CN103184710B - Coated manila - Google Patents
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- CN103184710B CN103184710B CN201210581360.6A CN201210581360A CN103184710B CN 103184710 B CN103184710 B CN 103184710B CN 201210581360 A CN201210581360 A CN 201210581360A CN 103184710 B CN103184710 B CN 103184710B
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Abstract
The object of the present invention is to provide one kind to do well in terms of blank sheet of paper gloss and smoothness, and the coated manila that glazing glossiness is good.By having on two layers or more the coated manila constituted with pigment and adhesive coating as main component on body paper, contain aciculiform and/or cylindrical precipitated calcium carbonate, the partial size of 50 volume % of the size distribution curve of the precipitated calcium carbonate obtained by laser diffractometry in the pigment for including in most surface coating（D50）It is 0.2~0.7 μm, and the partial size of 90 volume %（D90）With the partial size of 10 volume %（D10）The ratio between（D90/ D10）It is 8 or less.
Description
Technical field
The present invention relates to a kind of coated manilas.
Background technique
Coated manila, be manufacture paper with pulp in multilayer made of be coated with pigment and adhesive painting as main component on body paper
The white board of material is mainly used for the packing box of cosmetics, pharmaceuticals, soap, gift etc..These packing boxes, in order to meet display
Bandwagon effect in shop fronts, it is desirable that do well in terms of glossiness and beautifying and decorating effect, and require suitable
The durability displayed for a long time and surface protection effect aspect do well.
It is transparent using being coated on the surface of coated manila as the method for making packing box have glossiness and protective effect
Resin liquid method（Glazing）.In order to make packing box be further equipped with high gloss and smoothness, using pass through high temperature roll-in
The method of coated manila after squeezing processing glazing（Press mold）.Currently, by the way that glazing coating machine is arranged behind printing machine
With UV drying equipment, continuously glazing working process is directly carried out to the coated manila after printing, can more efficiently and
Packing box is economically fabricated, therefore, uses online glazing（UV glazing）The case where processing, is continuously increased.Surface in this way adds
Work improves the glossiness and smoothness of packing box, due to relying heavily on coated manila, therefore it is required that white to being coated with
Paperboard improves.
As the glossiness after glazing（Hereinafter referred to as glazing glossiness）What aspect did well is coated with the existing of paperboard
Technology, for example, proposing following scheme, copolymer emulsion of the setting containing the gel for containing specific quantity, tool in patent document 1
There are the copolymer emulsion of specified particle diameter and the coating of pigment.
In addition, in patent document 2, being proposed as the prior art for obtaining the good coated manila of glossiness after press mold
Following scheme, median particle diameter in most surface coating containing specific quantity be 0.8 μm of kaolin below and cube and/or
The cylindrical precipitated calcium carbonate of person.
（Existing technical literature）
（Patent document）
（Patent document 1）Special open 2008-248431 bulletin
（Patent document 2）Special open 2005-200805 bulletin
Summary of the invention
（Problems to be solved by the invention）
But coating paperboard described in patent document 1 confirms through the inventors of the present invention, finds due to making in most surface coating
The reason of type of pigment, partial size, size distribution, the smoothness of blank sheet of paper is poor, damages beautifying and decorating effect.
In addition, coated manila described in patent document 2, the size distribution of precipitated calcium carbonate is worked as in the inventors of the present invention's discovery
When uneven, glazing glossiness may be reduced and generated concave-convex.
As described above, up to the present, do well in terms of glossiness and smoothness and printing adaptability, and
The coated manila also to do well in terms of glazing glossiness is not yet known.
In view of the above circumstances, the object of the present invention is to provide one kind in blank sheet of paper gloss and smoothness and printing adaptability side
Face is done well, and the coated manila that glazing glossiness is good.
（The present invention is to solve the problems, such as the means taken）
The inventors of the present invention, to using the knot studied repeatedly in the pigment of the coating of the most surface coating of coated manila
Fruit, it is to solve technical problem that discovery, which contains in pigment with specific shape and partial size and the precipitated calcium carbonate of size distribution,
Important technology essential factor.
The present invention includes following composition.
（1）A kind of coated manila, characterized in that by body paper have two layers or more based on pigment and adhesive
The coating of ingredient is wanted on the coated manila that constitutes, contains aciculiform and/or column in the pigment that includes in most surface coating
The precipitated calcium carbonate of shape, the partial size of 50 volume % of the size distribution curve of the precipitated calcium carbonate obtained by laser diffractometry
（D50）It is 0.2~0.7 μm, and the partial size of 90 volume %（D90）With the partial size of 10 volume %（D10）The ratio between（D90/ D10）For 8 with
Under；
（2）According to（1）The coated manila, characterized in that the precipitated calcium carbonate, the 50 of size distribution curve
The partial size of volume %（D50）It is 0.3~0.6 μm, and the partial size of 90 volume %（D90）With the partial size of 10 volume %（D10）The ratio between（D90/
D10）It is 6 or less；
（3）According to（1）Or（2）Described in any item coated manilas, characterized in that containing described light in most surface coating
Matter calcium carbonate and powdered whiting, 50 bodies of the size distribution curve of the powdered whiting obtained by laser diffractometry
The partial size of product %（D50）It is 0.5~1.5 μm；
（4）According to（1）~（3）Described in any item coated manilas, characterized in that the precipitated calcium carbonate, by work
Sequence A, B and C are fabricated, and it is to add in 2.5 ranges below into quick lime that process A, which is in the molar ratio relative to quick lime,
Digestion（slaking）Water, by being mixed to get calcium hydroxide；Process B is to obtain calcium hydroxide by mixing the calcium hydroxide with water
Slurry；Process C is to be passed through the gas containing carbon dioxide into the niter mortar to be carbonated.
(The effect of invention)
By means of the invention it is possible to obtain doing well in terms of blank sheet of paper gloss, smoothness and printing adaptability, and glazing
The good coated manila of glossiness.
Specific embodiment
Hereinafter, the present invention is described in detail.
（Most surface coating）
The most surface coating of coated manila in the present invention（Or most surface coating）It is based on pigment and adhesive
Ingredient is wanted, further according to needing to add other various adjuvants.
（Pigment）
（Precipitated calcium carbonate）
Precipitated calcium carbonate used in the present invention passes through laser it is characterized in that having aciculiform and/or cylindrical shape
The partial size of 50 volume % of the size distribution curve for the precipitated calcium carbonate that diffraction approach obtains（D50）It is 0.2~0.7 μm, and
The partial size of 90 volume %（D90）With the partial size of 10 volume %（D10）The ratio between（D90/ D10）It is 8 or less.
The shape of precipitated calcium carbonate has aciculiform, cylindricality, cube, spindle etc., but lightweight carbonic acid used in the present invention
Calcium requires to be aciculiform and/or cylindricality.The reason for this is that since it is considered that aciculiform and/or cylindrical shape speciality, so
It is easy to be directed in coating surface and coating, and because gap appropriate has been easy in coating, what is be applied
Do well in terms of the coating performance of the concavo-convex portion of coating surface（That is, smoothness is improved）, and it is upper smooth when can be equal
It is coated with oil polish evenly, and then does well in terms of glazing gloss display degree.
The D of precipitated calcium carbonate used in the present invention50It is 0.2~0.7 μm, preferably 0.3~0.6 μm, more preferable 0.35~
0.55μm.Work as D50When 0.2 μm discontented, coating gap is easy compactly to be filled by pigment, coating performance decline and adhesive strength
It reduces.Work as D50When more than 0.7 μm, the precipitated calcium carbonate in coating pigment may be made to form localization, the coating table being applied
The coating performance in face declines, and smoothness reduces, and blank sheet of paper glossiness may be made to decline.
The D of precipitated calcium carbonate used in the present invention90With D10The ratio between be preferably 8 hereinafter, more preferable 6 hereinafter, further it is excellent
Select 5 or less.Work as D90With D10The ratio between more than 8 when, size distribution is uneven, may make blank sheet of paper glossiness decline, smoothness drop
Low, glazing glossiness is deteriorated and generates concave-convex.
Precipitated calcium carbonate used in the present invention, it is necessary to included in the coating of most surface.The reason for this is that blank sheet of paper gloss,
Smoothness, glazing gloss display degree are mainly to be determined by the coating of most surface.Furthermore lightweight carbonic acid used in the present invention
Calcium, it is not necessary to need to include most surface coating other than coating（Hereinafter referred to as primer coating）In.
Content of the precipitated calcium carbonate used in the present invention in most surface coating is not particularly limited, but should be most surface
More than 5% mass of the whole pigment contained in coating, more than preferably 15% mass, more than more preferably 30% mass.Furthermore
Precipitated calcium carbonate in the present invention it is more containing quantitative change when, one side blank sheet of paper quality and printing quality are improved, but may
Decline glazing glossiness, therefore, the upper limit of content should be 70% mass hereinafter, below preferably 60% mass.
The method for obtaining precipitated calcium carbonate used in the present invention is not particularly limited, conventionally known manufacturing method, example
Such as, make calcium hydroxide（Calcium hydroxide）With carbonic acid gas（Carbon dioxide）The method of reaction makes calcium chloride and natrium carbonicum calcinatum（Soda
Ash）The method of reaction, the method for reacting calcium hydroxide with soda ash etc., by the aciculiform obtained by these methods and/or
Cylindrical precipitated calcium carbonate crushed, progressive operation, to obtain meeting partial size specified in the present invention and size distribution
Precipitated calcium carbonate.It is especially easily dispersed, crushes, the method for making calcium hydroxide and carbon dioxide reaction of progressive operation, preferably making
With in the method, the precipitated calcium carbonate especially characterized by manufacturing to obtain by process A, B, C is easy to get desired
Grain shape, partial size, size distribution, more preferably use.It is 2.5 below that process A, which is in the molar ratio relative to quick lime,
Into quick lime, addition digests water in range, by being mixed to get calcium hydroxide；Process B be by the way that the calcium hydroxide is mixed with water,
Obtain niter mortar；Process C is to be passed through the gas containing carbon dioxide into the niter mortar to be carbonated.
It is just described in detail below by the method that described process A, B, C obtain precipitated calcium carbonate.
Quick lime can be calcined lime stone, about calciner, be not particularly limited, Beckenbach sleeve kiln
（Beckenbach kiln）, the double thorax kilns of wheat Wurz（Maerz furnace）, rotary kiln（Rotary kiln）, KHD furnace
（Kahardy）, shaft furnace, Calmatic furnace, fluidized bed furnace（Fluidized bed furnace, fluidizing-bed furnace）, mixing
Roaster（Oven baked mixture stand）Deng the device of conversion lime stone.Calcination temperature and calcination time can be with
Appropriate adjustment, but the quick lime made of low temperature and calcined limestone for a long time, than passing through high temperature and short time
Quick lime made of ground calcined limestone, it is easier to obtain the precipitated calcium carbonate of needle-like shape.In addition, when the dioxy in quick lime
When change carbon content ratio is low, it is easier to obtain the precipitated calcium carbonate of needle-like shape, as the calcining residual component of lime stone, preferably
According to JIS R9011:Barium carbonate specified in 2006（barium）The calcining residual component for the lime stone that back titration obtains
Carbon dioxide content ratio is 1.5% hereinafter, more preferably carbon dioxide content ratio is 1.0% or less.Since precipitated calcium carbonate is
It is used as paint pigment, therefore the lime stone for using whiteness high as far as possible is relatively good as raw material.In particular, Fe, Mn etc.
Coloring components be likely to occur problem, it is therefore desirable to pay attention to as far as possible use the poor lime stone of coloring components.
Manufacturing method as calcium hydroxide is, it is preferable to use add 2 times of left sides of theoretical aquation amount into quick lime, that is, calcium oxide
Right water, the dry state digestion method digested.In dry state digestion, the water of the digestion water added into quick lime, preferably phase
Molar ratio for quick lime is 2.5 or less.When digesting water and being more than 2.5 to the molar ratio of quick lime, due to quick lime
When middle addition digestion water, water forms localization, therefore generates the calcium hydroxide of a large amount of subparticles, the shape of obtained precipitated calcium carbonate
Shape is spindle, and when being coated on paper, the quality of smoothness, gloss display degree etc. declines.
As described above, when the subparticle that the hydrated lime particle as raw material contains is excessive, manufactured precipitated calcium carbonate
Quality decline.The inventors of the present invention thus have obtained the volume particle size distribution of hydrated lime particle by laser diffractometry measurement.When
When the partial size of volume particle size distribution is that the cumulative volume of 1.0 μm of fine hydrated lime particles below is more than 20%, as original
Material will generate fusiform precipitated calcium carbonate when using.In the precipitated calcium carbonate as its product, coarse is mixed
Grain causes partial size uneven, and it is severe to be accordingly used in quality when coating pigment.It is therefore preferable that partial size is 1.0 μm below fine
Hydrated lime particle cumulative volume be 20% or less.More preferable partial size is that the cumulative volume of 1.0 μm of hydrated lime particles below is
15% hereinafter, further preferably 10% or less.In addition, by the size distribution for sharpening hydrated lime particle, so that carbonation reaction
Uniformly, enable to the partial size of precipitated calcium carbonate more uniform.
In order to generate the calcium hydroxide that subparticle is mixed into few uniform particle sizes, the mixing arrangement of mixing quick lime and water is excellent
Select have mixture or reactant can three-dimensionally be flowed with the diffusion effect that suspends, stirring structure.Specifically, election makes
The small blender in the gap of the blender and container and agitator arm that are rotated with mixing vessel itself.Use such stirring
Machine, when stirring, will not generate dead angle, and since mixture flows always, into quick lime when addition digestion water, water not will form office
Portion can prevent the calcium hydroxide generated from flocking together, it is equal can to obtain all less partial size of subparticle and big particle
Even hydrated lime particle.When the floating diffusion effect in mixing arrangement reduces, into quick lime when addition digestion water, water may
Localization is formed, therefore the fine hydrated lime particle generated is more, the shape of obtained precipitated calcium carbonate is spindle, works as painting
Cloth is when on paper, it may appear that the case where quality of smoothness, gloss display degree etc. declines.
In order to improve suspension diffusion effect, by agitator arm be rotated in mixed in mixing arrangement when, the stirring
The circumferential speed of impeller rotation requires to be 0.5m/s or more, and the circumferential speed of preferably agitator arm rotation is 0.8m/s or more,
Further preferred 1.5m/s or more.In addition, by container itself be rotated in mixed in mixing arrangement when, the container itself rotation
The circumferential speed turned requires to be 0.2m/s or more, and the circumferential speed of the preferably container itself rotation is 0.4m/s or more.In turn, lead to
The shearing agitator arm that setting is used for dispersion mixing is crossed, can be improved shear effect, to obtain subparticle and coarse
The more uniform hydrated lime particle of all less partial size of grain.
Mixing arrangement as the work of suitable continuation mode passes through to recycle the reactant in mixing arrangement
It is preferable to use the diffusion agitator arms with feeding structure and return structure, and then by the way that it is preferable to use skiing type shovel impellers
（Ski type shovel）, zigzag shovel impeller etc. special agitator arm, to obtain better suspension diffusion effect.
When agitator arm circumferential speed reaches 2.0m/s or more, quick lime is enough equably mixed with water energy, can prevent hydrated lime particle
It flocks together.In addition, mixing arrangement can also can be used two or more with not only one.By using two or more mix
It attaches together and sets, thus it is possible to vary the stirring circumferential speed of every mixing arrangement, residence time, it is less so as to obtain big particle
More suitable calcium hydroxide.
When the mean size of quick lime is 5mm or less, if the temperature for the digestion water being added in quick lime is too low, disappear
Change reaction sharply to occur, wider range of the size distribution of obtained hydrated lime particle.For this purpose, when setting classification, pulverizing process,
For operation, the load becomes large, spends in classification, the increased costs on disintegrating apparatus.It is therefore preferable that the temperature of digestion water is 40
DEG C or more, more preferable 60 DEG C or more.When the mean size of quick lime is more than 5mm, it is added to the temperature of the digestion water in quick lime
Degree, is not particularly limited, 20 DEG C or so of normal-temperature water also can be used.
In order to mix quick lime equably with digestion water, the addition import of water is digested, more than one is can be, preferably sets
Set two or more.In addition, the adding method as digestion water, in addition to Nozzle methods, also can be used to spray in a wider range
The spray method of mist.In particular, for the substance of powdered quick lime and digestion reaction midway, since spray method can prevent
It digests water and forms localization, it is advantageous to use spray method.As the suitable method of addition digestion water in a batch manner, no
It is disposably addition digestion water, but it is preferred that adds or added to continuity within 5~30 minutes or so time by several times.
It as the suitable method of addition digestion water in a continuous manner, is mixed on one side feeding quick lime from one end of blender
It closes between the both ends moved while stirring to the other end, the top of blender, more than two digestion water supply ports is set,
The supply port especially exported close to blender, it is relatively good using spray method.
The incorporation time of quick lime and digestion water, is not particularly limited, still, after the digestion water for adding specified amount, mixed
It attaches together and sets middle stirring 1 minute or more preferably, preferably 3 minutes or more, more preferable 5 minutes or more.If it is considered that production, preferably
Incorporation time is 8~15 minutes.
The calcium hydroxide obtained in this way can directly carry out carbonation reaction, but if removing big particle, can make carbon
More evenly, the partial size of precipitated calcium carbonate is also more uniform for acidification reaction.The partial size of hydrated lime particle is that preferably 150 μm hereinafter, more
It is preferred that 75 μm hereinafter, further preferred 50 μm or less.
As the method for removing coarse hydrated lime particle, grader, oscillating flat sieve, the plansifter for using centrifuge separation formula are elected
Classifying equipoment etc..The coarse hydrated lime particle filtered out with grader etc. can also return to classification using after pulverizer is ground
The closed circulation of the classification grinding of process.Either dry method or wet process formula can be used in classification grinding process.If
Hydrated lime particle overmastication in pulverizer, obtained precipitated calcium carbonate just will form spindle, and quality is caused to decline
Key factor, therefore must prevent.
The solids level concentration of the niter mortar of carbonation reaction is supplied, if discontented 5 mass %, can be such that production efficiency reduces,
If it exceeds 40 mass %, can generate the precipitated calcium carbonate of subparticle, caking ability is improved, and operability is deteriorated.Therefore, calcium hydroxide
The solids level concentration of slurry is preferably 5~40 mass %.The preferred lower limit of the solids level concentration of niter mortar is 8 mass %, more
The preferred upper limit is 20 mass %.
In addition, the temperature of niter mortar when carbonation reaction starts, due to the crystalline of the precipitated calcium carbonate to product
Shape has an impact, so needing to be adjusted.If carbonation reaction start temperature is 20 DEG C discontented, it is passed through carbonic acid gas（Dioxy
Change carbon gas）Or contain carbonic acid gas（Carbon dioxide gas）Gas when, fine needle crystals will be agglomerated together,
On the other hand, if it exceeds 50 DEG C, aciculiform and fusiform crystallization can be mixed, and cannot form the calcium carbonate of uniform particle sizes
Particle, it may not be possible to embody the quality of coating paper.Therefore, needle-shaped particles, carbonation reaction start temperature are preferably in order to obtain
20~50 DEG C.
The intake of carbon dioxide or the gas containing carbon dioxide, is not particularly limited, but from crystal form
Angle is set out, and in the calcium hydroxide for reacting every 1kg before starting, is preferably passed through 100% carbon dioxide with 10L/ points of flows below（1
Air pressure, 20 DEG C of conversions）, more preferable 5L/ points or less.If it exceeds 10L/ points, it just will form spindle or agglomerate the carbonic acid of shape
Calcium particle, it may not be possible to embody the quality of coating paper.From the angle of production, preferably 1.5L/ points or more.
Carbonation reaction can be to be also possible in a continuous manner in a batch manner, and carbonation reaction slot can be passed through
Carbon dioxide.If it is the reactive tank of batch mode, it is contemplated that be passed through carbon dioxide more efficiently below from reactive tank, institute
Using it is preferable to use it is cylinder-shaped or only the lower section of cylinder as the reactive tank of the corn cylindrical shape of circular cone etc..In turn, by half batch
Multiple holes are beaten on the circular cone of the lower section of the reactive tank of batch mode, the carbon dioxide being passed through forms subtle bubble, these are subtle
Bubble contacted with niter mortar, it can be made efficiently and equably to be reacted.
In addition, agitating device is set in reactive tank, by way of carrying out carbonation reaction while stirring, so that
Carbon dioxide is subtleer, more preferable with the contact of niter mortar, so as to equably and efficiently be reacted.Agitating device
Stir circumferential speed, preferably 2.0m/s or more, more preferable 2.5m/s or more.As agitating device, can be used uniaxial or double
Agitator tank, the Ke Lesi blender of spindle-type（Cowles mixer）, high-speed stirred formula dispersion machine（Disperser）Deng.In turn, lead to
It crosses and baffle is set in reactive tank, so as to improve the shearing force of niter mortar.
Furthermore it is also possible to add crystal seed in niter mortar before carbonation reaction.By being added in advance as crystal seed
Aragonitic aciculiform precipitated calcium carbonate can efficiently generate similar needle crystals.The adding proportion of crystal seed is, preferably hydroxide
The ratio between calcium and aragonitic aciculiform precipitated calcium carbonate are 99.7:0.3~95:5.
As the gas containing carbon dioxide of suitable carbonation reaction, the gaseous mixture containing carbon dioxide can be enumerated
Body, for example, the discharge gas of the lime calcining discharge gas of lime stone combustion gas, pulp production device, manufacture of cement kiln
The discharge gas etc. that body, the discharge gas of electricity generation boiler, rubbish destroy by fire.When the discharge gas is as the gas containing carbon dioxide
Body is in use, it is preferred that by using sack cleaner, electrostatic precipitator, dry collector, wet scrubber or these group
It closes, the dust of lime stone, lime, oxysulfide, unburned carbon in discharge gas etc. is removed, to purify discharge gas.
In order to use calcium carbonate slurry as paint pigment, need to be arranged following process：It is dehydrated and generates dehydration group
It closes the dehydration procedure of object and adds the discrete sets that moisture generates pulpous state in the water displacement composition obtained by the dehydration procedure
It closes the dispersion step of object and is adjusted to the pulverizing process of desired partial size.
Dehydration procedure can be operated by filtering, centrifuge separation, pressurizing and dehydrating, squeezing etc., dehydration to solids level concentration
70% degree.As suitable dehydration device, there are filter press, belt filter press etc..Dehydrated sludge cake after dehydration procedure
（Cake）Solids level concentration it is low when, drying process can be increased and be increased to desired solids level concentration.As drying device,
Including rotary drier, disk（Disk）Drier, pneumatic conveying dryer, fluidized bed dryer etc..Furthermore it is also possible to make
With the filter press of the integrated subsidiary functions/drying of dehydration procedure and drying process.
Furthermore to make precipitated calcium carbonate reach partial size as defined in the scope of the invention, dispersion is set preferably after dehydration procedure
Process and pulverizing process, but when the average grain diameter after decentralized processing is in the range of desired average grain diameter, be not necessarily to
It is crushed, directly as coating pigment use.
As the manufacturing method of calcium hydroxide, in addition to dry state digestion method, also can be used a large amount of more than theoretical aquation amount
Water under digested, to obtain the hygrometric state digestion method of the state of niter mortar.It is manufactured by hygrometric state digestion method
Hydrated lime particle, since partial size is that 1.0 μm of subparticles below are more, and mix coarse particle, therefore, in order to obtain
Precipitated calcium carbonate particle of the invention needs to remove coarse hydrated lime particle and fine hydrated lime particle.
As the method for removing coarse hydrated lime particle, elect clear using carry out such as oscillating flat sieve, plansifter classifying equipoments
It removes.The niter mortar comprising fine hydrated lime particle for penetrating oscillating flat sieve etc., is able to use centrifugal separation equipment, whirlwind
Type classifying equipoment etc. removes fine hydrated lime particle.
（May pigment）
Pigment used in the present invention for most surface coating, except the present invention specified in precipitated calcium carbonate with
Outside, can from powdered whiting, the present invention other than precipitated calcium carbonate, kaolin, talcum, silica, satin white, hard charcoal,
In the inorganic or organic pigment of aluminium hydroxide, alumina silicate, magnesium silicate, magnesium carbonate, titanium dioxide, plastic pigment etc., fit
Locality selects one or two kinds of combination of the above to use.In these pigment, since kaolin and powdered whiting are available
Higher glazing gloss, therefore it is preferable to use still, since kaolinic whiteness is low, select kaolin for more demanding
When the white board of whiteness, preferably selects and be applied in combination with powdered whiting.
Furthermore as powdered whiting, it is preferable to use 50 volume % of the size distribution curve obtained by laser diffractometry
Partial size（D50）For 0.5~1.5 μm of powdered whiting.Work as D50When 0.5 μm discontented, the coating of coating surface may be made
D can be worked as with surface strength decline50When more than 1.5 μm, smoothness may be made to reduce.When powdered whiting and other pigment simultaneously
The content of powdered whiting is not particularly limited in used time, but the 5~60 of the whole pigment preferably contained in most surface coating
Quality %, more preferably 10~50 mass %.As discontented 5 mass %, it may not be possible to desired whiteness is obtained, when more than 60
When quality %, blank sheet of paper glossiness and smoothness may be made to decline.
（Adhesive）
Adhesive used in the present invention for most surface coating, can be from oxidized starch, enzyme denaturation starch, phosphorus
The starch such as acidified starch, the protides such as casein, soybean protein, synthetic proteins, carboxymethyl cellulose, hydroxyethyl cellulose etc.
Cellulose family, the conjunction of the compositions such as polyvinyl alcohol, styrene-butadiene copolymer, metacrylate-butadiene copolymer etc.
At rubber, in the vinyl polymerizations species such as vinylacetic acid lipin polymer, Acryl analog copolymer, one is properly selected
Kind or two or more uses.
（Auxiliary agent）
Auxiliary agent used in the present invention for most surface coating, within the scope of the effect of the invention,
Can from blue and/or the dyestuff and pigment of purple, fluorescent dye, thickener, water-retaining agent, antioxidant, defoaming agent, point
Powder, pH value adjusting control agent, parting compound（Parting agent）, water resistant additive, in waterproofing agent etc., properly select it is one or two kinds of with
Upper use.
（Primer coating）
For primer coating（Or bottom coating）It is not particularly limited, can be wanted according to the quality to coated manila
Ask, from be generally used on coated manila to be suitably designed choosing in pigment and adhesive coating as main component
Select use.
As pigment, precipitated calcium carbonate specified in such as powdered whiting, the present invention can be enumerated, other than the present invention
Precipitated calcium carbonate, kaolin, talcum, silica, satin white, hard charcoal, aluminium hydroxide, alumina silicate, magnesium silicate, magnesium carbonate, two
The inorganic or organic pigment of titanium oxide, plastic pigment etc..
As adhesive, the starch such as oxidized starch, enzyme denaturation starch, phosphorylated starch can be enumerated, casein,
The protides such as soybean protein, synthetic proteins, the cellulose families such as carboxymethyl cellulose, hydroxyethyl cellulose, the combination such as polyvinyl alcohol
The synthetic rubber class of object, styrene-butadiene copolymer, metacrylate-butadiene copolymer etc., vinylacetic acid esters
The vinyl polymerization species of copolymer, Acryl analog copolymer etc..
In addition, as needed, blue and/or the dyestuff and pigment of purple, fluorescent dye, thickening can also be used
Agent, water-retaining agent, antioxidant, defoaming agent, dispersing agent, pH value adjusting control agent, parting compound（Parting agent）, water resistant additive, waterproofing agent
Deng auxiliary agent.
（Body paper）
Body paper used in the present invention, is not particularly limited, and can properly select using white commonly used in being coated with
Each square metre of paper weight of paperboard is 150~650g/m2Body paper made of the multilayer of degree is manufactured paper with pulp.The paper pulp of body paper is former
Material is also not particularly limited, can be from bleaching to unbleached mechanical pulp, chemical pulp or deinking to the old paper stock of non-deinking
Deng, usually as in the paper pulp raw material that uses of paper pulp raw material of coated manila, properly selecting one or two kinds of above make
With.
The single side in body paper for the purpose of being printed on one side is arranged the coated manila of this type of coating layer, by
Multilayer constitute body paper, each layer it is preferable to use paper pulp raw material be respectively the most surface layer that the body paper of one side of coating is set
（1st layer, superficial layer）Using bleach chemical pulp, adjoin with the most surface layer the 2nd layer（Superficial layer lower layer）It is useless using deinking
Paper paper pulp, the 3rd layer of later each layer（Each middle layer）And lowest level（Internal layer）Use the old paper stock of non-deinking.In addition, right
In the coated manila of this type in the two sides of body paper setting coating layer for the purpose of printed on both sides, each layer preferably makes
Paper pulp raw material is respectively the most surface layer on body paper two sides（1st layer, superficial layer）Using bleach chemical pulp, with the most table
Adjoin the 2nd layer of surface layer（Superficial layer lower layer）Use deinked waste paper paper pulp.
As described above, body paper middle layer using the low presentation grey of whiteness non-deinking old paper stock, but by
It, can in the old paper stock of the next layer of bleach chemical pulp and deinking for using whiteness high of the superficial layer and superficial layer in body paper
The whiteness of body paper is improved, therefore cannot see that the grey of middle layer from body paper surface or make the grey of middle layer unobtrusively, from
And it can be improved the presentation quality after printing processing quality and paper-made vessel processing.
In addition, multilayer manufacture paper with pulp made of in body paper, as needed, can also suitably add filler, blue and/or
The dyestuff and pigment of purple, sizing agent, paper strengthening agent, retention agent etc..
（Coating and processing）
It, can be from knife type coater as the device that coating is arranged on body paper（blade coater）, roll coater
（roll coater）, Kohler coater（Air knife coater）, rod coater（rod coater）, curtain streaming coating
Machine（Curtain coater）, flush coater（spray coater）Deng conventionally known apparatus for coating in properly select combination
It uses.In order to preferably embody effect of the invention, rod coater or blade coating is preferred when primer coating is set
Knife type coater or Kohler coater is preferred when most surface coating is arranged in machine.Certainly, these apparatus for coating, it can
It is on-line coater（on-machine）Form is also possible to paper-dope spreading（off-machine）Form.
Furthermore the solids level concentration of coating, for the coating of bottom coating and most surface coating, all there is no particular limitation,
But it is usually adjusted in the range of 20~70 mass %.In addition, to coating weight, also there is no particular limitation, still, in general, bottom
Layer coating and most surface coating are all in terms of dry weight, respectively in every 3~30g/m of single side2It is adjusted in the range of degree.
The coated manila obtained in this way, it may be necessary to by supercalender, soft press-polishing machine, gloss calender etc.,
Pressurizeed and improved the processing of smoothness.Furthermore to body paper and the coated manila of primer coating, thing can also be provided with
First pass through the processing that these calenders were pressurizeed and improved smoothness.
（Embodiment）
Embodiment will be enumerated below and explains the present invention, but cannot be understood as to limitation of the invention.Furthermore it manufactures
Example, embodiment, " % " and " part " in comparative example, all expression " quality % " and " mass parts ".
（The preparation of precipitated calcium carbonate）
（Production Example 1）
As mixing arrangement, using chopping impeller is removed, the plough of the WA150 type of the continuation mode of shovel impeller is all changed into
Knife mixing machine（Ploughshare Mixer）（The manufacture of Pacific Ocean Ji Gong company）, from one end of mixing arrangement, with 4kg/ points of throwing
Enter amount and puts into industrial quick lime（Carbon dioxide containing ratio is 0.3%）, it stops 8 minutes, until calcium hydroxide is discharged from the other end,
Within this 8 minutes time, in the case where shovel impeller circumferential speed is the speed of 3.0m/s, by nozzle mode, with 2.58kg/ points
Flow add 30 DEG C of digestion water from two places.After obtained calcium hydroxide is classified with 35 μm of cut point, 35 DEG C of mixing
Water prepares the niter mortar 10kg of 10% concentration.Under the speed that stirring circumferential speed is 5.0m/s, with 16L/ points of flow
It is passed through carbon dioxide/air gas mixture（Gas concentration is 20%）, carbonate to pH=7~8, to obtain precipitated calcium carbonate.
The precipitated calcium carbonate slurry passes through dehydration pressure-filteration drying machine（ROLLFIT）（The wild pool group ironworker of Co., Ltd.'s space is made
It makes）It is dehydrated, drying operation, obtains the mud cake that solids level concentration is 73%（Cake）.Then, addition is relative to lightweight carbonic acid
The adding proportion of calcium is 1.0 parts（Solid content）Sodium Polyacrylate（sodium polyacrylate）Dispersing agent（Trade name:
AronT-50, the manufacture of East Asia Synesis Company）, dispersed using intensive mixer, prepare precipitated calcium carbonate slurry.Then, make
It uses the bead that diameter is 1.0~1.4mm as crushing medium, the precipitated calcium carbonate is starched, is carried out 60 minutes with sand mill
Wet pulverizing processing, prepare solids level concentration be 71% precipitated calcium carbonate.
（Production Example 2）
Except the obtained calcium hydroxide in Production Example 1 to be classified with 100 μm of cut point, other than the water of 45 DEG C of mixing, with manufacture
Example 1 is similarly obtained precipitated calcium carbonate.
（Production Example 3）
The digestion water 9kg that 60 DEG C are injected in the container of subsidiary agitating device, adds the industrial of 1kg while stirring
Quick lime（Carbon dioxide containing ratio is 0.3%）, carry out digestion in 120 minutes.By 330 fineness of obtained calcium hydroxide（45μm）
Plansifter classification after, using centrifugal separating device, isolate the niter mortar of subparticle and big particle.It is thick by what is isolated
The niter mortar of bulky grain is cooled to 40 DEG C, prepares 12% niter mortar 10kg.Then, conduct is added in niter mortar
The aciculiform precipitated calcium carbonate of crystal seed（Trade name:The manufacture of TP123CS, Ao Duomo industrial group）, adding proportion is to be changed with solid content
It calculates, the ratio between calcium hydroxide and aciculiform precipitated calcium carbonate are 99:1.Under the speed that stirring circumferential speed is 5.0m/s, with 12L/ points
Flow is passed through carbon dioxide gas（Gas concentration is 100%）, carbonate to pH=7~8, to obtain precipitated calcium carbonate.
（Production Example 4）
Use the spindle precipitated calcium carbonate of market sale（Trade name:The manufacture of TP121-7C, Ao Duomo industrial group）.
（Production Example 5）
Use the cylindricality precipitated calcium carbonate of market sale（Trade name:The manufacture of TP123CS, Ao Duomo industrial group）, with grinding
Grinding machine is crushed, classification is handled, and obtains the cylindricality precipitated calcium carbonate of fine particle.
（Production Example 6）
Use the cylindricality precipitated calcium carbonate of market sale（Trade name:The manufacture of TP123CS, Ao Duomo industrial group）.
（Production Example 7）
Use the cube precipitated calcium carbonate of market sale（Trade name:Brilliant S15, the manufacture of shiraishi calcium company）.
To cylindricality precipitated calcium carbonate obtained in Production Example, following observation and measurement are carried out, as the result is shown in table 1
In.
（Grain shape observation）
Use scanning electron microscope（Hitachi, Ltd manufactures S-3500N）It takes pictures, is amplified to 7000 times of observation granulateds
Shape.
（Grain diameter measurement）
Pass through laser diffractometry（Day machine dress corporation granulation grade analyzer HRAX-100）Measurement obtains size distribution.It will wait
The partial size for being same as cumulative volume 10%, 50%, 90% is expressed as D10、D50、D90, with 50 volume %（D50）Partial size as average grain diameter,
And then obtain the partial size of 90 volume %（D90）With the partial size of 10 volume %（D10）The ratio between（D90/ D10）.
（Table 1）
（Embodiment 1）
（The production of body paper）
The superficial layer that the 1st layer of body paper uses bleach chemical pulp, and the 2nd layer of superficial layer lower layer uses the old paper stock of deinking,
3rd layer of middle layer, the 4th layer of middle layer and the 5th layer of internal layer use the old paper stock of non-deinking respectively, 5 layers manufacture paper with pulp it is compound
Afterwards, it is smoothed, so that the paper weight for obtaining each square metre is 290g/m2Coated manila body paper.
（The preparation of bottom coating）
In the powdered whiting by 100 parts（Trade name：Hydrocarb90, standby northern dusting industrial group manufacture, D50=1.11
μm）In the graining paste of composition, sodium polyacrylate disperant is added（Trade name:AronT-50, the manufacture of East Asia Synesis Company）0.25
Part, oxidized starch（Trade name：Prince Ace Y, the manufacture of prince's cornstarch company）3 parts, styrene-butadiene copolymer latex
（Trade name：PA7070, the manufacture of A&L company of Japan）14 parts（Solid content）, prepare the bottom coating that solids level concentration is 62%.
（The preparation of most surface coating material）
30 parts, kaolin are starched in the precipitated calcium carbonate obtained by Production Example 1（Trade name：UW-Y, BASF (BASF) company
Manufacture）30 parts, powdered whiting（Trade name：Hydrocarb90, standby northern dusting industrial group manufacture, D50=1.11μm）35 parts,
Titanium dioxide（Trade name：KA-100, the manufacture of COSMO Chemical company of South Korea）In the graining paste of 5 parts of compositions, addition poly- third
Olefin(e) acid sodium dispersing agent（Trade name:AronT-50, the manufacture of East Asia Synesis Company）0.25 part, oxidized starch（Trade name：Prince Ace
Y, prince's cornstarch company manufactures）3 parts, styrene-butadiene copolymer latex（Trade name：PA4046, A&L company of Japan
Manufacture）12 parts（Solid content）, prepare the most surface coating material that solids level concentration is 64%.
（The production of coated manila）
In the body paper for the coated manila, the bottom coating is coated with by rod coater, is dried,
The dry weight for reaching every single side is 10g/m2, to obtain bottom coating paper.Then, in obtained bottom coating paper, lead to
It crosses knife type coater and is coated with the most surface coating material, be dried, the dry weight for reaching every single side is 10g/m2, to obtain
2 layers of coating paper.In 2 layers of obtained coating paper, the soft press-polishing machine for being 200 DEG C by metalling roll surface temperature carries out two pressures
The paper feeding in area is handled, to obtain coated manila.
（Embodiment 2）
It is logical except the precipitated calcium carbonate obtained by Production Example 1 in the preparation of the most surface coating material of embodiment 1 is changed into
It crosses other than the precipitated calcium carbonate that Production Example 2 obtains, obtains coated manila similarly to Example 1.
（Embodiment 3）
It is logical except the precipitated calcium carbonate obtained by Production Example 1 in the preparation of the most surface coating material of embodiment 1 is changed into
It crosses other than the precipitated calcium carbonate that Production Example 3 obtains, obtains coated manila similarly to Example 1.
（Embodiment 4）
The lightweight obtained by Production Example 3 is changed into except the pigment in the preparation of the most surface coating material of embodiment 3 is constituted
Calcium carbonate starches 65 parts, kaolin（Trade name：UW-Y, the manufacture of BASF (BASF) company）30 parts, titanium dioxide（Trade name：KA-
100, South Korea COSMO Chemical company manufactures）Other than 5 parts, coated manila is obtained similarly to Example 3.
（Embodiment 5）
Except the powdered whiting in the preparation of the most surface coating material of embodiment 1 is changed into obtained by Production Example 4 it is light
Other than matter calcium carbonate, coated manila is obtained similarly to Example 1.
（Embodiment 6）
It is logical except the precipitated calcium carbonate obtained by Production Example 1 in the preparation of the most surface coating material of embodiment 1 is changed into
It crosses other than the precipitated calcium carbonate that Production Example 5 obtains, obtains coated manila similarly to Example 1.
（Embodiment 7）
（The preparation of most surface coating material）
40 parts, kaolin are starched in the precipitated calcium carbonate obtained by Production Example 1（Trade name：UW-Y, BASF (BASF) company
Manufacture）55 parts, titanium dioxide（Trade name：KA-100, the manufacture of COSMOChemical company of South Korea）In the graining paste of 5 parts of compositions,
Add sodium polyacrylate disperant（Trade name:AronT-50, the manufacture of East Asia Synesis Company）0.25 part, oxidized starch（Trade name：
Prince Ace Y, the manufacture of prince's cornstarch company）2 parts, styrene-butadiene copolymer latex（Trade name：PA4046, Japan
The manufacture of A&L company）15 parts（Solid content）, prepare the most surface coating material that solids level concentration is 40%.
（The production of coated manila）
It is noted earlier except the most surface coating material of embodiment 1 is changed into（Embodiment 7）Most surface coating material, most surface coating
Coating method change into and be coated with using Kohler coater other than, obtain coated manila similarly to Example 1.
（Comparative example 1）
It is logical except the precipitated calcium carbonate obtained by Production Example 1 in the preparation of the most surface coating material of embodiment 1 is changed into
It crosses other than the precipitated calcium carbonate that Production Example 6 obtains, obtains coated manila similarly to Example 1.
（Comparative example 2）
It is logical except the precipitated calcium carbonate obtained by Production Example 1 in the preparation of the most surface coating material of embodiment 1 is changed into
It crosses other than the precipitated calcium carbonate that Production Example 7 obtains, obtains coated manila similarly to Example 1.
（Comparative example 3）
It is logical except the precipitated calcium carbonate obtained by Production Example 1 in the preparation of the most surface coating material of embodiment 1 is changed into
It crosses other than the precipitated calcium carbonate that Production Example 4 obtains, obtains coated manila similarly to Example 1.
（Comparative example 4）
Except by the kaolin in the preparation of the most surface coating material of embodiment 1（Trade name：UW-Y, BASF (BASF) company
Manufacture）It is changed to other than 100 parts, obtains coated manila similarly to Example 1.
（Comparative example 5）
Except by the powdered whiting in the preparation of the most surface coating material of embodiment 1（Trade name：Hydrocarb90, standby northern powder
The manufacture of chemical industry company, D50=1.11 μm）It is changed to other than 100 parts, obtains coated manila similarly to Example 1.
（Comparative example 6）
It is logical except the precipitated calcium carbonate obtained by Production Example 1 in the preparation of the most surface coating material of embodiment 7 is changed into
It crosses other than the precipitated calcium carbonate that Production Example 6 obtains, obtains coated manila similarly to Example 7.
The coated manila that will be obtained by each Examples and Comparative Examples is evaluated, result by following method
It is shown in table 2.
（Whiteness）
According to JIS P8148（2001）, use spectrum whiteness measuring instrument SC-10WT（The manufacture of Sugatest machines corporation）
Measurement obtains.
（Blank sheet of paper glossiness）
According to JIS P8142, measurement obtains the glossiness in blank sheet of paper face when paper angle is 75 degree.
（PPS smoothness）
Roughness tester is printed using Parker（PPS）（Device model：MODEL M-569 type, Britain MESSMER
The manufacture of BUCHEL company）, under conditions of liner are soft rubber, folder sample pressure is 1.96MPa, 5 smoothness measurements are carried out, are taken
Its average value.
（Print gloss）
Pass through RI printing machine（Manufactured by bright production）, use the printing ink of 0.6cc（Trade name：FUSION-G ink, S type,
Big Japanese ink chemical industrial company manufacture）It is printed, uses vancometer（Color research institute manufactures on GM-26D, village）It surveys
Measure glossiness when paper angle is 60 degree.
（Printing smooth）
Pass through RI printing machine（Manufactured by bright production）, use the printing ink of 0.2cc（Trade name:FUSION-G EZ ink, S
Type, the manufacture of DIC Graphic company）It is printed, visual assessment is transferred to the transfer uniformity of the ink on blank sheet of paper（Printing is flat
Slip）Effect is imprinted with ink.
◎：Printing smooth, ink coining effect are very outstanding.
〇：Printing smooth, ink coining effect are outstanding.
△：Printing smooth, ink coining effect are slightly worse.
╳：Printing smooth, ink coining effect are poor.
（Picking speed）
Testing machine is printed by RI（Manufactured by bright production）, use the printing ink of 0.6ml（Trade name：Paper test is used
Ink SD50 is red, Toyo Ink company manufactures）It is printed, the degree of the hair loss of visual assessment printing surface.
◎：Hair loss absolutely not occurs, well.
〇：Although a small amount of hair loss, the degree that there is no problem occurs.
△：Hair loss, unacceptable degree in actual use occurs.
╳：Hair loss has generation more, poor.
（Ink solidification evaluation）
Testing machine is printed by RI（Manufactured by bright production）, use the printing ink of 0.6cc（Trade name：FUSION-G ink,
It is S type, the same）It is printed, it is after 3 minutes, blank sheet of paper is Chong Die with printing surface, it is imprinted again by RI printing machine, visual assessment turns
Print to the printing ink concentration on blank sheet of paper.
◎：There is no ink to be transferred on blank sheet of paper, ink solidification is fast.
〇：There is few ink to be transferred on blank sheet of paper, ink solidification is very fast.
△：There is a small amount of ink to be transferred on blank sheet of paper, ink solidification is slightly slow.
╳：There is ink to be transferred on blank sheet of paper, ink solidification is slow.
（UV glazing gloss）
Pass through Cai's grace（Zahn cup）Flow cup #4 is by UV solidification polish oil（Trade name：Dai cure clear
UV1603, the manufacture of DIC Graphic company）Delivery time be adjusted to 10 seconds after, use the coating of subsidiary UV solidification equipment
Device（Model：SG610UV, precious (Duplo) company manufacture is obtained）, the UV solidification polish is coated on coated manila surface
Oil carries out UV drying, the processing of light oil meter face.Part is processed for the polish oil of obtained coated manila, uses glossiness
Instrument（Color research institute manufactures on GM-26D, village）Measurement obtains glossiness when paper angle is 60 degree.
（Table 2）
It will be clear that by means of the invention it is possible to obtaining adapting in blank sheet of paper gloss and smoothness, printing from table 2
Property aspect do well, and the coated manila that glazing glossiness is good.
Claims (5)
1. a kind of coated manila, characterized in that by have on body paper two layers or more with pigment and adhesive be mainly at
Point coating and on the coated manila that constitutes, aciculiform and/or cylindrical is contained in the pigment that includes in most surface coating
The partial size of precipitated calcium carbonate, 50 volume % of the size distribution curve of the precipitated calcium carbonate obtained by laser diffractometry is
0.2~0.7 μm, and the ratio between partial size of the partial size of 90 volume % and 10 volume % is 8 or less, wherein the precipitated calcium carbonate
Content be the 5 mass %-70 mass % of whole pigment contained in most surface coating.
2. coated manila according to claim 1, characterized in that the precipitated calcium carbonate, size distribution curve
The partial size of 50 volume % is 0.3~0.6 μm, and the ratio between partial size of the partial size of 90 volume % and 10 volume % is 6 or less.
3. according to claim 1 or 2 described in any item coated manilas, characterized in that containing described light in most surface coating
Matter calcium carbonate and powdered whiting, 50 volume % of the size distribution curve of the powdered whiting obtained by laser diffractometry
Partial size be 0.5~1.5 μm.
4. according to claim 1 or 2 described in any item coated manilas, characterized in that the precipitated calcium carbonate, by process
A, B and C are fabricated, and it is to add to disappear into quick lime in 2.5 ranges below that process A, which is in the molar ratio relative to quick lime,
Change water, by being mixed to get calcium hydroxide；Process B is to obtain niter mortar by mixing the calcium hydroxide with water；Process C be to
The gas containing carbon dioxide is passed through in the niter mortar to be carbonated.
5. coated manila according to claim 3, characterized in that the precipitated calcium carbonate, by process A, B and C system
It makes, it is that into quick lime, addition digests water in 2.5 ranges below that process A, which is in the molar ratio relative to quick lime, is led to
It crosses and is mixed to get calcium hydroxide；Process B is to obtain niter mortar by mixing the calcium hydroxide with water；Process C is to the calcium hydroxide
The gas containing carbon dioxide is passed through in slurry to be carbonated.
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| JP5810901B2 (en) * | 2011-12-27 | 2015-11-11 | 王子ホールディングス株式会社 | Inkjet recording paper |
| CN103909683B (en) * | 2014-03-24 | 2016-09-28 | 山东泰宝防伪制品有限公司 | A kind of preparation method of high abrasion glazing anti-counterfeit package box |
| EP3388575A1 (en) * | 2017-04-12 | 2018-10-17 | BillerudKorsnäs AB | Pigment-coated board having improved pe adhesion |
| CN109004107B (en) * | 2018-07-02 | 2020-01-31 | 陕西科技大学 | paper light-emitting structures and preparation method based on full printing process |
| CN112681004A (en) * | 2020-12-30 | 2021-04-20 | 天能电池(芜湖)有限公司 | Novel super-permeability coated paper |
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| CN1327436A (en) * | 1999-10-26 | 2001-12-19 | 矢桥工业株式会社 | Calcium carbonate, and method for producing the same |
| CN1789552A (en) * | 2005-12-12 | 2006-06-21 | 金东纸业(江苏)有限公司 | High-whiteness coated paper and its production method |
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| JP2005139012A (en) * | 2003-11-04 | 2005-06-02 | Yahashi Kogyo Kk | Method for producing acicular calcium carbonate |
| JP2005200805A (en) * | 2004-01-19 | 2005-07-28 | Hokuetsu Paper Mills Ltd | Coated whiteboard paper |
| JP5114729B2 (en) * | 2005-12-15 | 2013-01-09 | 王子ホールディングス株式会社 | Calcium carbonate particles and news paper for cold offset printing |
| JP2011208299A (en) * | 2010-03-29 | 2011-10-20 | Mitsubishi Paper Mills Ltd | Coated paper for lithographic offset printing |
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| CN1327436A (en) * | 1999-10-26 | 2001-12-19 | 矢桥工业株式会社 | Calcium carbonate, and method for producing the same |
| CN1789552A (en) * | 2005-12-12 | 2006-06-21 | 金东纸业(江苏)有限公司 | High-whiteness coated paper and its production method |
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