 0～5 mM/100 grams in this solid.The basic paper of this record-paper can further comprise filler.Described Cypres can comprise the above metal of divalence or divalence, and under 23 ℃, the condition of 50%RH, the surface resistivity of this record-paper and the ratio of specific insulation are 0.1～1, and its surface resistivity is 1.0 * 10
9Ω/sq～1.0 * 10
11Ω/sq, and specific insulation is 5.0 * 10
9Ω cm～5.0 * 10
11Ω cm.
The starch that uses in the above-mentioned aspect can be that this method comprises by the starch of following method preparation: starch and water are mixed to form amidin; Heat this amidin, so that this amidin gelation; Under the temperature that is lower than this gelation heating-up temperature, make this amidin slaking then; Then by in this amidin, adding enzyme so that this starch is carried out enzyme modification; Heat this amidin then so that this enzyme deactivation and stop the reaction.
Description of drawings
Fig. 1 is the schematic diagram that is used to explain the method that is used for measuring the curling height of being represented by h.
The specific embodiment
Hereinafter, will use title " first embodiment " and " second embodiment " to explain the present invention.
First embodiment
Record-paper
In the first embodiment, the invention provides a kind of record-paper, the basic paper that the Cypres coating that described record-paper employing is main component with starch comprises paper pulp obtains, wherein, with this record-paper after leaving standstill 5 hours under 23 ℃, the condition of 50%RH, on the surface of this recording medium with 10ml/m
2Amount PVP-I concentration is provided is that 70mg/ml and available iodine content are the Betagen Solution of 7mg/ml, then with this record-paper after leaving standstill 5 hours under 23 ℃, the condition of 50%RH, the reflection density on surface with described Betagen Solution is for smaller or equal to 0.60.
When using the record-paper of first embodiment to carry out the image record by electro photography or ink jet type duplicator or printer, can suppress described and curl.
Reflection density is the index of the lip-deep coloring degree with lower area of expression record-paper, and this zone is by the zone of the dyeing of the chromogenic reaction between iodine and the starch.This coloring degree is subjected to the influence of the form of described starch.Be known that if the grape sugar chain of starch is short more, the impossible more helical structure that mixes this grape sugar chain of iodine, thus can reduce reflection density.Also known, the starch crystallization that is caused by slaking can improve hydrophobicity, and the hydrophobicity that improves will reduce the ability of absorption iodine, thereby reduces reflection density.
In other words, the hydrophobicity raising of starch can cause reflection density to reduce.Therefore, along with the reflection density step-down, the record-paper that causes because of the heat of heat fixation in the electrophotographic image record can diminish in the variation near the moisture of the part on surface, thereby can more easily suppress curling.In the ink jet image record, if reflection density is lower, the water that absorbs immediately after then printing is less, thereby reduced the former infiltration record-paper amount of moisture evaporated in the drying process after printing then, what take place immediately after therefore making it possible to suppress with comparalive ease to print curls and record-paper curling after air-dry.
Therefore, in order to suppress curling, under the situation of the record-paper that uses first embodiment, described reflection density can be smaller or equal to 0.6, preferably smaller or equal to 0.57, is more preferably less than and equals 0.55, more preferably smaller or equal to 0.53.Reflection density is low more preferred more among the present invention.
Yet, must provide the spread and sink in paper of a certain amount of at least starch when preventing inkjet printing to record-paper.Described starch can mix before copying paper with the composition of paper, and/or was applied to record-paper after copying paper.Therefore, reflection density is more preferably more than or equal to 0.35 preferably more than or equal to 0.30.
Reflection density is to measure by the following method: this record-paper is left standstill 5 hours with the control water content under 23 ℃, the condition of 50%RH; Then to the surface of this recording medium with 10ml/m
2Amount PVP-I concentration is provided is that 70mg/ml and available iodine content are the Betagen Solution of 7mg/ml; Then this record-paper was left standstill 5 hours under 23 ℃, the condition of 50%RH; Measure this surperficial reflection density with the reflection density measuring instrument afterwards.
Though quote PVP-I liquid herein as the iodine source that is used for starch-iodine reaction, also can use commercially available PVP-I gargle to replace, as long as the iodine of identical effective dose is provided to the lip-deep unit are of this record-paper.Can provide PVP-I liquid to the surface of this record-paper with rubbing method or spray-on process, as long as with 10ml/m
2The amount of (calculating with undiluted solution) provides described liquid to get final product on this surface equably.
In the measurement of reflection density (vision concentration), will be used as measuring instrument by the X-RITE 938 that X-rite produces, as light source, measuring the visual field is 2 ° of visuals field with the D50 light source, aperture scale is 8mm.In the measurement, measure the reflection density value of ten points in the scraps of paper of 50mm * 50mm size, regard the mean value of these ten values the reflection density of this paper as, wherein, these scraps of paper at random are selected from the zone by starch-iodine reaction dyeing.
The scope of the term of Shi Yonging " starch " comprises starch and starch derivatives herein, for example the enzymically modified starch of having handled with enzyme.The starch that uses in the Cypres is not particularly limited with the processing that is applied to starch, as long as the record-paper that obtains demonstrates the packing density smaller or equal to 0.6 in above-mentioned measurement.In one embodiment, can be used in combination two or more starch.
The starch that uses in the record-paper of first embodiment is preferably in the past as the oxidized starch of Cypres, or the starch that has a high hydrophobicity more than common starch enzymically modified starch for example.This starch can be the enzymically modified starch by following method preparation.
Preferred enzymically modified starch (below be sometimes referred to as " enzymically modified starch F ") makes by the following method: the heating amidin, so that this amidin gelation; Under the temperature that is lower than above-mentioned gelation heating-up temperature, make this amidin slaking then; Then by in this amidin, adding enzyme so that this starch is carried out enzyme modification; Heat this amidin then so that this enzyme deactivation and stop the reaction.
On the other hand, when preparing traditional enzymically modified starch, the heating amidin adds enzyme simultaneously, then cooling.In the conventional method, omitted the curing step in the said method of the present invention, in fact, be used for the heating of the gelling starches aqueous solution simultaneously and be used to make the heating of enzyme deactivation.
When enzymically modified starch F when the Cypres, obtain in above-mentioned measurement, demonstrating record-paper easily smaller or equal to 0.6 reflection density.Therefore, enzymically modified starch F is very effective for suppressing and preventing to curl.This estimation is because enzymically modified starch F has higher hydrophobicity than traditional starch.It is believed that, the reason that enzymically modified starch F hydrophobicity is high should be as described below: when carrying out slaking after the heating that is being used for the gelling starches aqueous solution, pine for the starch crystallization once again of dissolving and expanding being used for adding of the gelling starches aqueous solution, the suction of the starch of crystallization has obtained inhibition again, thereby has strengthened the hydrophobicity of the enzymically modified starch F that obtains.Preferably carry out the preparation of enzymically modified starch F with following condition.
-gelation
The starch that uses in the preparation is not particularly limited, and can be for example cornstarch, tapioca, farina, wheaten starch or rice starch of traditional starch.
The concentration of starch preferably 8 weight %～20 weight %, more preferably 10 weight %～15 weight % in the amidin.Preferably 90 ℃～120 ℃ of heating-up temperatures (heating-up temperature that is used for the gelling starches aqueous solution), more preferably 95 ℃～100 ℃.Preferably 20 minutes～60 minutes processing time, more preferably 30 minutes～45 minutes.
-slaking
Amidin after the gelation is cooled off naturally or force cooling, carry out slaking at low temperature then with frozen water etc.Preferably 20 ℃～50 ℃ of curing temperatures, more preferably 25 ℃～40 ℃.Preferably 60 minutes～180 minutes processing time, more preferably 60 minutes～120 minutes.
-modification
Carry out enzyme modification by adding the amidin of enzyme after to slaking.Described enzyme can be for example AMS, beta amylase or glucoamylase.The amount of the enzyme that uses (enzyme concentration) is 0.01 weight % of amount of starch～1.00 weight % preferably, are more preferably the 0.02 weight %～0.5 weight % of amount of starch.Reaction time (adding the time span between enzyme and the beginning enzyme deactivation operation subsequently) is preferably 1 minute～10 minutes, more preferably 1 minute～3 minutes.
-inactivation
After the modification, starch solution is heated to high temperature, so that enzyme deactivation and stop enzyme modification reaction.Heating-up temperature is preferably 90 ℃～120 ℃, more preferably 95 ℃～100 ℃.Processing time is preferably 5 minutes～and 20 minutes, more preferably 6 minutes～10 minutes.
The instantiation of preparation enzymically modified starch F is described below.
Put hot bath (be higher than and equal 95 ℃) into holding the container that 180g contains the liquid of 8 weight % cornstarch, and make cornstarch liquid boil 30 minutes (gelation).Then, by container is put into ice-water bath etc., made cornstarch liquid be cooled to 40 ℃ through about 30 minutes.Cornstarch liquid is put into ampoule, and bottle is left standstill 30 minutes (slaking) in 40 ℃ hot bath.Then, in each bottle, add the enzyme (AMS, name of product " KLEISTASE PA ") of scheduled volume, and with about 2 minutes of the cornstarch liquid strong agitation (modification) in the bottle.After the stirring, bottle is put into the hot bath (be higher than and equal 95 ℃) of boiling, and leave standstill 6 minutes, so that make enzyme deactivation (inactivation).Then, this starch fluid is cooled to room temperature also as Cypres.
For the purpose of reference, the preparation method of traditional enzymically modified starch is described below.In the preparation, put into hot bath (be higher than and equal 95 ℃), and make starch fluid boiling 30 minutes having held the liquid that comprises 20 weight %～30 weight % cornstarch and the container of scheduled volume enzyme (AMS, name of product " KLEISTASE PA ").Then, this starch fluid is cooled to room temperature also as Cypres.
Can control the hydrophobicity of enzymically modified starch F by suitably adjusting the condition enzyme concentration when adjusting starch conversion for example in each operation.
In order to suppress curling, can select described condition, make the record-paper that obtains by the surface size coated base paper that comprises enzymically modified starch F with above-mentioned routine processes and when measuring, demonstrate reflection density smaller or equal to 0.6.The preferred production method of not only considering reflection density but also considering record-paper is selected described condition.For example, if this starch with enzyme modification exceedingly, the viscosity of surface size can be too low so, has the problem of the drippage of liquid for example probably.
Conventional art was once attempted to improve the permeability that Cypres infiltrates paper by the difference between the reduction paper two sides or by using traditional enzymically modified starch to wait, and suppressed to cause to occur in double-sided copying or the printing curling of paperboard.
Yet, when forming image with high humidity with duplicator with than the another side stronger frame for movement of being heated that makes paper one side or printer on traditional record paper, paperboard appears when double-sided copying or duplex printing probably.This is because the change in size of the one side of being heated is probably greater than the change in size of another side on the paper, thereby serious curling takes place.
On the other hand, when have higher hydrophobic starch for example enzymically modified starch F when the Cypres, the change in size of the one side of being heated can be not significantly greater than the change in size of another side.Therefore, the paperboard in the time of can suppressing double-sided copying or printing.
When preparing the record-paper of first embodiment, comprise the surface size coated base paper of Cypres by using, thereby provide Cypres to this record-paper surface.The concentration of Cypres preferably 5 quality %～15 quality %, more preferably 8 quality %～12 quality % in the surface size.
Described Cypres is enzymically modified starch F especially preferably.Can use other Cypres for example polyvinyl alcohol and traditional starch (for example traditional enzymically modified starch and oxidized starch) in addition, be smaller or equal to 0.6 as long as can keep reflection density.
The amount that is attached to the Cypres of paper is preferably 0.1～5.0g/m
2Every single face, more preferably 1.0～3.0g/m
2Every single face.
Surpass 5.0g/m if be attached to the amount of each surperficial Cypres
2, then the amount of the lip-deep Cypres of record-paper is bigger, thereby can increase the contact point between the cellulose fibre in the record-paper.The contact point that increases is strengthened sometimes curling and is wrinkling.Be lower than 0.1g/m if be attached to the amount of each surperficial Cypres
2, then the amount of the lip-deep Cypres of record-paper is less, thus Cypres can not make pigment of using simultaneously with Cypres etc. be fixed in basic paper surface.Therefore, when the record-paper of transfer printing gained in electro photography or ink jet type imaging device, during transfer printing probably generation can cause a large amount of paper powder of mechanical disorder.
The record-paper of first embodiment has preferred 10～50 evenness index, and more preferably this evenness index is 15～40.If evenness index is lower than 10, the inhomogeneities of quality may cause the inhomogeneous of image transfer printing in the xerography.If evenness index is higher than 50, paper must be pulled an oar to higher degree, guaranteeing uniformity, thereby can cause sometimes curling strengthens.
The evenness index of Shi Yonging is meant with little evenness tester (MFT:Micro FormationTester) with by M/K Systems herein, the value that the 3-D paper analyzer (M/K950) that Inc. produces is measured, and the diaphragm diameter of described paper analyzer is made as 1.5mm.
Specifically, sample (record-paper) is attached on the rotatable drum of 3-D paper analyzer.Use is installed in the light source on the axle of cylinder and is arranged on cylinder outside and towards the photodetector of light source, measures the localized variation of sample paper weight according to intensity variations.Diaphragm diameter by the incident light part that offers photodetector comes the control survey area.Amplify intensity variations (deviation), and A/D (analog/digital) conversion is done in this variation, be divided into the weight grade of 64 optical measurement then.1000000 measurements are carried out in each scan operation, and make histogram according to measured value.With the frequency (peak value) of histogrammic highest ranking quantity divided by frequency 100 or 100 above grades, again with the value (merchant) that obtains divided by 100.The value that finally obtains is described evenness index.The high more paper form that shows of evenness index is even more.
When carrying out electrophotographic image forming, the electrical characteristics of record-paper are important.For example, when using the saltcake may influence electrical characteristics or cationization material in the preparation at record-paper, different according to the combination of described material and consumption the inhomogeneous of image transfer printing may occur in the electrophotographic image forming.
Therefore, the surface resistivity of imaging one side preferably 1.0 * 10 on the record-paper
9Ω/sq to 1.0 * 10
11Ω/sq.The specific insulation of record-paper preferably 1.0 * 10
10Ω cm to 1.0 * 10
12Ω cm.If surface resistivity or specific insulation exceed above-mentioned scope, in the xerography the inhomogeneous of image transfer printing may appear.The another side of record-paper can have the surface resistivity of above-mentioned scope.
Surface resistivity more preferably 5.0 * 10
9Ω/sq to 7.0 * 10
10Ω/sq, preferred again 5.0 * 10
9Ω/sq to 2.0 * 10
10Ω/sq.Specific insulation more preferably 1.3 * 10
10Ω cm to 1.6 * 10
11Ω cm, more preferably 1.3 * 10
10Ω cm to 4.3 * 10
10Ω cm.In this specification, surface resistivity and specific insulation are the values of record-paper being measured after leaving standstill 24 hours under 23 ℃, 50%RH condition with the method for JIS-K-6911.The disclosed content of JIS-K-6911 is incorporated herein by reference herein.
The basic paper bag that uses in first embodiment contains paper pulp (cellulose pulp) as main component.Base paper can be selected from following basic paper, maybe can be the common paper that the mass treatment base paper surface with pigment for example or adhesive obtains.
The plain paper pulp of base paper bag fibre-bearing.As cellulose pulp, can use known paper pulp.Specifically, can use chemical pulp, more particularly, can use the paper pulp of producing by chemical treatment timber, for example bleached hardwood kraft pulp, broad leaf tree bleached kraft pulp, bleached hardwood sulfite pulp, broad leaf tree unbleached sulfite pulp, coniferous tree bleaching sulfite pulp, coniferous tree unbleached sulfite pulp of bleached kraft pulp, coniferous tree bleached kraft pulp, coniferous tree not; And by the chemical treatment paper pulp produced of fiber raw materials such as timber, cotton, hemp and bast for example.
For example can also use by timber or wood chip being carried out ground wood pulp that machinery pulping obtains, soaking into behind timber or the wood chip with chemical solution these timber or wood chip are carried out the thermomechanical pulp that chemi-mechanical pulp that machinery pulping obtains or boiling wood chip obtain with refiner slurrying subsequently until these wood chip deliquescing.These paper pulp that will use can only be made by primary slurry, or can sneak into waste paper in these paper pulp as required.
Especially, the paper pulp that only comprises primary slurry preferably uses method for bleaching (the element-free chlorine of chlorine dioxide not use chlorine; ECF) or the method for not using chlorine-containing compound to use ozone/hydrogen peroxide (completely without chlorine; The paper pulp of method bleaching such as TCF).
In addition,, can mix as the raw material of above-mentioned secondary stock: job lot paper not, for example by edging or the high white broken that produces or produce as the broken in bookbindery, printing house and the side cut factory of cutting edge, extra white broken, in white broken and white broken; The fine paper that printed, fine paper of for example printing or duplicating and senior coated paper; The waste paper of writing with for example printing ink or pencil; The disregard message paper that comprises flyer, matter paper in the fine paper that for example printed, coating fine paper, middle matter paper and the coating; Waste paper, matter paper and wood pulp fibre paper in for example middle matter paper, the coating.
As the secondary stock that uses in first embodiment, it is desirable handling the paper pulp that above-mentioned wastepaper as raw material obtains with at least a method in ozone bleaching and the hydrogen peroxide bleaching.In addition, in order to obtain having the basic paper of higher whiteness, the ratio of being handled the secondary stock that obtains by above-mentioned bleaching is preferably 50 weight %～100 weight %.In addition, consider resource reusing, the ratio of secondary stock is 70 weight %～100 weight % more preferably.
Above-mentioned ozone treatment has the effect of decomposing the fluorescent dye that comprises usually in the fine paper, hydrogen peroxide treatment have prevent to handle by deinking in the effect of the yellowing that causes of used alkali.Known processing in conjunction with above-mentioned two kinds of processing not only is easy to carry out deinking, and can improve the whiteness of paper pulp.In addition, described has the effect of decomposing and removing the residual chloride compound in the paper pulp in conjunction with handling, and has therefore used the content of the organohalogen compound in the waste paper of chlorine bleaching paper pulp to have remarkable effect to reduction.
In addition, add filler in the preferred basic paper that uses in the first embodiment with control opacity, whiteness and surface characteristic.Needing especially to reduce under the situation of halogen quantity, preferred use does not comprise the filler of halogen.The example of available filler comprises white inorganic pigment, for example powdered whiting, precipitated calcium carbonate, chalk (choke), kaolin, calcined clay, talcum, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, zinc sulphide, zinc carbonate, alumina silicate, calcium silicates, magnesium silicate, synthetic silica, aluminium hydroxide, aluminium oxide, sericite, white carbon, saponite, calcium montmorillonite, sodium montmorillonite and bentonite; And organic pigment, for example acrylic acid plastic pigments, polyethylene and urea resin.In addition, when mixed waste paper, must adjust the consumption of waste paper by estimating the content of ashes that comprises in the wastepaper as raw material in advance.
And, use sizing agent in adding in the preferred basic paper that uses in the first embodiment.As the interior sizing agent of using, can use the neutral colophony type sizing agent, alkenyl succinic anhydride (ASA), alkyl ketene dimer (AKD) and the Petropols type sizing agent that use when producing neutralized paper.
In the time will controlling record-paper surface, for example use hydrophily resin cation etc. to handle this surface as cationic materials for cationic.In this case, use before this resin cation, but the degree of sizing of described paper is preferably more than 10 seconds or 10 seconds less than 60 seconds, to suppress the infiltration of resin cation to inside.
By handling above-mentioned basic paper surface, can obtain the record-paper of first embodiment with the surface size that comprises starch.
Can for example size presser, gasket type sizing applicator (shim size), weir roller, roll coater, scraping strip coating machine, Kohler coater, bar type knife type coater (rod bladecoater) or knife type coater be applied to basic paper to carry out surface treatment with top sizing with solution with common application device.Through subsequently drying steps and obtain record-paper.
Though not to quantitatively being particularly limited of the record-paper of first embodiment, 60g/m preferably
2～128g/m
2, be more preferably 60g/m
2～100g/m
2, 60g/m preferably again
2～90g/m
2Quantitatively high more for suppressing curling and wrinkling favourable more.Yet, if quantitatively surpass 128g/m
2, the deflection of paper (rigidity) is too high, therefore has the situation that the paper service performance worsens in the printer.On the other hand, if quantitatively be lower than 60g/m
2, exist to be difficult to fully suppress to curl and wrinkling situation.Consider offset, such hanging down quantitatively also is undesirable.
In addition, when copying paper, preferably adjusting fiber orientation ratio is 1.0 to 1.55, more preferably 1.0 to 1.45, preferred again 1.0 to 1.35.When fiber orientation ratio is within this scope, can suppress to print curling of back record-paper with ink-jetting style.Above-mentioned " fiber orientation ratio " is the fiber orientation ratio of measuring with the ultrasonic propagation velocity method.This ratio is the value that the ultrasonic propagation velocity of paper MD (copying the direction that paper advances) is calculated divided by the ultrasonic propagation velocity of CD (perpendicular to the direction of copying the paper direction of advance), and is represented by following equation (1).Equation (1): fiber orientation ratio (T/Y ratio)=(ultrasonic propagation velocity of MD direction)/(ultrasonic propagation velocity of CD direction) of the basic paper that obtains by the ultrasonic propagation velocity method
In this case, use sound wave paper tester (SONIC SHEET TESTER; Produce by Nomura Shoji (K.K.)) measure the fiber orientation ratio that obtains by this ultrasonic propagation velocity method.
The record-paper of first embodiment preferably comprises the material that can make the paper dimensionally stableization.If this record-paper comprises such material, then can form covalent bond between the paper pulp fiber, thereby suppress change in size.The material that can make the paper dimensionally stableization can be for example aldehyde resin, poly-carbodiimide, ammonium zirconium carbonate or multivalence organic acid.Consider security and cost, this material is the multivalence organic acid preferably.
The surface of the record-paper of first embodiment preferably comprises cationic polymer or multivalent metal salt.In this case, when jetted ink comprised anionic polymer, this anionic polymer molecule can be crosslinked via described cationic polymer or multivalent metal salt.Because crosslinked, the colouring agent in the printing ink can very fast aggegation, can obtain high-quality print image.In addition because the infiltration of printing ink solvent to paper inside is prevented from, so curling of occurring immediately after can suppressing more efficiently to print and wrinkling, and after air-dry curl and wrinkling.
The example of above-mentioned multivalent metal salt comprises chloride, formates and the acetate of potassium, barium, calcium, magnesium and other polyvalent metal.The instantiation of multivalent metal salt comprises barium chloride, calcium chloride, calcium acetate, calcium nitrate, calcium formate, magnesium chloride, magnesium sulfate, magnesium acetate, magnesium formate and zinc chloride.Single multivalent metal salt of planting can be only used, maybe multiple multivalent metal salt can be used.In these multivalent metal salts, it is preferred having the slaine of highly dissoluble and the slaine of high valence mumber in water.In addition, if the gegenion of multivalent metal salt is a strong acid, coating back paper can yellowing.Therefore, calcium chloride, calcium formate, magnesium chloride, magnesium formate etc. are preferably used as multivalent metal salt.The example of cationic polymer comprises cationized cellulose and cationic starch; Yet the material that is different from these materials is also included within the scope of the invention.
Can be by above-mentioned cationic polymer that exemplifies or multivalent metal salt be added above-mentioned top sizing solution, or be applied to basic paper surface, thereby above-mentioned cationic polymer that exemplifies or multivalent metal salt are incorporated into the record-paper surface by other coating solution that will comprise described cationic polymer or multivalent metal salt.In one situation of back, can be in water dissolve polymer or slaine, forming coating solution, and directly this coating solution is applied to record-paper (or paper) and is coated with.Yet common described coating solution also comprises adhesive.
The cationic polymer that comprises in the record-paper surface and the content of multivalent metal salt are preferably 0.1g/m
2～2.0g/m
2, more preferably 0.5g/m
2～1.0g/m
2
If described content is less than 0.1g/m
2, then with printing ink in the extent of reaction of the pigment that comprises and anionic polymer lower, image quality may be lower, what occur immediately after the printing curls and wrinklingly may become serious, curling and wrinklingly also may become serious after air-dry.On the other hand, if described content surpasses 2.0g/m
2, then can damage the permeability of printing ink, and the ink setting performance may damage flying print the time.
(electrophotographic image recording method)
Electrophotographic image recording method in first embodiment comprises: charge in the surface to the electrostatic latent image holding member; The face exposure that makes this electrostatic latent image holding member is to form electrostatic latent image; The lip-deep latent electrostatic image developing that makes this electrostatic latent image holding member with developer is to form toner image; Toner image is transferred to the record-paper surface; The lip-deep toner image of this record-paper is fixed, and wherein, described record-paper is the above-mentioned record-paper of first embodiment.
According to the electrophotographic image recording method of first embodiment, what occur immediately after can suppressing to print curls.
Any device can be as the imaging device that uses in the electrophotographic image recording method of first embodiment, as long as it uses the electrophotographic system that has comprised above-mentioned charge step, step of exposure, development step, transfer step and fixing step.Under the situation of using four colour toners that for example comprise cyan, magenta, yellow and black toner, this device can be: use the coloured image of 4-circulation developing system to form device, in this developing system, the developer that comprises the toner of different colours is respectively offered photoreceptor successively, to form toner image; Coloured image with four developing cells corresponding with respective color forms device (so-called tandem machine) etc.
As the toner that is used for imaging, can use any known toner, without any particular determination.Yet, can use the spherical toner that for example has small particle diameter and narrow size distribution obtaining highly accurate image, and can use the toner that comprises the low melting point adhesive resin and fix so that can carry out low temperature.
(ink jet image recording method)
The ink jet image recording method of first embodiment comprises on the record-paper surface provides droplet of ink, thus on record-paper document image, wherein, described record-paper is the record-paper of first embodiment.Therefore, this ink jet image recording method has occurred after having suppressed to print immediately curl and air-dry after curl.
Can implement the ink jet recording method of first embodiment with for example hot ink-jet-type recording device of traditional ink jet recording device and piezoelectric ink jet recording equipment.This ink jet recording method can be applied to have be used for when printing, print before or print the system of the unit of back heating record-paper, described unit can be by being heated to record-paper and printing ink 50 ℃～200 ℃ absorptions that promote printing ink and fixing.
Then, description is suitable for put into practice the example of an ink-jet recording apparatus of the ink jet recording method of first embodiment.This example is known as multipass formula system, wherein, described record head is repeatedly scanned to form image to the surface of record-paper.
System as discharge printing ink from nozzle below illustrates so-called hot ink-jet system, in this system, energy is supplied to the heater that is arranged in the nozzle so that the printing ink foaming in the nozzle, thereby by the pressure that is produced by foaming printing ink is discharged.Also have a system to be, to the piezoelectric element supplying energy so that this piezoelectric element generation physical deformation, thereby will be used for printing ink is discharged from nozzle by the power that described distortion produces.
The common working pressure element of this system is as described piezoelectric element.In the ink-jet recording apparatus that uses in the ink jet recording method of first embodiment, being used for from the system of nozzle discharge printing ink can be above-mentioned arbitrary system, and is not limited to these systems.In this specification, this system is not subjected to any restriction.
Second embodiment
Record-paper
In second embodiment, the invention provides a kind of record-paper.This record-paper is that comprising with paper pulp fiber and filler is the common paper of the basic paper of main component, and wherein, described common paper does not have the coating layer that comprises pigment, and this common paper has been coated with the treatment fluid that comprises starch.This record-paper is such record-paper: when to 0.06m
2Record-paper when carrying out hot water extracting, the amount of solid of this extract is 0.01g～0.4g, and carboxyl-content is 0～5 mM/100 grams in this solid.
In the embodiment, described treatment fluid comprises the salt of the above metal of divalence or divalence, and under 23 ℃, the condition of 50%RH, the surface resistivity of this record-paper and the ratio of specific insulation are 0.1～1, and its surface resistivity is 1.0 * 10
9Ω/sq～1.0 * 10
11Ω/sq, and specific insulation is 5.0 * 10
9Ω cm～5.0 * 10
11Ω cm.
The record-paper of second embodiment is the common paper with the coating layer that comprises pigment.Therefore, described treatment fluid does not preferably contain pigment in fact.The term of the Shi Yonging content that " do not contain pigment in fact " and be meant pigment in the described treatment fluid is for smaller or equal to 10 weight % herein.
The example of the starch that uses in second embodiment has been described hereinafter.Starch is the natural water-soluble copolymer with small number of carboxylic acid groups.Be used at starch before the surface treatment of paper, usually starch reduced the processing of starch viscosity, to improve surface-treated efficient.This processing that is used to reduce viscosity normally reduces the processing of starch molecule amount.For example oxidation processes or enzyme modification are handled.By reducing the processing of starch molecule amount, might increase the quantity of carboxyl.
Although reason is unclear,, then in the electrophotographic recording method, can obviously suppress curling behind the heat fixation if the starch that carboxyl is less is used for record-paper.Similarly, when mixing and using when having the starch of different carboxyl amounts,, can suppress curling behind the heat fixation by being used in combination the less starch of carboxyl amount.
According to this observed result, the inventor has been found that if record-paper carboxyl-content in the solid that hot water extracting obtains of being handled by starch is 0～5 mM/100 grams, then can suppress curling behind the heat fixation.
Colouring agent in the water-based ink that uses in the ink jet recording method is anionic property normally.If exist the identical material of ion polarity of the colouring agent in its ion polarity and the printing ink on the record-paper surface, then this colouring agent can be had the area repels of this material.This repulsion meeting produces undesirable white point in should having the solid image-region of the uniform solid image of color, and this white point can reduce color rendition.The inventor thinks preferably do not have this specific character that can cause image quality to worsen on paper surface for the starch that uses.
If record-paper carboxyl-content in the solid that hot water extracting obtains of being handled by starch is 0～5 mM/100 grams, the then amount reduction of the component of anionic coloring agent in hydration and the repulsion printing ink in printing ink, thus improved color rendition.In addition, the inventor also finds, if satisfy " when to 0.06m
2Record-paper when carrying out hot water extracting, the amount of solid of this extract is 0.01g～0.4g " this condition, then in printing ink hydration and fixedly the amount of the component of colouring agent be suitable.
When providing printing ink to paper surface, if the amount of the said components of hydration is less in printing ink, then described colouring agent can not be fixed, thereby can infiltrate the inside of paper or sprawl arbitrarily on the thick-layer of the material of extremely difficult hydration, will cause even color rendition variation.If the amount of this component is too big, the molecular weight of starch is too little, and does not have the polymerizable compound of fixing in conjunction with the complex compound that forms or insoluble substance that makes by colouring agent and hydration component, then can reduce color rendition thus.
Carboxyl-content is preferably 0～5 mM/100 grams in the solid that is obtained by hot water extracting, more preferably 0～3 mM/100 grams.This is because carboxyl-content is low more, can suppress curling behind the heat fixation in the electrophotographic method more, and the content of the carboxyl of repulsion colouring agent is low more, with the color rendition that can improve more in the ink-jet method.
As mentioned above, the amount of the hot water extracting gained solid by limiting paper and the carboxyl-content of this solid can obtain favourable effect.
If further use the surface of multivalent metal salt handling of paper, can improve the color rendition in the ink jet recording method.Yet,, worsen the transfer printing of toner in the electrophotographic method probably if a large amount of cation multivalent metal salts are used for surface treatment.
Therefore, for the transfer printing in the electrophotographic recording method and the color rendition in the ink jet recording method importantly, the multivalent metal salt that is applied to paper surface remain in this surface near.Therefore, the inventor has been conceived to surface resistivity and the specific insulation as the index of reflection ionization material distribution.
In a preferred embodiment, under 23 ℃, the condition of 50%RH, the surface resistivity of this record-paper and the ratio of specific insulation are 0.1～1, and its surface resistivity is 1.0 * 10
9Ω/sq～1.0 * 10
11Ω/sq, and specific insulation is 5.0 * 10
9Ω cm～5.0 * 10
11Ω cm.In this specification, the ratio of this surface resistivity and specific insulation is meant the (value of surface resistivity (Ω/sq)/specific insulation (Ω cm)).This ratio is preferably 0.1～1, and more preferably 0.1～0.5.If this ratio is lower than 0.1, then specific insulation is too high with respect to surface resistivity; Therefore excessive charge can remain in the paper during electrophotographic printer, thus, when discharge can occurring when transfer member removes paper, thereby produces the image quality defective.If this ratio is greater than 1, then specific insulation is too low; This shows that the cation multivalent metal salt that is applied to the surface has infiltrated paper inside in a large number, and does not remain near surface.Color rendition when in this case, being difficult to improve inkjet printing.In addition, in electrophotographic method, electric charge does not keep from the teeth outwards, thereby but leaks to the back side and cause the transfer printing defective.
Surface resistivity on the printing surface of the record-paper of second embodiment is preferably 1.0 * 10
9Ω/sq～1.0 * 10
11Ω/sq, more preferably 5.0 * 10
9Ω/sq～7.0 * 10
10Ω/sq is more preferably 5.0 * 10
9Ω/sq～2.0 * 10
10Ω/sq.The term of Shi Yonging " printing surface " is meant that face of having handled with starch and multivalent metal salt herein.
Specific insulation is preferably 1.0 * 10
10Ω cm～1.0 * 10
12Ω cm, more preferably 1.3 * 10
10Ω cm～1.6 * 10
11Ω cm, more preferably 1.3 * 10
10Ω cm～4.3 * 10
10Ω cm.
Make the ratio of surface resistivity, specific insulation and surface resistivity and specific insulation respectively in above-mentioned scope by using the treatment fluid that comprises multivalent metal salt, the record-paper that can obtain the transfer printing problem in the electrophotographic recording method, not occurring and in ink jet recording method, demonstrate the color rendition of improvement.
The basic paper that is used to prepare the record-paper of second embodiment is described below.The basic paper that uses in this record-paper is main component with paper pulp fiber and filler.
This paper pulp fiber can be the chemical pulp fiber.The example of chemical pulp comprises the paper pulp that chemical treatment timber is produced, for example bleached hardwood kraft pulp, broad leaf tree bleached kraft pulp, bleached hardwood sulfite pulp, broad leaf tree unbleached sulfite pulp, coniferous tree bleaching sulfite pulp, coniferous tree unbleached sulfite pulp of bleached kraft pulp, coniferous tree bleached kraft pulp, coniferous tree not; And by the chemical treatment paper pulp produced of fiber raw materials such as timber, cotton, hemp and bast for example.
For example can also use by timber or wood chip being carried out ground wood pulp that machinery pulping obtains, soaking into behind timber or the wood chip with chemical solution these timber or wood chip are carried out the thermomechanical pulp that chemi-mechanical pulp that machinery pulping obtains or boiling wood chip obtain with refiner slurrying subsequently until these wood chip deliquescing.Thermomechanical pulp can be the chemical thermo-mechanical pulp that can obtain with high yield.These paper pulp that will use can only be made by primary slurry, or can sneak into waste paper in these paper pulp as required.
Especially, described primary slurry preferably uses method for bleaching (the element-free chlorine of chlorine dioxide not use chlorine; ECF) or the method for not using chlorine-containing compound to use ozone/hydrogen peroxide (completely without chlorine; The paper pulp of method bleaching such as TCF).
In addition,, can mix as the raw material of above-mentioned secondary stock: job lot paper not, for example by edging or the high white broken that produces or produce as the broken in bookbindery, printing house and the side cut factory of cutting edge, extra white broken, in white broken and white broken; The fine paper that printed, fine paper of for example printing or duplicating and senior coated paper; The waste paper of writing with for example printing ink or pencil; The disregard message paper that comprises flyer, matter paper in the fine paper that for example printed, coating fine paper, middle matter paper and the coating; Waste paper, matter paper and wood pulp fibre paper in for example middle matter paper, the coating.
As the secondary stock that uses in second embodiment, it is desirable handling the paper pulp that above-mentioned wastepaper as raw material obtains with at least a method in ozone bleaching and the hydrogen peroxide bleaching.In addition, in order to obtain having the basic paper of higher whiteness, the ratio of being handled the secondary stock that obtains by above-mentioned bleaching is preferably 50 weight %～100 weight %.In addition, consider resource reusing, the ratio of secondary stock is 70 weight %～100 weight % more preferably.
Above-mentioned ozone treatment has the effect of decomposing the fluorescent dye that comprises usually in the fine paper, hydrogen peroxide treatment have prevent to handle by deinking in the effect of the yellowing that causes of used alkali.Known processing in conjunction with above-mentioned two kinds of processing not only is easy to carry out deinking, and can improve the whiteness of paper pulp.In addition, described has the effect of decomposing and removing the residual chloride compound in the paper pulp in conjunction with handling, and has therefore used the content of the organohalogen compound in the waste paper of chlorine bleaching paper pulp to have remarkable effect to reduction.
In addition, add filler in the basic paper that preferably in second embodiment, uses with control opacity, whiteness and surface characteristic.Needing especially to reduce under the situation of halogen quantity, preferred use does not comprise the filler of halogen.The example of available filler comprises white inorganic pigment, for example powdered whiting, precipitated calcium carbonate, chalk, kaolin, calcined clay, talcum, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, zinc sulphide, zinc carbonate, alumina silicate, calcium silicates, magnesium silicate, synthetic silica, aluminium hydroxide, aluminium oxide, sericite, white carbon, saponite, dolomite, calcium montmorillonite, sodium montmorillonite and bentonite; And organic pigment, for example acrylic acid plastic pigments, polyethylene, chitosan particle, cellulose grain, polyaminoacid particle and urea resin.
In addition, when mixed waste paper, must adjust the consumption of these waste paper by estimating the content of ashes that comprises in the wastepaper as raw material in advance.
The amount of filler of mixing is not particularly limited.The amount of filler is 1～50 mass parts based on 100 mass parts paper pulp fibers more preferably based on 100 mass parts paper pulp fibers, 1～80 mass parts preferably.
In addition, when copying paper, preferably adjusting fiber orientation ratio is 1.0 to 1.55, more preferably 1.0 to 1.45, preferred again 1.0 to 1.35.When fiber orientation ratio within 1.0 to 1.55 the scope time, can in electrophotographic recording method and ink jet recording method, suppress to print curling of back record-paper simultaneously.The implication of fiber orientation ratio had been done to explain in the description of first embodiment.
Starch
Below the starch that uses in second embodiment will be described.
The scope of the starch that uses in second embodiment comprise from by plant through the starch of the synthetic polysaccharide extraction of photosynthesis reaction and the product that obtains by the starch of handling derived from natural origin.The example of described starch comprises: unmodified starch, for example tapioca, farina, cornstarch, glutinous property cereal starch and sugarcane starch; Modified starch, for example starch of cationic starch, oxidized starch, anionization starch, enzymically modified starch and introducing hydrophobic grouping.Because produce carboxyl hardly, the enzymically modified starch that obtains with enzymatic lysis α-glycosidic bond is preferred.Under the situation of using oxidized starch,, can produce a large amount of carboxyls by carrying out wet processed with the clorox that is generally used for oxidation; Yet, when with drying mode with periodate etc. during with the powdered form starch oxidation, this oxidation is gentle, oxidized portion keeps with the aldehyde form, thereby produces dialdehyde starch etc., wherein, described mild oxidation is preferred, because it has suppressed the generation of carboxyl.In wet method,, can make this oxidation become gentle by keeping high reaction pH; High pH with the short time handles the oxidized starch that can almost not had carboxyl.Yet even in this case, the carboxyl-content of the starch of wet oxidation is still than the carboxyl-content height of enzymically modified starch, and than the carboxyl-content height of the starch of dry oxidation.Therefore, the described starch that does not almost have the carboxyl starch that is preferably enzymically modified starch or obtains by dry oxidation process.In order to satisfy " carboxyl-content of the solid that is obtained by hot water extracting is 0～5 mM/100 grams " this condition, described starch is preferably the starch with carboxy lower content.The carboxyl-content of starch is preferably 0～5 mM/100 grams, and more preferably 0～4 mM/100 grams are more preferably 0～3 mM/100 grams.When IR (infrared) absorption spectrum of the solid of confirming to obtain, can be observed from 950cm by hot water extracting
-1To 1150cm
-1The exclusive absorption of starch, and can be observed at 1153cm
-1, 1078cm
-1And 1024cm
-1Near three peaks.
Slaine
Then, with the slaine that uses in explanation second embodiment.This slaine is the slaine that dissolving the time becomes cationic in pure water.In one embodiment, use at least a slaine that comprises divalence or the above metal ion of divalence.
The slaine that comprises divalence or the above metal ion of divalence can be known slaine.The above slaine of described divalence or divalence is preferably selected from: aluminium ion, beryllium ion, calcium ion, magnesium ion, strontium ion, barium ions, radium ion and zinc ion; Fe (II) ion; And Fe (III) ion.More preferably calcium ion and magnesium ion.
These metal ions have less molecular weight, can easily dissolve in the printing ink on being provided to record-paper.In addition, the needed time of hydration is shorter during ionization; These ions can make the ion polarity colouring agent opposite with described metal ion not dissolving and/or gathering thus.
The preparation of record-paper and the characteristic of record-paper
Then, explanation is used to prepare the method for record-paper of second embodiment and the preferred characteristics of described record-paper.
Method with the treatment fluid coated base paper surface that comprises starch and slaine is not particularly limited.Usually, this treatment fluid is used as coating fluid (size press liquid), and preferably size press-treated is carried out on basic paper surface with this treatment fluid.
As mentioned above, this treatment fluid does not preferably contain pigment (this is meant that the pigment content in the treatment fluid is smaller or equal to 10 weight %) in fact.In other words, the record-paper of having made surface-treated second embodiment is the common paper with the coating layer that comprises pigment.This coating layer that comprises pigment is used for the coated paper different with the record-paper of second embodiment.Because coated paper as the electrophotographic recording in the general office with or ink mist recording when using record-paper, there is the problem of cost, infringement transfer member and paper powder, in the scope of second embodiment, gets rid of so will have this coated paper of the coating layer that comprises pigment.
Can for example size presser, gasket type sizing applicator, weir roller, roll coater, scraping strip coating machine, Kohler coater, bar type knife type coater or knife type coater be coated on coating fluid on the basic paper surface with the general application device.With being coated with the basic paper drying of the treatment fluid that comprises starch and slaine, to make the record-paper of second embodiment.
When basic paper surface was coated with the treatment fluid that comprises starch and slaine, the amount of the treatment fluid of each face was 0.4g/m with amount of solid calculating on the basic paper
2～6g/m
2, be more preferably 0.5gg/m with amount of solid calculating
2～3g/m
2The weight ratio of starch and slaine preferably 1/5 to 5/0.1 in the treatment fluid, and more preferably 2/3 to 5/1.
If the amount of solid of the amount of solid of starch or slaine is less than 0.1g/m
2, then can not obtain the effect that top sizing is handled, the effect of the surface strength that also promptly can not be improved.If amount of solid is greater than 5g/m
2, then the quality of record-paper unlikely is suitable for common paper.Therefore, be applied to preferably 0.6g/m of the starch on surface and the total solid of slaine
2～5g/m
2
Amount that can be by the control amount of starch and kind, other water-soluble polymer and kind etc. are adjusted to appropriate value with the degree of sizing of the record-paper of second embodiment.If can not obtain required degree of sizing by controlling those factors, can also add Cypres.Cypres can be for example rosin sizing agent, synthetic sizing agent, petroleum resin sizing agent, neutral sizing agent or polyvinyl alcohol.
Can by in copying the slurry preparation step of paper, adding with sizing agent so that when copying paper, control degree of sizing.In wishing record-paper the amount of halogen hour, not halogen-containing Cypres and interior be preferred with sizing agent.This sizing agent can be rosin sizing agent, synthetic sizing agent, petroleum resin sizing agent or neutral sizing agent.
Can use the combination of sizing agent and fiber with fixative.In this case, fixative can be for example aluminum sulfate or cationic starch.Consider the storability of improving record-paper, described sizing agent is neutral sizing agent preferably.Can control degree of sizing with the addition of sizing agent.
The st ckigt degree of sizing of described record-paper is preferably 10 seconds～and 60 seconds, more preferably 15 seconds～30 seconds.If st ckigt degree of sizing was less than 10 seconds, then in inkjet printing, the paper of spreading and sinking in worsens and little literal may be beyond recognition; When inkjet printing bar code etc., bar code may be beyond recognition.Therefore, the st ckigt degree of sizing that is lower than 10 seconds may damage practicality.
If st ckigt degree of sizing is greater than 60 seconds, but then in the electrophotographic printer stationarity of toner may worsen.
St ckigt degree of sizing is at JIS P8122:1976 (JIS: Japanese Industrial Standards; Its disclosure is incorporated herein by reference herein) middle definition, and in JIS P8111:1988 (its disclosure is incorporated herein by reference herein), record in the specified standard environment (23 ℃, 50%RH).
Consider transfer printing and the graininess of improving toner, the smoothness of record-paper preferably 20 seconds～100 seconds, more preferably 70 seconds～100 seconds.If smoothness is lower than 20 seconds, graininess may worsen.If smoothness is higher than 100 seconds, need under moisture state, carry out high-pressure compressing during production to obtain high smoothness; Serious curling takes place after may causing the transparency increase of paper or causing heat fixation in high-pressure compressing.In this manual, smoothness is meant the value that the method with JIS-P-8119:1998 (its disclosure is incorporated herein by reference) regulation records herein.
Consider the generation that suppresses cloud form spot in the electrophotographic image forming, the evenness index of record-paper is preferably more than and equals 20, more preferably greater than equaling 30.If evenness index is lower than 20, in electrophotographic recording, toner is easy to infiltrate unevenly record-paper during heat fusing, thereby produces spot, the infringement image quality.The method that is used for measuring evenness index was done to explain in the explanation of first embodiment.
When the record-paper usefulness of second embodiment acts on the recording medium of electrophotography, hot transfer printing or its combination, preferably control the surface resistivity of this record-paper by adding conductive agent.The preferably not halogen-containing conductive agent of this conductive agent is so that reduce the amount of halogen in the record-paper.
The example of conductive agent comprises: inorganic electrolyte, for example sodium sulphate, sodium carbonate, lithium carbonate, sodium metasilicate, sodium phosphate trimer and sodium metaphosphate; Anion surfactant, for example sulfonate, sulfuric acid, carboxylate and phosphate; Cationic surfactant; Nonionic surface active agent and amphoteric surfactant, for example polyethylene glycol, glycerine and D-sorbite (sorbit); And polymer dielectric.As mentioned above, especially preferably use the salt of the above metal of divalence or divalence in second embodiment, and the use of this slaine can improve the color rendition in the inkjet printing.
Before the treatment fluid coating that comprises starch and slaine, the gas permeability of paper preferably 10 seconds～30 seconds.For example can handle, with the control gas permeability by basic paper being carried out press polish.When using the treatment fluid coated base paper surface that comprises starch and slaine,, can suppress the permeability of treatment fluid in record-paper by increasing gas permeability.Yet, if gas permeability is too high, also can suppress the permeability of printing ink in the inkjet printing, paper (intercolor bleed) and may damage drying property thus may occur spreading and sinking between look.Therefore, preferably under the condition of considering this problem, adjust gas permeability.
By to drying but the basic paper that does not carry out size press carries out size press, can suppress the infiltration of treatment fluid in basic paper.
(electrophotographic image recording method)
Electrophotographic image recording method in second embodiment comprises: charge in the surface to the electrostatic latent image holding member; The face exposure that makes this electrostatic latent image holding member is to form electrostatic latent image; The lip-deep latent electrostatic image developing that makes this electrostatic latent image holding member with developer is to form toner image; Toner image is transferred to the record-paper surface; The lip-deep toner image of this record-paper is fixed, and wherein, described record-paper is the above-mentioned record-paper of second embodiment.
According to the electrophotographic image recording method of second embodiment, that can suppress significantly to occur behind the heat fixation curls, kept simultaneously with conventional method in the same high image quality.
Any device can be as the imaging device that uses in the electrophotographic image recording method of second embodiment, as long as it uses the electrophotographic system that has comprised above-mentioned charge step, step of exposure, development step, transfer step and fixing step.Under the situation of using four colour toners that for example comprise cyan, magenta, yellow and black toner, this device can be: use the coloured image of 4-circulation developing system to form device, in this developing system, the developer that comprises the toner of different colours is respectively offered photoreceptor successively, to form toner image; Coloured image with four developing cells corresponding with respective color forms device (so-called tandem machine) etc.
As the toner that is used for imaging, can use any known toner, without any particular determination.Can use the spherical toner that for example has small particle diameter and narrow size distribution to obtain highly accurate image, and can use the toner that comprises the low melting point adhesive resin so that can carry out low temperature fixes, this angle from energy savings is preferred.
(ink jet image recording method)
Then, will the ink jet image recording method (being sometimes referred to as " ink jet recording method " hereinafter) of second embodiment be described.The ink jet image recording method of second embodiment comprises by using printing ink document image on record-paper.Described printing ink is not particularly limited, and can be selected from known printing ink.This printing ink preferably comprises the printing ink of water and colouring agent.
The example of this colouring agent comprises: dyestuff; The hydrophobicity pigment that is used in combination with pigment dispersing agent, described pigment dispersing agent have can make this hydrophobicity pigment be dispersed in hydrophilic radical in the printing ink; And from pigment dispersion.Solvent can be water or known water-miscible organic solvent.As required, solvent can comprise for example surfactant of additive.
When record-paper was used for inkjet printing, each dripped preferably 1～20pl (pl:10 from the amount of the printing ink of nozzle ejection
-12Rise), more preferably 3pl～18pl.
The ink jet recording method of second embodiment is when the printing that is used for any known ink-jet apparatus, and the concrete mode regardless of ink mist recording has all realized fabulous print quality.Ink jet recording method can be applied to have be used for when printing, print before or print the system of the unit of back heating record-paper, this unit can be by being heated to record-paper and printing ink 50 ℃～200 ℃ absorptions that promote printing ink and fixing.
Method as discharge printing ink from nozzle below illustrates so-called hot ink-jet system, in this system, energy is supplied to the heater that is arranged in the nozzle so that the printing ink foaming in the nozzle, thereby by the pressure that is produced by foaming printing ink is discharged.Also have a system to be, to the piezoelectric element supplying energy so that this piezoelectric element generation physical deformation, thereby will be used for printing ink is discharged from nozzle by the power that described distortion produces.The common working pressure element of this system is as piezoelectric element.In the ink-jet recording apparatus that uses in the ink jet recording method of second embodiment, being used for from the system of nozzle discharge printing ink can be above-mentioned arbitrary system, but is not limited to these systems.
Although used title " first embodiment " and " second embodiment " in the above description, the feature of each embodiment can freely combine with the feature of other embodiment.Therefore, scope of the present invention comprises the combination of the embodiment of describing in the specification.
Embodiment
Hereinafter, will quote embodiment and Comparative Examples the present invention will be carried out specific description more.Yet, should not be considered as limitation of the present invention to embodiment.
The preparation of record-paper
(record-paper 1)
Will be by the dry pulp defibre of broad leaf tree kraft pulp preparation, and carry out refining and make its freedom become 420ml.Then, preparation paper pulp dispersion liquid makes that the solids content of paper pulp is 0.3 quality %.
Sizing agent (FIBRAN-81 will be used in the 0.3 mass parts alkenyl succinic anhydride (ASA), by NipponNSC, Ltd. produce) and 0.5 mass parts cationic starch (CATO-304, by Nippon NSC, Ltd. production) be added to the paper pulp dispersion liquid that comprises 100 mass parts paper pulp solids.By by KumagaiRiki Kogyo Co., the experiment that Ltd. (K.K.) produces is copied paper with 80 mesh sieve twines to mixture: copy the chart speed rate under the following conditions with fiber orientation paper machine: 1000 meters/minute, and paper discharge pressure: 1.5kg/cm
2
After this, by by Kumagai Riki Kogyo Co., the paper machine that Ltd. produces is with rectangle squeezer (rectangular press), at 10kg/cm
2Pressure under with this batch product squeezing 3 minutes, and with Kumagai Riki Kogyo Co., the rotary-type drying machine of KRK of Ltd. production carries out drying with 0.5 meter/minute condition at 120 ℃, quantitatively being 68g/m
2Basic paper.
Being prepared as follows of surface size.The container that will hold the solution that contains 8 weight % cornstarch (cornstarch Y, by Nihon Shokuhin Kako Co., Ltd. produces) is put into the hot bath of boiling, and places 30 minutes so that the starch gel gel.Then, this container is put into 40 ℃ water-bath, and place 1 hour with this solution of slaking.Then, be that the enzyme (AMS of being produced by Daiwa Kasei K.K.) of 0.3 weight % of the dry weight of unmodified starch in the starch solution adds in the starch solution with consumption, and stirred this starch solution 1 minute.Subsequently, container is put into the hot bath of boiling, and place 10 minutes so that enzyme deactivation.Then, this container is cooled to 23 ℃ to obtain starch A, it is enzymically modified starch F.
Preparation comprises the 8 weight % aqueous solution (surface size) of starch A and saltcake.In this solution, the weight of the amount of solid of starch A is 10 times of saltcake weight.Solution is heated to 50 ℃, and by by Kumagai Riki Kogyo Co., the test that Ltd. produces is used for the size press of gained base paper with size presser with this solution, makes that the amount of solid that is applied to basic paper is 2g/m
2Then, should base paper with Kumagai Riki Kogyo Co., the rotary-type drying machine of KRK that Ltd. produces with 0.5 meter/minute condition 120 ℃ of dryings, quantitatively being 70g/m
2Record-paper (1).
(record-paper 2)
Using the method identical with preparing starch A to obtain starch B is enzymically modified starch F, and difference is that the amount with enzyme changes 0.10 weight % of unmodified starch dry weight into.Except using starch B to replace the starch A, use the method identical to obtain record-paper (2) with preparing record-paper (1).The quantitative of record-paper (2) is 70g/m
2
(record-paper 3)
Will be by the paper pulp defibre of matter waste paper preparation in dry broad leaf tree kraft pulp of 3 mass parts and 7 mass parts, and carry out refining, make freedom become 350ml.Then, preparation paper pulp dispersion liquid makes that the solids content of paper pulp is 0.3 quality %.Except the paper pulp dispersion liquid being changed into the above-mentioned paper pulp dispersion liquid that obtains, use the method identical to obtain record-paper (3) with preparing record-paper (1).The quantitative of record-paper (3) is 70g/m
2
(record-paper 4)
Except the amount with enzyme changes 0.03 weight % of unmodified starch dry weight into, use the method identical to obtain starch C with preparing starch A, it is enzymically modified starch F.Except using starch C to replace the starch A, use the method identical to obtain record-paper (4) with preparing record-paper (1).The quantitative of record-paper (4) is 70g/m
2
(record-paper 5)
Except commercially available enzymically modified starch (HI-COASTER, by Sanwa Cornstarch Co., Ltd. produces) is used to replace outside the starch A as Cypres, use the method identical to obtain record-paper (5) with preparing record-paper (1).The quantitative of record-paper (5) is 70g/m
2
(record-paper 6)
Except commercially available oxidized starch (ACE A, by Oji Cornstarch Co., Ltd. produces) is used to replace outside the starch A as Cypres, use the method identical to obtain record-paper (6) with preparing record-paper (1).The quantitative of record-paper (6) is 70g/m
2
(record-paper 7)
Except with unprocessed starch (cornstarch Y, by Nihon Shokuhin Kako Co., Ltd. produce) be used to replace outside the starch A as Cypres, use the method identical to obtain record-paper (7) with preparing record-paper (1), this unprocessed starch is the initiation material of starch A.The quantitative of record-paper (7) is 70g/m
2
(record-paper 8)
Except with the oxidized starch of dry oxidation preparation (by the oxidized starch of dry oxidation preparation, by OjiCornstarch Co., Ltd. produce) in statu quo be used to replace outside the starch A as Cypres, use the method identical to obtain record-paper (8) with preparing record-paper (1).The quantitative of record-paper (8) is 70g/m
2
(record-paper 9)
Except starch material is changed into the wheaten starch by cornstarch, use the method identical to obtain starch D with preparing starch A, it is enzymically modified starch F.Except starch D is used to replace the starch A, use the method identical to obtain record-paper (9) with preparing record-paper (1).The quantitative of record-paper (9) is 70g/m
2
The preparation condition of record-paper (composition) is listed in table 1.The performance of record-paper, for example reflection density is listed in table 2.
Table 1
| The record-paper numbering | Paper pulp | The composition of Cypres (weight ratio) | Amount (the g/m of Cypres 2) | The starch kind |
| (1) | Freedom is the broad leaf tree paper pulp of 420ml | Starch A: saltcake=100: 10 | 2.0 | Starch A |
| (2) | Freedom is the broad leaf tree paper pulp of 420ml | Starch B: saltcake=100: 10 | 2.0 | Starch B |
| (3) | Middle matter waste paper: broad leaf tree paper pulp=7: 3, freedom are 350ml | Starch A: saltcake=100: 10 | 2.0 | Starch A |
| (4) | Freedom is the broad leaf tree paper pulp of 420ml | Starch C: saltcake=100: 10 | 2.0 | Starch C |
| (5) | Freedom is the broad leaf tree paper pulp of 420ml | PC-11: saltcake=100: 10 | 2.0 | (traditional) enzymically modified starch |
| (6) | Freedom is the broad leaf tree paper pulp of 420ml | ACE A: saltcake=100: 10 | 2.0 | Oxidized starch by the wet oxidation preparation |
| (7) | Freedom is the broad leaf tree paper pulp of 420ml | Cornstarch Y: saltcake=100: 10 | 2.0 | Unmodified starch |
| (8) | Freedom is the broad leaf tree paper pulp of 420ml | Oxidized starch by the dry oxidation preparation: saltcake=100: 10 | 2.0 | Oxidized starch by the dry oxidation preparation |
| (9) | Freedom is the broad leaf tree paper pulp of 420ml | Starch D: saltcake=100: 10 | 2.0 | Starch D |
*Starch A～D is an enzymically modified starch, and they are in the scope of the enzymically modified starch F that produces by the method for embodiment of the present invention.
Table 2
| The record-paper numbering | Quantitative (g/m 2) | Reflection density | Evenness index | Surface resistivity (Ω/sq)/specific insulation (Ω cm) |
| (1) | 70 | 0.51 | 25 | 1.0×10 10/1.0×10 11 |
| (2) | 70 | 0.50 | 25 | 1.0×10 10/1.0×10 11 |
| (3) | 70 | 0.51 | 25 | 1.0×10 10/1.0×10 11 |
| (4) | 70 | 0.58 | 25 | 1.0×10 10/1.0×10 11 |
| (5) | 70 | 0.64 | 25 | 1.0×10 10/1.0×10 11 |
| (6) | 70 | 0.82 | 25 | 1.0×10 10/1.0×10 11 |
| (7) | 70 | 0.85 | 22 | 1.0×10 10/1.0×10 11 |
| (8) | 70 | 0.71 | 23 | 1.0×10 10/1.0×10 11 |
| (9) | 70 | 0.48 | 25 | 1.0×10 10/1.0×10 11 |
＜assessment 〉
Record-paper is used for electrophotographic image forming and ink-jet imaging.Curling after the assessment imaging.Carry out the assessment of record-paper in the following manner.Assessment result is shown in table 3.
(1) curling in the assessment electrophotographic recording
Record-paper (1)～(9) are placed 12 hours to control its moisture in 23 ℃, the environment of 65%RH.The record recto is meant that the opposite face of one side that dewaters when copying paper.Service recorder recto surface is as imaging surface, and by Fuji Xerox Printing Systems Co., this record-paper of DOCUPRINT 260 usefulness that Ltd. produces carries out single-sided copying, then the curling height of assessment.
Record-paper is cut into B5, and (scraps of paper of size of 182mm * 257mm) make MD (copying the direction that paper advances) direction for vertically.The blank sheet of paper that use does not have an image is as the original paper that will duplicate, and the record-paper of B5 size is used for aforesaid single-sided copying.Since with blank sheet of paper as the original paper that will duplicate, so on the record-paper of B5 size, forming image.Use following evaluation criteria to assess the curling height h of each record-paper.Having only grade A and B is acceptable level.
Illustrate the height h that curls among Fig. 1.As shown in Figure 1, the height h that curls is meant and connects on the plane 1 a bit and the length of the nose of any on the edge 3 of record-paper 2 that this longest line is perpendicular to plane 1, and wherein, record-paper 2 is the record-paper behind the heat fixation, and record-paper 2 is positioned on the plane 1.
Grade A:h＜45mm
Grade B:45mm≤h＜55mm
Grade C:h 〉=55mm
(2) curling in the assessment ink mist recording
To the assessment of curling that takes place immediately after printing
Record-paper is cut into the postcard size (scraps of paper of 100mm * 148mm).(amount of the printing ink of being used is: 10g/m with the red 100% solid image of ink jet recording device (N2100, by Canon Inc. produce) printed product on the single face of each record-paper (margin with 5mm) of every postcard size
2).Measure and print the back, change measured value into curvature being different from the unsettled amount of crimp that occurs immediately on the another side of printing surface.Use this curvature of following criterion evaluation.Having only grade A and B is acceptable level.
Grade A: less than 35m
-1
Grade B:35m
-1～50m
-1
Grade C: greater than 50m
-1
To the assessment of curling after air-dry
Record-paper is cut into the postcard size (scraps of paper of 100mm * 148mm).With ink jet recording device (N2100 is produced by Canon Inc.) red 100% solid image (amount of the printing ink of being used: 10g/m of printed product on the single face of each record-paper (margin) of every postcard size with 5mm
2).The print surface of record-paper is upwards kept flat, and it is rested under 23 ℃, the condition of 50%RH.This paper being placed under this condition after 100 hours, measure unsettled amount of crimp, and change measured value into curvature.Use this curvature of following criterion evaluation.Having only grade A and B is acceptable level.
Grade A: less than 30m
-1
Grade B:30m
-1～75m
-1
Grade C: greater than 75m
-1
The results are shown in down in the tabulation 3.
| The record-paper numbering | Assessment result | Remarks | ||
| Electrophotographic recording | Ink mist recording | |||
| Height curls | What take place immediately after the printing curls | Curling after air-dry | ||
| 1 | A | A | A | The present invention |
| 2 | A | A | A | The present invention |
| 3 | B | B | B | The present invention |
| 4 | B | B | B | The present invention |
| 5 | C | C | C | Comparative Examples |
| 6 | C | C | C | Comparative Examples |
| 7 | C | C | C | Comparative Examples |
| 8 | C | C | C | Comparative Examples |
| 9 | A | A | A | The present invention |
The broad leaf tree kraft pulp is carried out the bleaching of ECF multistep, and this ECF multistep bleaching comprises oxygen bleaching, alkalescence extraction and gas phase chlorine dioxide treatment.The paper pulp of bleaching is carried out refining makes freedom become 450ml.The paper pulp of 100 mass parts gained is mixed with sizing agent with 10 mass parts bentonite fillers, 10 mass parts precipitated calcium carbonate fillers and 0.1 mass parts alkyl ketene dimer (AKD) are interior, then mixture is copied paper.
Prepare coating fluid (as surface size) independently, it comprises 88 mass parts water, 6 mass parts sodium chloride and 6 mass parts by handle the enzymically modified starch that commercially available cornstarch obtains with AMS.To the above-mentioned paper that the obtains size press of coating fluid, thereby obtain quantitatively being 64g/m
2Record-paper, wherein, this record-paper surface has 1.0g/m
2Sodium chloride and 1.0g/m
2Enzymically modified starch.
The broad leaf tree kraft pulp is carried out the bleaching of TCF multistep, and this TCF multistep bleaching comprises zytase processing, alkaline extraction, hydrogen peroxide treatment and ozone treatment.Paper pulp to bleaching carries out refining, makes freedom become 450ml.The paper pulp that 100 mass parts are obtained mixes with sizing agent with 3 mass parts kaolin fillers, 6 mass parts precipitated calcium carbonate fillers and 0.2 mass parts alkenyl succinic anhydride (ASA) are interior, then mixture is copied paper.
Prepare coating fluid (as surface size) independently, it comprises 80 mass parts water, 12 mass parts calcium bicarbonates and the 8 mass parts oxidized starch by the dry oxidation preparation.To the above-mentioned paper that the obtains size press of coating fluid, thereby obtain quantitatively being 68g/m
2Record-paper, wherein, this record-paper surface has 1.5g/m
2Calcium bicarbonate and 1.0g/m
2The oxidized starch that passes through dry oxidation preparation.
Embodiment 4
Use bisulfite salt pair coniferous tree kraft pulp to bleach processing, carry out refining then, make freedom become 450ml.Mix with sizing agent in the paper pulp that 100 mass parts are obtained and 8 mass parts precipitated calcium carbonate fillers and the 0.02 mass parts alkenyl succinic anhydride (ASA), then mixture is copied paper.
Prepare coating fluid (as surface size) independently, it comprises 75 mass parts water, 15 mass parts magnesium hydroxides and 10 mass parts by handle the enzymically modified starch that commercially available farina obtains with AMS.To the above-mentioned paper that the obtains size press of coating fluid, quantitatively being 82g/m
2Record-paper, wherein, this record-paper surface has 2.0g/m
2Magnesium hydroxide and 1.5g/m
2Enzymically modified starch.
Embodiment 5
Use the method identical, the broad leaf tree kraft pulp is carried out ECF bleach with embodiment 2.Paper pulp refiner with bleaching makes freedom become 450ml.Mix with sizing agent in the paper pulp that 100 mass parts are obtained and 15 mass parts precipitated calcium carbonate fillers and the 0.1 mass parts alkenyl succinic anhydride (ASA), then mixture is copied paper.
Prepare coating fluid (as surface size) independently, it comprises oxidized starch and the 5 mass parts calcium hydroxides that use among 90 mass parts water, the 5 mass parts embodiment 3.To the above-mentioned paper that the obtains size press of coating fluid, quantitatively being 55g/m
2Record-paper, wherein, this record-paper surface has 0.6g/m
2Oxidized starch and 0.6g/m
2Calcium hydroxide.
Embodiment 6
Use the method identical to copy paper with embodiment 5.Prepare coating fluid (as surface size) independently, it comprises oxidized starch and the 10 mass parts calcium lactates that use among 60 mass parts water, the 30 mass parts embodiment 3.To the above-mentioned paper that the obtains size press of coating fluid, quantitatively being 55g/m
2Record-paper, wherein, this record-paper surface has 4.5g/m
2Oxidized starch and 1.5g/m
29 calcium lactate.
Embodiment 7
Use the method identical to copy paper with embodiment 5.Mix commercially available cornstarch aqueous liquid dispersion and aqueous sodium hypochlorite solution independently, and be to place 2 hours to obtain oxidized starch under 10 the condition in the pH value.Preparation coating fluid (as surface size), it comprises above-mentioned oxidized starch that obtains of enzymically modified starch, 5 mass parts and the 10 mass parts calcium lactates that use among 75 mass parts water, the 10 mass parts embodiment 2.To the above-mentioned paper that the obtains size press of coating fluid, quantitatively being 55g/m
2Record-paper, wherein, this record-paper surface has 1.5g/m
2Enzymically modified starch, 0.8g/m
2Oxidized starch and 1.5g/m
2Calcium lactate.
Comparative Examples 1
Use with embodiment 3 in identical method the broad leaf tree kraft pulp carried out TCF bleach.Paper pulp to bleaching carries out refining, makes freedom become 450ml.The paper pulp that 100 mass parts are obtained mixes with the neutral rosin sizing agent of 3 mass parts precipitated calcium carbonate fillers, 3 mass parts saponite fillers and 2 mass parts, and this mixture is copied paper.
In addition, commercially available cornstarch aqueous liquid dispersion being mixed with aqueous sodium hypochlorite solution, is to place 3 hours under 8 the condition to obtain oxidized starch at pH then.Preparation coating fluid (as surface size), it comprises 65 mass parts water, the above-mentioned oxidized starch that obtains of 15 mass parts and 20 mass parts calcium hydroxides.To the above-mentioned paper that the obtains size press of coating fluid, quantitatively being 100g/m
2Record-paper, wherein, this record-paper surface has 2.0g/m
2Oxidized starch and 2.5g/m
2Calcium hydroxide.
Comparative Examples 2
Use with embodiment 3 in identical method the broad leaf tree kraft pulp carried out TCF bleach.Paper pulp to bleaching carries out refining, makes freedom become 450ml.The paper pulp that 100 mass parts are obtained mixes with 15 mass parts precipitated calcium carbonate fillers and 0.1 mass parts alkenyl succinic acid acid anhydrides (ASA) sizing agent, and this mixture is copied paper.
In addition, preparation coating fluid (as surface size), it comprises 80 mass parts water, 10 mass parts sodium chloride and 10 mass parts calcium hydroxides.To the above-mentioned paper that the obtains size press of coating fluid, quantitatively being 64g/m
2Record-paper, wherein, this record-paper surface has 2.0g/m
2Sodium chloride and 2.0g/m
2Calcium hydroxide.
Comparative Examples 3
Use with embodiment 3 in identical method the broad leaf tree kraft pulp carried out TCF bleach.Paper pulp to bleaching carries out refining, makes freedom become 450ml.The paper pulp that 100 mass parts are obtained mixes with 20 mass parts kaolin fillers and 0.05 mass parts alkyl ketene dimer (AKD) sizing agent, and this mixture is copied paper.
In addition, preparation coating fluid (as surface size), it comprises 92 mass parts water, 5 mass parts oxidized starch and the 3 mass parts calcium thiocyanates as preparation as described in the Comparative Examples 1.To the above-mentioned paper that the obtains size press of coating fluid, quantitatively being 64g/m
29 record-paper, wherein, this record-paper surface has 0.05g/m
2Calcium thiocyanate and 0.07g/m
2Oxidized starch.
Comparative Examples 4
Use with embodiment 3 in identical method the broad leaf tree kraft pulp carried out TCF bleach.Paper pulp to bleaching carries out refining, makes freedom become 450ml like this.Mix paper pulp, 20 mass parts kaolin fillers, 0.05 mass parts alkyl ketene dimer (AKD) sizing agent that 100 mass parts obtain, and this mixture is copied paper.
In addition, preparation coating fluid (as surface size), it comprises enzymically modified starch used among 40 mass parts water, the 30 mass parts embodiment 2 and 30 mass parts calcium thiocyanates.To the above-mentioned paper that the obtains size press of coating fluid, quantitatively being 68g/m
2Record-paper, wherein, this record-paper surface has 5.0g/m
2Calcium thiocyanate and 5.0g/m
2Enzymically modified starch.
Comparative Examples 5
Use with embodiment 5 in identical method copy paper.In addition, preparation coating fluid (as surface size), it comprises used enzymically modified starch among 77 mass parts water, the 15 mass parts embodiment 2, the commercially available oxidized starch of 5 mass parts (ACE C, by Oji Comstarch Co., Ltd. produces) and 3 mass parts sodium sulphate.To the above-mentioned paper that the obtains size press of coating fluid, quantitatively being 70g/m
2Record-paper, wherein, this record-paper surface has 2.0g/m
2Enzymically modified starch, 0.7g/m
2Oxidized starch and 0.06g/m
2Sodium sulphate.
The performance of surveying record paper
Measure the performance of resulting records paper as follows.Measure St ckigt degree of sizing according to JIS-P-8122:1976 down in standard conditions (23 ℃, 50%RH).According to JIS-K-6911 meter surface resistivity and specific insulation under standard conditions.According to JIS-P-8119:1998, show gas permeability smoothness measurement device EY type (by Asahi Seiko Co., Ltd. produces) measurement smoothness with the Ohken numeral.Measure evenness index with little evenness tester, and adopt by M/K Systems, the 3-D paper analyzer (M/K950) that Inc. produces, the aperture of this analyzer is made as diameter 1.5mm.
Assessment to hot water extract's character
It is 0.06m that each record-paper is cut into area
2Sheet.100 ℃ of Soxhlets that this sheet carried out 8 hours are extracted.Then, dry this extract and make its curing.Measure the weight of this solid, the carboxyl-content of solid and the infrared absorption spectroscopy of solid.The measurement of carboxyl-content is carried out as follows.
According to Matisson﹠amp; The direct titrimetric method of Legendre is measured carboxyl-content.Detailed process is as described below.0.1N hydrochloric acid is added in the solid that 0.15g obtains with hot water extracting, and this mixture was stirred 30 minutes.Mixture is placed glass filter, and, from filtrate, disappear, wherein, be added drop-wise to liquor argenti nitratis ophthalmicus in the filtrate and check whether the adularescent precipitation produces, and proves conclusively whether there is chlorion in the filtrate with this up to chlorion with pure water washing.The solid of washing is placed beaker, and be dispersed in the pure water of 300ml, heat then and dissolve.After this, as indicator, use this solution of 0.01N sodium hydroxide solution titration with phenolphthalein.Calculate carboxyl-content according to following equation.The amount (ml) * 0.01 of the sodium hydroxide solution of carboxyl-content (mM/100 grams)=consumption (equivalent concentration of sodium hydroxide solution, mol/l) * 100/0.15
The measurement result of hot water extracting properties is listed in table 4 and 5 with the composition of the treatment fluid that is used to prepare record-paper.
According to following standard, use the curling and transfer printing after the electrophotographic recording equipment DOCUCENTRECOLOR 400CP that is produced by company of Fuji-Xerox comes the printing of evaluate recorded paper.The results are shown in table 4 and 5.
To the assessment of curling after printing
Each record-paper (being cut into the A4 size) was positioned over 23 ℃, 65%RH condition following 8 hours, to regulate moisture.Only use black ink, on 10 record-papers of each embodiment or Comparative Examples, print identical text image successively respectively with 5% image color.At once record-paper is placed smooth test desk after the printing.Then, the vertical range between four of measuring table and each record-paper summits.Determine the maximum normal distance (certainty of measurement is the mm level) on 40 summits (4 summit * 10 paper).According to following criterion evaluation maximum normal distance, wherein, it is actual acceptable having only grade A.
Grade A: maximum normal distance is less than 25mm
Grade B: maximum normal distance is 26mm～35mm
Grade C: maximum normal distance is greater than 36mm
The assessment transfer printing
Check the above-mentioned print image that obtains, and determine appearance degree by the spot of transfer printing defective generation.Evaluation criteria is as described below, and it is actual acceptable wherein having only grade A.
Grade A: do not observe the image color spot
Grade A: observe slight image color spot
Grade C: on image, can observe serious image color spot everywhere
The evaluate image optical concentration
The ink jet recording device WORKCENTRE B900 that use is produced by company of Fuji-Xerox is according to following criterion evaluation image optical concentration.The results are shown in table 4 and 5.During printing, condition is 23 ℃, 50%RH; Injector spacing is 800dpi (dpi (dots per inch)); Nozzle number is 256; The amount of dripping approximately is 15pl; The maximum injection quantity of printing ink and pretreatment fluid is about 15ml/m
2Printing model is printed for the single face batch (-type); The sweep speed of record head is about 1100mm/ second.In ink jet recording device, black ink is a pigmented ink and colored ink is a dye type printing ink.Evaluation criteria is explained as follows.
Printed back first day, use X-RITE 369 (producing) to measure the image optical concentration of black and the solid color block areas of magenta, and calculate its mean value (promptly trying to achieve the mean value of the concentration of the concentration of solid black color block areas and the solid color block areas of magenta) by X-rite.Evaluation criteria is as follows, and it is actual acceptable wherein having only grade A and B.
Grade A: mean value is more than 1.5 or 1.5
Grade B: mean value is more than 1.0 or 1.0, but less than 1.5
Grade C: mean value is less than 1.0
In table 4 and the table 5, L-BKP represents Laulholz bleached kraft pulp (bleached hardwood kraft pulp), N-BMP represents Nadelholz bleached mechanical pulp (coniferous tree bleached mechanical pulp), N-BKP represents Nadelholz bleached kraft pulp (coniferous tree bleached kraft pulp), and L-BSP represents Laulholz bleaching sulfite pulp (bleached hardwood sulfite pulp).In table 4 and the table 5, the oxidized starch that is prepared by dry oxidation is expressed as " dry oxidation starch ".
Table 4
| Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | |
| Paper pulp | L-BKP | L-BKP | N-BMP | L-BKP | L-BKP | L-BKP |
| ECF | TCF | Bisulfites | ECF | ECF | ECF | |
| Freedom | 450ml | 450ml | 450ml | 450ml | 450ml | 450ml |
| Quantitative (g/m 2) | 64 | 68 | 82 | 55 | 55 | 55 |
| Filler (with respect to the percentage (%) of paper pulp) | Bentonite 10 | Kaolin 3 | ||||
| Precipitated calcium carbonate 10 | Precipitated calcium carbonate 6 | Precipitated calcium carbonate 8 | Precipitated calcium carbonate 15 | Precipitated calcium carbonate 15 | Precipitated calcium carbonate 15 | |
| Interior with sizing agent (with respect to the percentage (%) of paper pulp) | AKD 0.1 | ASA 0.2 | ASA 0.02 | ASA 0.1 | ASA 0.1 | ASA 0.1 |
| The composition of surface size (weight %) | Enzymically modified starch 6 | Dry oxidation starch 8 | Enzymically modified starch 10 | Dry oxidation starch 5 | Dry oxidation starch 30 | Enzymically modified starch 10, oxidized starch 5 |
| Sodium chloride 6 | Calcium bicarbonate 12 | Magnesium hydroxide 15 | Calcium hydroxide 5 | Calcium lactate 10 | Calcium lactate 10 | |
| Amount of application (g/m 2 The amount of solid of each face) | Enzymically modified starch 1.0 | Dry oxidation starch 1.0 | Enzymically modified starch 1.5 | Dry oxidation starch 0.6 | Dry oxidation starch 4.5 | Enzymically modified starch 1.5; Oxidized starch 0.8 |
| Sodium chloride 1.0 | Calcium bicarbonate 1.5 | Magnesium hydroxide 2.0 | Calcium hydroxide 0.6 | Calcium lactate 1.5 | Calcium lactate 1.5 | |
| From 0.06m 2The amount of solid that the hot water extracting of the scraps of paper obtains (g) | 0.07 | 0.12 | 0.13 | 0.06 | 0.35 | 0.22 |
| Carboxyl-content in the solid (meq/100g) | 0.56 | 2.00 | 1.30 | 2.10 | 2.60 | 2.93 |
| The distinctive infrared absorption peak of starch | Can be observed | Can be observed | Can be observed | Can be observed | Can be observed | Can be observed |
| Surface resistivity/specific insulation | 0.83 | 0.43 | 0.38 | 0.33 | 0.11 | 0.11 |
| Surface resistivity (Ω/sq) | 1.5×10 10 | 3.2×10 10 | 1.5×10 10 | 6.5×10 9 | 7.5×10 9 | 7.5×10 9 |
| Specific insulation (Ω cm) | 1.8×10 10 | 7.5×10 10 | 4.0×10 10 | 2.0×10 10 | 6.7×10 10 | 6.7×10 10 |
| Carboxyl-content in the starch (meq/100g) | 1.3 | 2.6 | 1.5 | 2.6 | 2.6 | 2.87 |
| St ckigt degree of sizing (s) | 10 | 16 | 10 | 20 | 15 | 15 |
| Smoothness (s) | 25 | 70 | 85 | 100 | 100 | 100 |
| Evenness index | 20 | 30 | 38 | 35 | 30 | 30 |
| Curling behind the heat fixation | B | B | B | B | B | B |
| Transfer printing in the electrofax | A | A | A | A | B | B |
| The ink jet image optical concentration | B | A | B | B | B | A |
Table 5
| Comparative Examples 1 | Comparative Examples 2 | Comparative Examples 3 | Comparative Examples 4 | Comparative Examples 5 | |
| Paper pulp | L-BKP | L-BSP | N-BKP | L-BSP | L-BKP |
| TCF | TCF | TCF | TCF | TCF | |
| Freedom | 450ml | 450ml | 450ml | 450ml | 450ml |
| Quantitative (g/m 2) | 100 | 64 | 64 | 68 | 70 |
| Filler (with respect to the percentage (%) of paper pulp) | Precipitated calcium carbonate 3 | ||||
| Saponite 3 | Precipitated calcium carbonate 15 | Kaolin 20 | Kaolin 20 | Kaolin 20 | |
| Internal sizing agent (with respect to the percentage (%) of paper pulp) | Neutral rosin 2 | ASA 0.1 | AKD0.05 | AKD 0.05 | AKD 0.05 |
| The composition of surface size (weight %) | Oxidized starch 15 | Sodium chloride 10 | Oxidized starch 5 | Enzymically modified starch 30 | Oxidized starch 5; Enzymically modified starch 15 |
| Calcium hydroxide 20 | Calcium hydroxide 10 | Calcium thiocyanate 3 | Calcium thiocyanate 30 | Sodium sulphate 3 | |
| Amount of application (g/m 2 The amount of solid of each face) | Oxidized starch 2.0 | Sodium chloride 2.0 | Oxidized starch 0.07 | Enzymically modified starch 5.0 | Oxidized starch 0.7; Enzymically modified starch 2.0 |
| Calcium hydroxide 2.5 | Calcium hydroxide 2.0 | Calcium thiocyanate 0.05 | Calcium thiocyanate 5.0 | Sodium sulphate 0.06 | |
| From 0.06m 2The amount of solid that the hot water extracting of the scraps of paper obtains (g) | 0.19 | 0.19 | 0.004 | 0.480 | 0.23 |
| Carboxyl-content in the solid (meq/100g) | 5.78 | 0.00 | 7.58 | 0.55 | 5.37 |
| The distinctive infrared absorption peak of starch | Can be observed | Do not observe | Can be observed | Can be observed | Can be observed |
| Surface resistivity/specific insulation | 0.02 | 0.06 | 0.5 | 0.06 | 0.11 |
| Surface resistivity (Ω/sq) | 1.0×10 9 | 5.0×10 8 | 6.5×10 11 | 8.9×10 9 | 7.5×10 10 |
| Specific insulation (Ω cm) | 5.0×10 10 | 7.8×10 9 | 1.3×10 12 | 1.5×10 11 | 6.7×10 11 |
| Carboxyl-content in the starch (meq/100g) | 13.9 | - | 13.9 | 1.3 | 4.62 |
| St ckigt degree of sizing (s) | 25 | 10 | 5 | 80 | 25 |
| Smoothness (s) | 120 | 18 | 90 | 100 | 100 |
| Evenness index | 35 | 6 | 38 | 20 | 20 |
| Curling behind the heat fixation | C | B | C | A | C |
| Transfer printing in the electrofax | A | C | A | B | B |
| The ink jet image optical concentration | B | A | B | C *1 | C |
*1 printing ink almost can not infiltrate record-paper, therefore spot occurs in the zone of solid image.
Can clearly be seen that from table 4 and table 5 when carrying out electrophotographic printer on record-paper of the present invention, curling behind the heat fixation is suppressed and the transfer printing defective do not occur.When on record-paper of the present invention, carrying out inkjet printing, can obtain higher color rendition.
As mentioned above, the present invention can provide the formation method of a kind of record-paper and this record-paper of use.This record-paper can be used for electrophotographic recording and ink mist recording.When record-paper of the present invention is used for electrophotographic recording, suppressed the appearance of curling, kept the same high transfer printing simultaneously with traditional paper.When record-paper of the present invention is used for ink mist recording, can obtain fabulous color rendition.
In addition, the present invention can also provide the record-paper that is obtained by the method for using starch as Cypres.When this record-paper is used for electro photography or ink jet type duplicator and printer, can suppress curling.The present invention also provides the image recording process that uses this record-paper.
Claims (16)
1. it is that the basic paper that the Cypres coating of main component comprises paper pulp obtains that record-paper, this record-paper adopt with starch, wherein, with this record-paper after leaving standstill 5 hours under 23 ℃, the condition of 50%RH, on the surface of this record-paper with 10ml/m
2Amount PVP-I concentration is provided is that 70mg/ml and available iodine content are the PVP-I liquid of 7mg/ml, then with this record-paper after leaving standstill 5 hours under 23 ℃, the condition of 50%RH, the reflection density on surface with described PVP-I liquid is for smaller or equal to 0.60.
2. record-paper as claimed in claim 1, wherein, described starch prepares by the following method, and this method comprises:
Starch and water are mixed to form amidin;
Heat this amidin, so that this amidin gelation; Then
Under the temperature of the heating-up temperature that is lower than described gelation, make this amidin slaking; Then
By in this amidin, adding enzyme so that this starch is carried out enzyme modification; Then
Heat this amidin so that this enzyme deactivation and stop the reaction.
3. record-paper as claimed in claim 1, wherein, when to 0.06m
2This record-paper when carrying out hot water extracting, the amount of solid of extract is 0.01g～0.4g, and carboxyl-content is 0～5 mM/100 grams in this solid.
4. record-paper as claimed in claim 3, wherein, described record-paper also comprises filler.
5. record-paper as claimed in claim 1, wherein, described Cypres comprises the above metal of divalence or divalence, and under 23 ℃, the condition of 50%RH, the surface resistivity of this record-paper and the ratio of specific insulation are 0.1～1, and described surface resistivity is 1.0 * 10
9Ω/sq～1.0 * 10
11Ω/sq, and described specific insulation is 5.0 * 10
9Ω cm～5.0 * 10
11Ω cm.
6. record-paper as claimed in claim 3, wherein, described Cypres comprises the above metal of divalence or divalence, and under 23 ℃, the condition of 50%RH, the surface resistivity of this record-paper and the ratio of specific insulation are 0.1～1, and described surface resistivity is 1.0 * 10
9Ω-/sq～1.0 * 10
11Ω/sq, and described specific insulation is 5.0 * 10
9Ω cm～5.0 * 10
11Ω cm.
7. the method for a record of production paper, this method comprises:
Starch and water are mixed to form amidin;
Heat this amidin, so that this amidin gelation; Then
Under the temperature of the heating-up temperature that is lower than described gelation, make this amidin slaking; Then
By in this amidin, adding enzyme so that this starch is carried out enzyme modification; Then
Heat this amidin so that this enzyme deactivation and stop the reaction, thereby obtain enzymically modified starch;
Preparation is the Cypres of main component with described enzymically modified starch; And
Use described Cypres coating to comprise the basic paper of paper pulp.
8. electrophotographic image recording method, this method comprises:
Uniform charging is carried out on surface to the electrostatic latent image holding member;
The face exposure that makes this electrostatic latent image holding member is to form electrostatic latent image;
Make this latent electrostatic image developing to form toner image with electrostatic developer;
Described toner image is transferred to the surface of record-paper; And
This toner image is fixed on the described surface of this record-paper,
Wherein, to adopt with starch be that the basic paper that the Cypres coating of main component comprises paper pulp obtains for this record-paper; And, with this record-paper after leaving standstill 5 hours under 23 ℃, the condition of 50%RH, on the surface of this record-paper with 10ml/m
2Amount PVP-I concentration is provided is that 70mg/ml and available iodine content are the PVP-I liquid of 7mg/ml, then with this record-paper after leaving standstill 5 hours under 23 ℃, the condition of 50%RH, the reflection density on surface with described PVP-I liquid is for smaller or equal to 0.60.
9. ink jet image recording method, this method comprises the surface that ink droplet is applied to record-paper, on this surface, forming image,
Wherein, to adopt with starch be that the basic paper that the Cypres coating of main component comprises paper pulp obtains for this record-paper; And, with this record-paper after leaving standstill 5 hours under 23 ℃, the condition of 50%RH, on the surface of this record-paper with 10ml/m
2Amount PVP-I concentration is provided is that 70mg/ml and available iodine content are the PVP-I liquid of 7mg/ml, then with this record-paper after leaving standstill 5 hours under 23 ℃, the condition of 50%RH, the reflection density on surface with described PVP-I liquid is for smaller or equal to 0.60.
10. it is that the surface of the basic paper of main component makes with paper pulp and filler that record-paper, this record-paper adopt the treatment fluid coating that comprises starch, wherein, and when to 0.06m
2Described record-paper when carrying out hot water extracting, the amount of solid of extract is 0.01g～0.4g, and carboxyl-content is 0～5 mM/100 grams in this solid.
11. record-paper as claimed in claim 10, wherein, described treatment fluid comprises the salt of the above metal of divalence or divalence, and under 23 ℃, the condition of 50%RH, the surface resistivity of this record-paper and the ratio of specific insulation are 0.1～1, and described surface resistivity is 1.0 * 10
9Ω/sq～1.0 * 10
11Ω/sq, and described specific insulation is 5.0 * 10
9Ω cm～5.0 * 10
11Ω cm.
12. record-paper as claimed in claim 10, wherein, the carboxyl-content of the starch in the described treatment fluid is 0～5 mM/100 grams.
13. record-paper as claimed in claim 10, wherein, described starch prepares by the following method, and this method comprises:
Starch and water are mixed to form amidin;
Heat this amidin, so that this amidin gelation; Then
Under the temperature of the heating-up temperature that is lower than described gelation, make this amidin slaking; Then
By in this amidin, adding enzyme so that this starch is carried out enzyme modification; Then
Heat this amidin so that this enzyme deactivation and stop the reaction.
14. record-paper as claimed in claim 11, wherein, described starch prepares by the following method, and this method comprises:
Starch and water are mixed to form amidin;
Heat this amidin, so that this amidin gelation; Then
Under the temperature of the heating-up temperature that is lower than described gelation, make this amidin slaking; Then
By in this amidin, adding enzyme so that this starch is carried out enzyme modification; Then
Heat this amidin so that this enzyme deactivation and stop the reaction.
15. the method for an electrophotographic image record, this method comprises:
Uniform charging is carried out on surface to the electrostatic latent image holding member;
The face exposure that makes this electrostatic latent image holding member is to form electrostatic latent image;
Make this latent electrostatic image developing to form toner image with electrostatic developer;
Described toner image is transferred to the surface of record-paper; And
This toner image is fixed on the described surface of this record-paper,
Wherein, to adopt the treatment fluid coating that comprises starch be that the surface of the basic paper of main component makes with paper pulp and filler for this record-paper; And, when to 0.06m
2Described record-paper when carrying out hot water extracting, the amount of solid of extract is 0.01g～0.4g, and carboxyl-content is 0～5 mM/100 grams in this solid.
16. an ink jet image recording method, this method comprises the surface that ink droplet is applied to record-paper, and to form image on this surface, described ink droplet comprises colouring agent and is selected from water and at least a material of water-soluble solvent,
Wherein, to adopt the treatment fluid coating that comprises starch be that the surface of the basic paper of main component makes with paper pulp and filler for this record-paper; And, when to 0.06m
2Described record-paper when carrying out hot water extracting, the amount of solid of extract is 0.01g～0.4g, and carboxyl-content is 0～5 mM/100 grams in this solid.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004262628A JP4529601B2 (en) | 2004-09-09 | 2004-09-09 | Recording paper and image recording method using the same |
| JP2004262303 | 2004-09-09 | ||
| JP2004262628 | 2004-09-09 |
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| CN2007101680375A Division CN101173488B (en) | 2004-09-09 | 2005-02-28 | Recording sheets and image forming method using the recording sheets |
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| CN1746038A true CN1746038A (en) | 2006-03-15 |
| CN100391750C CN100391750C (en) | 2008-06-04 |
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| CN2007101680375A Expired - Fee Related CN101173488B (en) | 2004-09-09 | 2005-02-28 | Recording sheets and image forming method using the recording sheets |
| CNB2005100511474A Expired - Fee Related CN100391750C (en) | 2004-09-09 | 2005-02-28 | Recording sheets and image forming method using the recording sheets |
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| Application Number | Title | Priority Date | Filing Date |
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| CN2007101680375A Expired - Fee Related CN101173488B (en) | 2004-09-09 | 2005-02-28 | Recording sheets and image forming method using the recording sheets |
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| JP (1) | JP4529601B2 (en) |
| CN (2) | CN101173488B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102574406A (en) * | 2009-08-21 | 2012-07-11 | 株式会社理光 | Image forming method, and image formed matter |
| CN101109913B (en) * | 2006-07-21 | 2012-09-26 | 富士施乐株式会社 | Recording medium and sheet |
| CN103076323A (en) * | 2012-12-28 | 2013-05-01 | 金红叶纸业集团有限公司 | Method for assessing distribution uniformity of starch in paper |
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| CN101328236B (en) * | 2007-06-18 | 2011-06-15 | 陕西邦希化工有限公司 | Cation surface sizing agent emulsion |
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| US8092874B2 (en) * | 2009-02-27 | 2012-01-10 | Eastman Kodak Company | Inkjet media system with improved image quality |
| CN102493280A (en) * | 2011-12-02 | 2012-06-13 | 牡丹江恒丰纸业股份有限公司 | Device and method for manufacturing cigarette paper with flame-retardant belt |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP3213630B2 (en) * | 1991-07-25 | 2001-10-02 | 三菱製紙株式会社 | Inkjet recording sheet |
| JP3205971B2 (en) * | 1992-08-27 | 2001-09-04 | 日本製紙株式会社 | Neutral paper manufacturing method |
| JP3186271B2 (en) * | 1992-12-10 | 2001-07-11 | 三菱製紙株式会社 | Inkjet recording sheet |
| EP0602494B1 (en) * | 1992-12-10 | 1996-10-09 | Mitsubishi Paper Mills, Ltd. | Ink jet recording sheet |
| JP2936996B2 (en) * | 1994-03-03 | 1999-08-23 | 王子製紙株式会社 | Newsprint paper for offset printing |
| GB9511482D0 (en) * | 1995-06-07 | 1995-08-02 | Wiggins Teape Group The Limite | Ink jet printing paper |
| MY125712A (en) * | 1997-07-31 | 2006-08-30 | Hercules Inc | Composition and method for improved ink jet printing performance |
| JPH11188968A (en) * | 1997-12-25 | 1999-07-13 | Kimoto & Co Ltd | Ink jet recording material |
| KR100403534B1 (en) * | 1998-04-21 | 2003-10-30 | 미쓰비시 세이시 가부시키가이샤 | Ink jet recording paper |
| JP4119012B2 (en) * | 1998-07-16 | 2008-07-16 | 三菱製紙株式会社 | Inkjet recording / electrophotographic recording paper |
| JP4147631B2 (en) * | 1998-07-28 | 2008-09-10 | 荒川化学工業株式会社 | Surface coating agent for papermaking and surface coated paper |
| JP2001303473A (en) * | 2000-04-19 | 2001-10-31 | Oji Paper Co Ltd | Offset printing paper and method for producing the same |
| JP4091748B2 (en) * | 2001-03-19 | 2008-05-28 | ピーティー・パブリク ケルタス チウィ キミア ティービーケー | Information recording paper |
| JP2002348798A (en) * | 2001-05-30 | 2002-12-04 | Mitsubishi Paper Mills Ltd | Curling-prevented paper and method for producing the same |
| JP2003001924A (en) * | 2001-06-21 | 2003-01-08 | Konica Corp | Ink jet recording method |
| JP2003076051A (en) * | 2001-08-31 | 2003-03-14 | Fuji Xerox Co Ltd | Recording paper, and image recording method using the same |
| JP2003145921A (en) * | 2001-08-31 | 2003-05-21 | Tomoegawa Paper Co Ltd | Ink jet recording sheet |
-
2004
- 2004-09-09 JP JP2004262628A patent/JP4529601B2/en not_active Expired - Fee Related
-
2005
- 2005-02-28 CN CN2007101680375A patent/CN101173488B/en not_active Expired - Fee Related
- 2005-02-28 CN CNB2005100511474A patent/CN100391750C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101109913B (en) * | 2006-07-21 | 2012-09-26 | 富士施乐株式会社 | Recording medium and sheet |
| CN102574406A (en) * | 2009-08-21 | 2012-07-11 | 株式会社理光 | Image forming method, and image formed matter |
| CN102574406B (en) * | 2009-08-21 | 2015-01-07 | 株式会社理光 | Image forming method, and image formed matter |
| CN103076323A (en) * | 2012-12-28 | 2013-05-01 | 金红叶纸业集团有限公司 | Method for assessing distribution uniformity of starch in paper |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2006077360A (en) | 2006-03-23 |
| JP4529601B2 (en) | 2010-08-25 |
| CN100391750C (en) | 2008-06-04 |
| CN101173488A (en) | 2008-05-07 |
| CN101173488B (en) | 2011-07-13 |
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