Patent Application
20050103458
1. Field of the Invention
This invention relates to a high-bulk, wood containing printing paper offering high brightness, very low density, high flexibility (low stiffness), and excellent printability.
2. Description of the Related Art
High bulk (low density) is one of important qualities required by paper products of late. Responding to the growing pro-environmental sentiment, the users are demanding paper products that offer lower weight, or lower density, while maintaining sufficient thickness, in order to achieve more effective utilization of paper pulp produced from forest resource.
One traditional method for reducing paper density (increasing paper bulk) is to use high-bulk pulp. In general, wood pulp is used widely in paper production. It is known that ground pulp produced by grinding wood material using a grinder, or refiner mechanical pulp produced by refining wood material using a refiner, or yet mechanical pulp such as thermomechanical pulp, offers stiffer fibers and is therefore more effective in reducing paper density, compared with chemical pulp produced by extracting a reinforcing substance called lignin from wood fibers through chemical processing. However, today's mechanical pulp is mostly produced from softwood trees containing large amounts of lignin, which makes it difficult to produce pulp offering high brightness. A number of issues have therefore been encountered in the effort to produce a high-bulk paper offering high brightness.
Among various types of mechanical pulp, softwood thermomechanical pulp has relatively long and stiff fibers. Therefore, paper made from such pulp had poor formation and lower smoothness, and also caused ink impression problem during offset printing. Paper made from softwood thermomechanical pulp containing stiff fibers also resulted in lower foldability—a factor that affects offset printing efficiency—and made it difficult to turn pages of printed/bound books. Regarding the use of softwood thermomechanical pulp, therefore, improvement of flexibility, or reduction of flexural stiffness, of printing paper remained an issue.
To solve the above problems, the applicant filed a patent application regarding a technology used to produce from specific hardwood trees a mechanical pulp offering high bulk, high brightness and high relative scattering coefficient (Japanese Patent Application Laid-open No. 2003-27385). The applicant also filed a patent application regarding a printing paper containing hardwood mechanical pulp, which offers low density, high brightness, high opacity and excellent printability (Japanese Patent Application Laid-open No. 2003-49386). However, when what happens to the strength, printability and other properties of paper as a result of increasing paper bulk are put into overall perspective based on the use of hardwood mechanical pulp, these conventional technologies can only achieve a paper density of around 0.50 g/cm3 at the lowest for printing paper fit for practical use, and therefore further increase in paper bulk (reduction of density) remained difficult.
Another known method for reducing paper density is to use a bulk-increasing agent. Known bulk-increasing agents include a bulk-increasing agent for paper containing specified alcohol and/or its polyoxyalkylene adduct (PCT International Publication No. 98/03730), nonionic surfactant (Japanese Patent Application Laid-open No. 11-200283) and bulk-increasing agent for paper consisting of polyvalent alcohol and fatty acid ester compound (Registered Japanese Patent No. 2971447), and a technology that applies these bulk-increasing agents for paper to paperboard is also disclosed (Registered Japanese Patent No. 3041294).
As for the bulk-increasing agent based on a non-surfactant, a bulk-increasing agent for paper that contains at least one type of compound selected from a cationic compound having a specified structure, amine, acid salt of amine, or amphoteric compound is disclosed (Japanese Patent Application Laid-open No. 11-269799). A bulk-increasing agent of fatty acid polyamide polyamine type is also known. Also known is a compound with a water separation degree of 4% or more that provides the effect of increasing two or more paper qualities including bulk, brightness and opacity (Registered Japanese Patent No.3283248). Additionally, a method for producing a pulp sheet is also disclosed, where the method uses a compound with a water separation degree of 4% or more that provides the effect of increasing one or more paper qualities including bulk, brightness and opacity (Japanese Patent Application Laid-open No. 2003-105685).
Efforts to increase paper bulk using these known bulk-increasing agents cannot reduce the density of obtained printing paper to levels below 0.50 g/cm3 or so, which is similar to the case when hardwood mechanical pulp is used as mentioned above, and therefore ways to further reduce paper density are needed.
Even if paper bulk can be successfully reduced and a low-density paper is obtained, when offset printed such paper would cause “bleeding,” or oozing out of ink onto the back face over time. This problem, which affects printing quality, became a major issue in the effort to reduce paper density.
Based on the above background, development of a high-bulk, wood containing printing paper offering high brightness, low density, high flexibility (low stiffness) and excellent printability, while also preventing bleeding, has been awaited.
The purpose of the present invention is to provide a high-bulk, wood containing printing paper that offers high brightness, very low density, high flexibility (low stiffness) and excellent printability, and also prevents bleeding.
After conducting diligent studies to solve the aforementioned problems, the inventors found that a wood containing printing paper, made from a paper material that blends mechanical pulp produced from chemically processed hardwood pulp and also contains a bulk-increasing agent, would offer very low density, excellent paper strength and printability, and sufficient fitness for practical use, and discovered that coating a starch-based surface-paper-strengthening agent would solve the bleeding problem associated with a low-density paper. These findings led to the present invention.
In the present invention, it is desirable that of the various types of hardwood mechanical pulp produced by chemical processing, those having a single fiber density of 0.91 g/cm3 or less as calculated in accordance with formula (1) shown below, or those having a single fiber density index of 0.20 or more as calculated in accordance with formula (2) shown below, be blended. The blending amount of hardwood mechanical pulp in the present invention should preferably be 10 to 60 weight-% of.the total weight of pulp. The adding amount of bulk-increasing agent should preferably be 0.1 to 1.2%, or more preferably 0.5 to 1.2%, of the total bone-dry weight of pulp.
Single fiber density=ρ×(1−Single fiber density index) Formula (1)
(ρ: Calculated by assuming the true fiber density as 1.14 g/cm3)
Single fiber density index={(Fiber width−2×Wall thickness)/Fiber width}2 Formula (2)
On the other hand, the coating amount of starch-based surface-paper-strengthening agent on the obtained base paper should ideally be 0.3 to 3.0 g/m2, or preferably 0.5 to 2.0 g/m2.
The present invention provides a remarkable benefit in that it allows for production of a high-bulk, wood containing printing paper offering high brightness, significantly low density, high flexibility (low stiffness) and excellent printability, while also preventing bleeding, by blending chemically processed hardwood mechanical pulp, adding a bulk-increasing agent, and coating a surface-starch-based paper-strengthening agent on the obtained paper.
The present invention also offers a significant advantage in terms of helping achieve effective utilization of hardwood resource, and therefore makes a great contribution to society.
The chemically processed hardwood pulp used in the present invention may be any known refiner groundwood pulp (RGP), thermomechanical pulp (TMP), chemi-thermomechanical pulp (CTMP), alkali peroxide mechanical pulp (APMP) or alkali peroxide thermomechanical pulp (APTMP) made from hardwood, including the hardwood mechanical pulp specified in Japanese Patent Application Laid-open No. 2003-27385. Of these, use of APMP and APTMP is desired, because they can yield pulp offering high bulk, high opacity, high brightness and high strength.
When APMP is used, woodchip is impregnated with an alkali peroxide solution containing sodium hydroxide, hydrogen peroxide or sodium silicate, and then refined in atmospheric pressure. Production of APTMP involves a refining process at high temperature under pressure. After the refining process, the woodchip is held for at least 5 minutes in the alkali peroxide solution at normal or raised temperature to produce high brightness pulp.
The above APMP or APTMP should desirably be produced through steps (a) through (i) described below:
In step (a) above, it is desirable that the chelate agent be used by 0.05 to 0.4 solid-content weight-% of the bone-dry weight of woodchip. In step (c), it is desirable that the alkali reagent be an aqueous solution containing sodium hydroxide by 0.2 to 2.0 solid-content weight-%, sodium silicate by 0.2 to 2.0 solid-content weight-%, magnesium sulfate by 0.01 to 0.2 solid-content weight-%, chelate agent by 0.05 to 0.4 solid-content weight-%, and hydrogen peroxide by 0.2 to 5 solid-content weight-%, of the bone-dry weight of woodchip.
In step (e) above, an alkali peroxide containing chelate agent is added to the bleached, softened woodchip immediately before the primary refining process, where the woodchip is loosened into pulp fibers in a refiner set to a raised or atmospheric pressure.
As for the refiner, a general fiber-loosening system is sufficient. Preferably, a single-disc refiner, conical-disc refiner, double-disc refiner or twin-disc refiner should be used to loosen fibers.
To achieve the target brightness for the high-bulk, wood containing printing paper provided by the present invention, one or more known bleaching steps may be added to further bleach the hardwood mechanical pulp if a higher brightness level is required. In this case, an oxidizing agent such as hydrogen peroxide, ozone or peracetic acid, or a reducing agent such as hydrosulfite (sodium dithionite), sodium hydrogensulfate, sodium borohydride or formamidinesulfinic acid (FAS) can be used.
Among the aforementioned types of hardwood mechanical pulp, it is desirable that those having a single fiber density of 0.91 g/cm3 or less, or those having a single fiber density index of 0.20 or more, be blended. The higher the single fiber density index, the lower the single fiber density becomes.
For your reference, the single fiber density index is calculated from the fiber width and fiber wall thickness measured on a Fiber Lab. (manufactured by Kajaani).
Since fibers of 0.20 or higher single fiber density index have a low single fiber density, paper in which such pulp is blended maintains a high bulk structure and thus a lower density. Among the applicable trees, those in the Eucalyptus family, particularly Eucalyptus Globulus, Eucalyptus Grandis, Eucalyptus Urophylla, Eucalyptus Nitens and Eucalyptus Regnance, and others in the Maple family are desired.
In addition, hardwood mechanical pulp that yields a handmade paper with a density of 0.45 g/cm3 or less when the paper is made in accordance with JIS P 8222: 1998 at a Canadian standard freeness (hereinafter referred to as “CSF”) of 100 ml is suitable for the present invention. By using this pulp, production of high-bulk printing paper becomes possible.
The wood containing printing paper provided by the present invention can use, as its material pulp, chemical pulp (softwood bleached kraft pulp (NBKP) or unbleached kraft pulp (NUKP), hardwood bleached kraft pulp (LBKP) or hardwood unbleached kraft pulp (LUKP), etc.), softwood mechanical pulp (groundwood pulp (GP), refiner groundwood pulp (RGP), thermomechanical pulp (TMP), chemi-thermomechanical pulp (CTMP), etc.) or de-inked pulp (DIP), either alone or in any combination at desired ratios, in addition to the aforementioned hardwood mechanical pulp, to the extent not reducing the effects of the present invention.
An appropriate blending ratio of hardwood mechanical pulp to total pulp is 10 to 60 weight-%, or preferably 20 to 40 weight-% when economy and other factors are considered, although the specific blending ratio will vary depending on the single fiber density index of the hardwood mechanical pulp, target density for the resulting high-bulk, wood containing printing paper, type and amount of the bulk-increasing agent used, and the pressure in press part and the pressure in calender part of the papermachine, among others.
There are no specific limitations as to which bulk-increasing agents can be used with the present invention, as long as the agent is known.
For example, the aforementioned bulk-increasing agents specified in PCT International Publication No. 98/03730, Japanese Patent Application Laid-open No. 11-200283, Registered Japanese Patent No. 2971447, Japanese Patent Application Laid-open No. 11-269799, Registered Japanese Patent No. 3283248, Japanese Patent Application Laid-open No. 2003-105685, etc., may be used. In addition, the bulk-increasing agents specified in Japanese Patent Application Laid-open No. 2001-355197 and Japanese Patent Application No. 2003-288328, both filed by the applicant, may also be used.
The compounds that are specified in the above publications as bulk-increasing agents are as follows:
The present invention can reduce paper density multi-folds by using the above bulk-increasing agents together with hardwood mechanical pulp.
In other words, the present invention blends chemically processed hardwood mechanical pulp having a single fiber density of 0.91 g/cm3 or less, or single fiber density index of 0.20 or more, where the blending amount of such hardwood mechanical pulp is 10 to 60 weight-% of the total weight of pulp. The adding amount of bulk-increasing agent should preferably be 0.1 to 1.2%, or more preferably 0.5 to 1.2%, of the total bone-dry weight of pulp. If the amount of bulk-increasing agent is less than 0.1%, little bulk-increasing effect can be expected. On the other hand, adding a bulk-increasing agent by more than 1.2% will not result in further bulk increase. Even if a lower paper density (higher bulk) can be achieved, however, such printing paper is not fit for practical use, as explained below.
As mentioned above, while the present invention successfully increased the bulk of paper material, a new problem arose that affects printing property. Specifically, the wood containing printing paper obtained by combining hardwood mechanical pulp and bulk-increasing agent has a very low density and porous paper layer. Therefore, despite its high bulk the paper caused “bleeding,” or oozing out of dye ink over time, during offset printing. As result, a measure to prevent bleeding became necessary.
To prevent bleeding, the effects of various surface-paper-strengthening agents applied were examined. The result found that coating 0.3 to 3.0 g/m2, or preferably 0.5 to 2.0 g/m2, of starch-based surface-paper-strengthening agent on the surface of the base paper produced from hardwood mechanical pulp and bulk-increasing agent would prevent bleeding. This finding led to the present invention.
There are no specific limitations as to which starches can be used as the starch-based surface-paper-strengthening agent, and raw starch, or processed starch such as oxidized starch, dialdehyde starch, phosphoric acid modified starch, hydroxy ethylated starch, hydroxy propylated starch, cationized starch or enzyme modified starch can be used.
As for the coating amount of starch-based surface-paper-strengthening agent, bleeding cannot be suppressed if the coating amount is less than 0.1 g/m2, while the paper density will increase if the starch-based surface-paper-strengthening agent is coated to 3.0 g/m2 or more.
The high-bulk, wood containing printing paper provided by the present invention can be made using a fourdrinier papermachine, gap former or hybrid former (on-top former), or other known papermachine.
Since the obtained wood containing printing paper has higher bulk, desirably the pressure in press part of the papermachine should be minimized to the extent not affecting the machine operation. The pressure in calender part should also be minimized to the extent not reducing the smoothness of the high-bulk, wood containing printing paper.
There are no limitations as to which types of machines can be used to coat starch-based surface-paper-strengthening agent, and 2-roll size press coater, gate roll coater, blade metering coater or rod metering coater can be used in the application process. Other papermaking conditions are not specified, and the pH level during the papermaking process may be in the acid, neutral or alkali range.
The high-bulk, wood containing printing paper provided by the present invention may contain a filler.
Any known filler can be used, such as white carbon, talc, kaolin, clay, heavy calcium carbonate, precipitated calcium carbonate, titanium oxide or synthetic resin filler.
If necessary, the high-bulk, wood containing printing paper provided by the present invention can also use additives applied during the papermaking process, such as aluminum sulfate, as well as various anionic, cationic, nonionic or amphoteric retention-improving agent, drainage-improving agent, paper-strengthening agent or internal sizing agent.
In addition, adding dye, fluorescent whitening agent, pH-adjusting agent, defoaming agent, pitch-control agent or slime-control agent, if necessary, will not produce any problem.
As explained above, the present invention requires a starch-based surface-paper-strengthening agent to be coated on surface to prevent bleeding. To improve surface strength and sizing property, other water-soluble polymer may also be mixed into the coating material.
As this water-soluble polymer, carboxy methyl cellulose, polyacrylic amide, polyvinyl alcohol or other materials normally used as surface treatment agents can be used alone or in any combination. In addition, a paper-strengthening agent may be added for waterproofing and improvement of surface strength, or a surface sizing agent may be added for addition of sizing property.
As explained above, the present invention achieves its intended purpose of providing a high-bulk, wood containing printing paper offering a density much lower than the practical limit of 0.50 g/cm3 achieved by conventional methods, by way of blending hardwood mechanical pulp offering high bulk and brightness, adding a bulk-increasing agent during the papermaking process, and then coating a starch-based surface-paper-strengthening agent. Specifically, a high-bulk base paper of a density ranging from 0.35 to 0.50 g/cm3 can be obtained. By coating a starch-based coating material on this high-bulk base paper, a high-bulk, wood containing printing paper offering high brightness, very low density, high flexibility (low stiffness) and excellent printability, and also preventing bleeding, can be produced.
Although the basis weight, ISO brightness, PPS roughness (average surface roughness of paper as measured by paper print-surf) of a high-bulk, wood containing printing paper are not specified, desirable values are 35 to 100 g/m2 for basis weight, 68.0% or more for ISO brightness, and 6.0 μm or less for PPS roughness.
The high-bulk, wood containing printing paper provided by the present invention can be suitably used as a paper for making books or used in offset printing, letterpress printing or gravure printing.
Examples of the present invention are explained below. Note that the present invention is not limited to these examples. The “%” used in the text indicates the weight percentage of solid content.
The mechanical pulps, bulk-increasing agents and a surface-paper-strengthening agent used to make the samples are specified below.
The methods used to measure the respective paper qualities are also explained.
(1) Sample Mechanical Pulps
Mechanical pulp A: Hardwood Maple TMP by Tembec; single fiber density index 0.22, ISO brightness 78.3%
Mechanical pulp B: Hardwood Eucalyptus Globulus APMP by Nippon Paper Industries; single fiber density index 0.28, ISO brightness 78.5%
Mechanical pulp C: Softwood Aspen TMP by Miller Western; single fiber density index 0.18, ISO brightness 77.1%
Mechanical pulp D: Softwood Radiata BCTMP by Winston; single fiber density index 0.16, ISO brightness 76.8%
(2) Sample Bulk-Increasing Agents
Bulk-increasing agent A: KB-1 15 (pentaerythritol distearin acid ester by Kao)
Bulk-increasing agent B: KB-08W (high-grade alcohol alkyl ether adduct by Kao)
Bulk-increasing agent C: DZ-2220 (oleic acid diamide by NOF)
Bulk-increasing agent D: 3-distearyl aminopropyl trimethyl ammonium chloride (by Nippon Paper Industries)
Bulk-increasing agent E: Lauric acid amide (by Nippon Paper Industries)
Bulk-increasing agent F: Oleic acid amide (by Nippon Paper Industries)
The preparation methods for bulk-increasing agents D, E and F are explained below:
Bulk-increasing agent D: A mixture consisting of 2.61 g of distearyl amine being second-grade amine and 1.00 g of 2,3-epoxy propyl trimethyl ammonium chloride as cationizing agent was dissolved in 15 ml of isopropanol. Then, 48% NaOH aqueous solution was added to adjust the pH to 10, and the substances were chemically reacted for 6 hours at 70° C. After the reaction period, water and chloroform were added to the mixture to extract organic substance, which was then dried on anhydrous magnesium sulfate. The residue obtained after vacuum distilling the solvent was refined by alumina column chromatography to obtain 0.66 g of white, wax-like 3-distearyl amino propyl trimethyl ammonium chloride.
Bulk-increasing agent F: A mixture of 25 g of oleic acid amide, 2.5 g of fatty acid potassium as emulsifying agent, and 472.5 g of hot water heated to 95° C. was placed in a high-pressure homogenizer (by A.P.V. Gaulin Inc.) and processed for 10 minutes under a pressure of 550 kg/cm2. The maximum processing temperature was approx. 120° C. After the processing in the high-pressure homogenizer, the mixture was immediately diluted with 15° C. pure water to obtain an oleic acid amide emulsion. The average grain size as measured by a laser grain-size analyzer was 2.3 μm.
(3) Sample Surface-Paper-Strengthening Agent
Surface-paper-strengthening agent A: Oxidized starch (Mermaid M200 by Shikishima Starch)
(4) Measuring Methods for Paper Qualities
Basis weight: Measured in accordance with JIS P 8124.
Paper thickness and density: Measured in accordance with JIS P 8118.
Brightness: Measured in accordance with JIS P 8123.
Tear length: Measured in accordance with JIS P 8113.
Pure flexural stiffness: Measured in accordance with the method explained on p. 123 of “Paper Pulp Test Methods” (by Japan TAPPI).
PPS roughness: Measured in accordance with ISO 8791 and also by soft backing.
Bleed test: The sample paper was printed on using a Roland R202 press, with damping water containing 1% etching solution (by Tokyo Ink; H solution No. 8, used by Dai Nippon Printing) and an ink prepared by adding 20% of compound to Purple A by Hayashi Ink. The printed paper was kept in a dark place for 30 days, after which bleeding of ink onto the back face was visually evaluated.
The result of the above visual evaluation was rated on the following three-point scale:
A pulp slurry, prepared from 5 parts of NBKP (ISO brightness 83.5%, CSF 440 ml), 70 parts of softwood RGP (ISO brightness 70.5%, CSF 90 ml) and 25 parts of mechanical pulp A (CSF 390 ml) and then adjusted to a CSF of 110 ml, was mixed with 1.6% of aluminum sulfate, 0.2% of paper-strengthening agent (EX-230 by Harima Chemicals), 1.0% of bulk-increasing agent A and 200 ppm of retention-improving agent (DR-3600 by HYMO), and then the mixture was introduced to a Duo Former FM papermachine at a speed of 550 m/min to make paper. The produced basepaper was coated with surface-paper-strengthening agent A using a gate roll coater to a coating amount of 1.2 g/m2, after which it was calendered at a nip pressure of 10 kgf to obtain a high-bulk, wood containing printing paper.
Paper was made under the same conditions as in example 1, except that bulk-increasing agent B was used instead of bulk-increasing agent A as specified in example 1.
Paper was made under the same conditions as in example 1, except that bulk-increasing agent C was used instead of bulk-increasing agent A as specified in example 1.
Paper was made under the same conditions as in example 1, except that bulk-increasing agent D was used instead of bulk-increasing agent A as specified in example 1.
Paper was made under the same conditions as in example 1, except that bulk-increasing agent E was used instead of bulk-increasing agent A as specified in example 1.
Paper was made under the same conditions as in example 1, except that bulk-increasing agent F was used instead of bulk-increasing agent A as specified in example 1.
Paper was made under the same conditions as in example 1, except that mechanical pulp B was used instead of mechanical pulp A as specified in example 1.
Paper was made under the same conditions as in example 3, except that 50 parts of mechanical pulp A and 45 parts of softwood RGP were blended.
Paper was made under the same conditions as in example 1, except that the coating amount of surface-paper-strengthening agent A as specified in example 1 was changed to 0.2 g/m2.
Paper was made under the same conditions as in example 2, except that the coating amount of surface-paper-strengthening agent A as specified in example 2 was changed to 0.2 g/m2.
Paper was made under the same conditions as in example 1, except that mechanical pulp C was used instead of mechanical pulp A as specified in example 1.
Paper was made under the same conditions as in example 1, except that mechanical pulp D was used instead of mechanical pulp A as specified in example 1.
Paper was made under the same conditions as in example 1, except that no bulk-increasing agent was added.
Paper was made under the same conditions as in example 7, except that no bulk-increasing agent was added.
Paper was made under the same conditions as in comparison example 4, except that 2% of bulk-increasing agent A was added. If softwood Radiata BCTMP is blended as mechanical pulp and a bulk-increasing agent is used, increasing the amount of bulk-increasing agent to 1.0% would not reduce the density below a certain level. The density-reduction effect of this formulation is therefore limited.
Paper was made under the same conditions as in example 1, except that 65 parts of mechanical pulp A and 30 parts of softwood RGP were blended and no bulk-increasing agent was added. Adding 65 parts of mechanical pulp A slightly reduced the density, but the surface strength was reduced and the amount of paper powder increased, resulting in lower printability.
When the results of examples 1 and 7 and comparison examples 3 and 4 are compared, it is clear that the density of the obtained wood containing printing paper cannot be reduced to 0.50 g/cm3 or below using mechanical pulp with a single fiber density index of less than 0.20.
Comparison example 4 in which softwood BCTMP is blended resulted in lower brightness, higher PPS roughness and increased stiffness (higher pure flexural stiffness in the CD direction). When examples 1 through 6 and comparison example 5 are compared, it is clear that a combination of hardwood mechanical pulp and bulk-increasing agent would significantly lower the density and also reduce the pure flexural stiffness in the CD direction. From comparison example 8, it is possible to reduce the density of the obtained wood containing printing paper to 0.50 g/cm3 or below by increasing the blending amount of hardwood mechanical pulp to 65%. However, it would increase the amount of paper powder and therefore the resulting paper would not be fit for practical use. On the other hand, a comparison of examples 1 and 2 and comparison examples of 1 and 2 shows that the problem of bleeding can be solved by coating a starch-based surface-paper-strengthening agent on the wood containing printing paper produced from hardwood mechanical pulp with a bulk-increasing agent added.
It will be understood by those of skill in the art that numerous and various modifications can be made without departing from the spirit of the present invention. Therefore, it should be clearly understood that the forms of the present invention are illustrative only and are not intended to limit the scope of the present invention.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2003-384516 | Nov 2003 | JP | national |
| 2004-227377 | Aug 2004 | JP | national |
