JP4953379B2 - Paper density modifier composition - Google Patents

Description

  The present invention relates to a paper density adjuster composition capable of improving the bulk of paper and imparting a volume feeling.

  In recent years, papers have been required to reduce costs, improve printing suitability, give a high-class volume, and reduce the use of raw pulp and chemicals and increase the utilization rate of used paper from the viewpoint of protecting forest resources. However, the increase in the waste paper utilization rate has caused problems such as a decrease in bulkiness because waste paper pulp fibers are shorter than virgin pulp fibers, resulting in an increase in the amount of pulp used. In addition, alkali agents such as sodium hydroxide and sodium silicate used for waste paper recycling, and chemicals such as hydrogen peroxide and bleaching agents such as hypochlorite flow into the papermaking process. The effect of a drug imparting functionality such as a drug is weakened, resulting in an increase in the amount used. As a method for increasing the bulk of paper, a method of making paper by mixing a cross-linked pulp or heat-fusible fiber reacted with a cross-linking agent, a method of mixing a core-sheath type or side-by-side type polyester fiber with a pulp, or an interface Methods using activators are known. As the surfactant, at least one of a fatty acid polyhydric alcohol ester and its alkylene oxide adduct (Patent Document 1), an oil-based nonionic surfactant, a sugar alcohol-based nonionic surfactant, and a sugar-based nonionic surfactant. Containing at least one of cationic compounds, amines, amine acid salts, amphoteric compounds (Patent Document 3), and having amines having hydroxyl groups as main components (Patent Documents) 4) etc. are known.

JP 11-350380 A JP-A-11-200263 JP-A-11-269799 JP 2005-325492 A

  However, the method of making paper by mixing cross-linked pulp or heat-fusible fiber reacted with a cross-linking agent, and the method of mixing core-sheath type or side-by-side type polyester fiber with pulp use materials different from pulp. Therefore, the original properties of the paper may be impaired, and the effect of increasing the bulk is not sufficient. In addition, the nonionic surfactants described in Patent Documents 1 and 2 are likely to cause problems such as a decrease in paper strength and a decrease in size when an amount capable of obtaining a sufficient bulkiness effect is added. The surfactant described in Patent Document 3 is a drug from the viewpoint of achieving both bulkiness and paper strength. (1) In a cationic drug, a chemical such as an alkali agent or a bleaching agent used for recycling used paper is used in the papermaking process. The performance of the cationic drug becomes insufficient. (2) Amine chemicals have problems in corrosiveness and safety, and further deteriorate in size, and tend to be alkaline paper-making, thus affecting printing ink characteristics. (3) In the drugs described in the examples as amine acid salts, the disadvantages of Cl, Br, and acetic acid as counterions are the safety of raw materials that form counterions (corrosion and odor problems), pH in small amounts Fluctuation is large and there is a risk that the preparation and stability of the chemicals may corrode the paper machine and pump, which may hinder the operation. Further, when paper products are incinerated, there is a risk of air pollution caused by chemicals and other pollutants such as dioxins. There is. (4) In amphoteric drugs, the bulkiness effect is originally insufficient, and a decrease in size occurs. In the surfactant described in Patent Document 3, the problem of size as listed in the above (1) to (4), the increase in the used paper usage rate, the closure, the increase and safety of drugs, the increase in trash, the paper quality Stability, operability, dioxin production problems, environmental characteristics of use (papermaking process problems), and environmental conservation were not considered.

  The papermaking process includes anionic trash such as fine fibers, fillers, additive chemicals, resin pitch, and dissolved lignin, but these anionic trashes are increasing due to increased use of waste paper pulp and closure of the papermaking process. . Anion trash adheres to various machines in the paper making process and causes pitch troubles, and problems such as a decrease in felt life, paper breakage, a decrease in productivity, and generation of oil spots are becoming more serious. Since these anionic trashes are negatively charged, a strong cationic drug cannot form a sufficient bulky effect by forming a complex with the anionic trash, and the complex exists as a pitch and causes contamination such as oil spots. There was a problem of generating a process trouble. In addition, when the dispersed particles in the papermaking system are large, there is a problem that the uniform adhesion is insufficient and the effect of bulk is difficult to be obtained, and the dispersed particles are also likely to aggregate, and therefore, when present as a pitch, they are likely to become a contamination source.

  On the other hand, the paper density adjusting agent of Patent Document 4 has an effect of increasing the bulk of paper and has a feature that there is little decrease in paper strength, but it is poor in dispersibility in the papermaking system and is sufficiently stirred when used. It was necessary to disperse uniformly. If the dispersion state of the paper density adjusting agent is insufficient, the coarse particles of the paper density adjusting agent are further aggregated and adhere to the equipment, etc., causing contamination, and the uniform adherence to the pulp is reduced. Further improvement is required because it is difficult to express the effect of increasing the bulk and the paper strength and printability are reduced due to the uneven adhesion.

  The present invention was made to solve the above-mentioned problems of the prior art, and even when the amount of used paper pulp increases in the papermaking process or when anion trash increases due to the closure of the papermaking process, poor drug dispersibility and It is an object of the present invention to provide a paper density adjusting composition that can prevent process troubles due to the generation of aggregates due to complex formation and can obtain low-density papers that are bulky and suppress paper strength reduction and printing suitability reduction.

That is, the present invention
(1) (A) 2 to 100 moles of alkylene oxide having 2 to 4 carbon atoms was added to a hydroxyamine derivative in which alkylene oxide having 10 to 22 carbon atoms was added to nitrogen of primary or secondary alkylolamine. One or more of the compounds represented by the following general formulas (a) and (b) and (B) alkylolamide compound are (A) :( B) = 99.9: 0. 1 to 80.0: a paper density adjuster composition characterized by containing it in a ratio of 20.0,

(2) The compound represented by the general formulas (a) and (b) is converted to propylene oxide 2 to a hydroxyamine derivative in which an alkylene oxide having 10 to 22 carbon atoms is added to nitrogen of a primary or secondary alkylamine. The paper density modifier composition according to the above (1), which is a compound added with ˜50 mol,

(3) The compounds represented by the general formulas (a) and (b) are prepared by adding ethylene oxide 2 to a hydroxyamine derivative in which an alkylene oxide having 10 to 22 carbon atoms is added to nitrogen of a primary or secondary alkylolamine. The paper density adjusting composition according to (1) above, wherein 10 moles and 15 to 40 moles of propylene oxide are random or block-added compounds,

(4) The paper density modifier composition according to any one of (1) to (3), wherein the alkylolamide compound is a compound represented by the following general formula (c):

(5) The paper density adjuster composition according to any one of (1) to (4), further containing 0.1 to 15.0% by weight of a fatty acid and / or a salt thereof in the composition,

(6) Any of the above (1) to (5), wherein the particle size (median diameter) of the 1% by weight aqueous dispersion is in the range of 0.5 μm to 200 μm at the same temperature as the papermaking system slurry temperature. A paper density modifier composition,
Is a summary.

  The paper density adjusting composition of the present invention reduces the corrosiveness and contamination of equipment such as paper machines and pumps, and papers treated with the paper density adjusting composition of the present invention are harmful substances when incinerated. Since there is no possibility of discharging, there is an effect that no environmental pollution problem occurs. Furthermore, since the paper density modifier composition of the present invention has excellent dispersibility in the papermaking system, it has uniform adhesion to the pulp, and even when the amount of used paper pulp increases and anion trash increases. In addition, it is possible to prevent process troubles due to the generation of aggregates such as poor dispersibility and complex formation, and to obtain low-density papers with little reduction in paper strength.

  In the present invention, the primary alkylol amine constituting the compound represented by the general formula (a) in the compound (A) and the primary alkylol amine constituting the compound when a in the general formula (b) is 0, For example, monomethanolamine, monoethanolamine, 3-amino-1-propanol, 1-amino-2-propanol, 4-amino-1-butanol, 4-amino-2-butanol, 5-amino-1-pentanol, And monoalkylolamines such as 6-amino-1-hexanol. Examples of the secondary alkylolamine constituting the compound when a in the general formula (b) is 1 include dialalkylolamines such as dimethanolamine, diethanolamine, dipropanolamine, and diisopropanolamine. . Among the primary alkylolamines and secondary alkylolamines, monomethanolamine, monoethanolamine, dimethanolamine, and paper containing the compound (A) represented by formulas (a) and (b) using diethanolamine The density adjusting agent composition is preferable because it is excellent in bulkiness effect, but monoethanolamine and diethanolamine are more preferable in terms of raw material costs and effects.

  Examples of the alkylene oxide having 10 to 22 carbon atoms added to the nitrogen of the primary or secondary alkylolamine include 1,2-epoxydecane, 1,2-epoxydodecane, 1,2-epoxytetradecane, 1,2 -Epoxyhexadecane, 1,2-epoxyoctadecane, 1,2-epoxyeicosane, 1,2-epoxydocosane and the like. Of these, 1,2-epoxydodecane, 1,2-epoxytetradecane, 1,2-epoxyhexadecane, and 1,2-epoxyoctadecane are preferable. Particularly, in terms of high bulk effect and high paper strength retention, 1, 2-epoxyhexadecane and 1,2-epoxyoctadecane are more preferable. These C10-22 alkylene oxides may be used alone or in combination of two or more. In the case of a primary alkylolamine having two active hydrogens bonded to nitrogen, the alkylene oxide having a total carbon number of 10 to 22 is substituted with one or two of the active hydrogens and added to nitrogen, In the case of the secondary alkylolamine, it is substituted with one of the active hydrogens and bonded to nitrogen.

  Examples of the alkylene oxide having 2 to 4 carbon atoms added to the hydroxyamine derivative in which the alkylene oxide having 10 to 22 carbon atoms is added to the nitrogen of the primary or secondary alkylamine include ethylene oxide (EO), propylene oxide ( PO), butylene oxide (BO), and the like, and two or more alkylene oxides may be added. When two or more different alkylene oxides are added, they may be added randomly or in a block form.

  The total number of moles of alkylene oxide having 2 to 4 carbon atoms in the compound (A) represented by the general formulas (a) and (b) is in the range of 2 to 100 moles per mole of the hydroxyamine derivative. . If the total number of added moles of alkylene oxide having 2 to 4 carbon atoms is less than 2 moles, the cationicity becomes too strong to form an anion trash and a complex, and a sufficient bulk effect cannot be obtained. Even if it is used, no further increase in bulk is observed, which is not preferable in terms of time required for production, cost, and the like.

  In the case where the alkylene oxide having 2 to 4 carbon atoms is added with one kind of alkylene oxide, the addition of 2 to 50 mol of propylene oxide suppresses the reduction of paper strength in the paper making process, and the control of the dispersed particle size is easy. This is preferable. Further, a compound in which two or more different alkylene oxides are added in the form of a block is more preferable from the viewpoints of stabilizing the particle size at the time of dispersing the drug and improving the dispersibility in the papermaking system. As what added 2 or more types of different alkylene oxides, what added 2-10 mol of ethylene oxide and 15-40 mol of propylene oxide at random or block form is preferable. In the case of block addition of ethylene oxide and propylene oxide, block addition of ethylene oxide, block addition of propylene oxide, block addition of propylene oxide, block addition of ethylene oxide, block addition of ethylene oxide In addition, a block addition of propylene oxide and a block addition of ethylene oxide are exemplified, but the invention is not limited to these forms.

  Among the block adducts of alkylene oxide, after block addition of ethylene oxide forming a hydrophilic block, block addition of propylene oxide forming a hydrophobic block and block addition of propylene oxide forming a hydrophobic block Later, when compared with a block addition of ethylene oxide that forms a hydrophilic block, the latter, in which the ethylene oxide block that forms the hydrophilic block is located at the end, is excellent in dispersibility in the papermaking system, and thus is oily. It is preferable that coarse particles are not easily generated. On the other hand, the former one in which the propylene oxide block of the hydrophobic block is located at the end contains an oxyethylene group of the hydrophilic block, so that it maintains an appropriate dispersion state in the system and is further excellent in adhesion to pulp. Is particularly preferable since the effect is improved and the effect is sufficiently exhibited. In the case of consisting of ethylene oxide and propylene oxide, the total number of added moles of alkylene oxide is particularly preferably 2 to 5 moles, and the added mole number of propylene oxide is preferably 20 to 30 moles.

  As a reaction method for obtaining the compound (A) represented by the general formulas (a) and (b), a hydroxyamine derivative obtained by adding an alkylene oxide having 10 to 22 carbon atoms to the nitrogen of the primary or secondary alkylamine is: For example, by mixing and stirring at 100 ° C. to 180 ° C. while dropwise adding alkylene oxide to alkylolamine, a substitution reaction between alkylene oxide and active hydrogen of alkylolamine occurs and can be easily obtained. General formulas (a) and (b) in which an alkylene oxide having 2 to 4 carbon atoms is further added to the hydroxyamine derivative in which an alkylene oxide having 10 to 22 carbon atoms is added to nitrogen of a primary or secondary alkylolamine. For example, the compound (A) represented by () is added with a catalyst to the above hydroxyamine derivative and then purged with nitrogen, followed by dehydration under reduced pressure at 100 ° C. to 120 ° C. for about 1 hour. In the method, an alkylene oxide having 2 to 4 carbon atoms is added by a specified amount (2 to 100 moles of alkylene oxide) per mole of hydroxyamine derivative under a pressurized condition of about 1 to 4 atm. it can. A catalyst such as a conventionally known basic catalyst, Lewis acid catalyst, or coordination catalyst can be used as a catalyst for adding an alkylene oxide having 2 to 4 carbon atoms to the hydroxyamine derivative. Among these, a basic catalyst is preferable from the viewpoint of cost, and potassium hydroxide is more preferable among the basic catalysts. The catalyst remaining after the addition reaction is preferably removed or inactivated. For example, a distillation step, an adsorption treatment with a silicate-based adsorbent typified by acid clay, synthetic magnesium silicate, or synthetic aluminum silicate, ion exchange. The catalyst can be removed using a desalting apparatus having a membrane or the like, or the catalyst can be neutralized and inactivated using an organic or inorganic acidic agent or alkaline agent. In particular, when a basic catalyst is used, it is more preferable to neutralize using an adsorption treatment with a silicate-based adsorbent and / or an organic acid such as formic acid, acetic acid, and lactic acid, from the viewpoint of cost and workability.

  The paper density adjuster composition of the present invention has the above general formulas (a) and (a) for the purpose of improving dispersibility in a papermaking system, suppressing aggregation of dispersed particles, and preventing process troubles due to adhesion contamination to facilities and the like. In addition to the compound represented by b), an alkylolamide compound is blended, and as this alkylolamide compound, N-hydroxyalkylalkane (or alkene) amide, N, N-di (hydroxyalkyl) alkane ( Or alkene) amide, N-hydroxyalkylalkane (or alkene) imide, N-polyoxyalkylenealkane (or alkene) amide, N, N-di (polyoxyalkylene) alkane (or alkene) amide, N-polyoxyalkylene Examples include alkane (or alkene) imide, and compounds represented by the following general formula (c) are preferably used. That.

  In the general formula (c), R is an alkyl or alkenyl group having 7 to 21 carbon atoms, n is an integer of 0 or 1, AO is an oxyalkylene group having 2 to 3 carbon atoms, and l is an integer of 1 or 2. Indicates. Moreover, in said formula, m shows the integer of 0-20 by the average addition mole number of an oxyalkylene group. Examples of alkylolamide compounds represented by the general formula (c) include plant fatty acids derived from coconut oil, palm oil, etc., animal fatty acids derived from beef tallow, etc., or methyl esters thereof as raw materials. After the reaction with ethanolamine or diethanolamine, it can be produced by a known method such as addition of an oxyalkylene group as necessary. Examples of the alkylene oxide having 2 to 3 carbon atoms include ethylene oxide (EO) and propylene oxide (PO), which may be used alone or in combination of two kinds. When two kinds of alkylene oxides are added, they may be added randomly or in a block form, and ethylene oxide is more preferable as the alkylene oxide.

  Examples of alkylolamide compounds represented by the general formula (c) include polyoxyethylene (5 mol) coconut oil fatty acid monoethanolamide, polyoxyethylene (20 mol) coconut oil fatty acid monoethanolamide, poly Oxyethylene (15 mol) beef tallow fatty acid monoethanolamide, polyoxyethylene (5 mol) coconut oil fatty acid diethanolamide, polyoxyethylene (20 mol) beef tallow fatty acid diethanolamide, polyoxyethylene (5 mol) polyoxypropylene (3 mol) ) Palm oil fatty acid monoethanolamide, polyoxyethylene (10 mol) polyoxypropylene (5 mol) beef tallow fatty acid monoethanolamide, and the like, but are not limited thereto. Among these alkylolamide compounds, polyoxyethylene coconut oil fatty acid monoethanolamide having an average addition mole number of polyoxyethylene groups in the range of 2 to 10 moles improves dispersibility in papermaking systems, foaming, etc. This is particularly preferable in that it does not induce adverse effects on operations.

  The paper density adjuster composition of the present invention comprises (A) the compound (A) represented by the general formula (a) and / or (b) and (B) an alkylolamide compound in a weight ratio: (B) = 99.9: 0.1 to 80.0: 20.0. When the ratio of (B) is less than 0.1, the dispersibility in the papermaking system becomes insufficient, and the effect of suppressing the coarse particles from further agglomerating and adhering to the equipment or the like is insufficient. If it exceeds 0, it is preferable in terms of imparting dispersibility in the papermaking system, suppressing the aggregation of dispersed particles and adhesion to equipment, etc., but the dispersed particles are too fine, and the adhesion to pulp is low, yield. Is not preferable in that it is difficult to express the effect of increasing the bulk of the paper. The ratio of (A) to (B) is more preferably (A) :( B) = 99: 1 to 85:15.

  In the paper density adjusting composition of the present invention, a fatty acid and / or a salt thereof can be further contained in the composition in an amount of 0.1 to 15.0% by weight. The fatty acid and its salt may be any of saturated, unsaturated, straight chain and branched chain fatty acids. Fatty acids and salts thereof are preferably those having a total carbon number of 8 to 22, and examples of fatty acids having 8 to 22 carbon atoms include caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, and behenic acid. Natural fatty acid, myristoleic acid, oleic acid, erucic acid, linoleic acid, linolenic acid and other unsaturated fatty acids, and isopalmitic acid, isostearic acid and other synthetic fatty acids. Of these, fatty acids that are liquid at room temperature are preferable from the viewpoint of solubility and storage stability, and examples of preferable fatty acids include unsaturated fatty acids such as oleic acid, linoleic acid, and linolenic acid, and low saturated fatty acid content. Examples include mixed fatty acids mainly composed of saturated fatty acids.

  Examples of fatty acid salts include alkali metal salts of the above fatty acids and salts of amines. Examples of alkali metal salts include potassium salts and sodium salts. Examples of amine salts include monoamine salts, polyamine salts, and alkylolamine salts. Of these, alkali metal salts such as potassium salt and sodium salt, and alkylolamine salts such as monoethanolamine salt and diethanolamine salt are preferable in terms of solubility and storage stability. When 0.1 to 15% by weight of a fatty acid and / or a salt thereof is further contained in the paper density adjuster composition, the paper density adjuster composition is imparted with appropriate dispersibility into the papermaking system and pitch formation is suppressed. In addition, the yield to pulp can be controlled. If the blending ratio of the fatty acid and / or salt thereof in the paper density adjuster composition is less than 0.1% by weight, there is a risk of insufficient dispersibility in the papermaking system and pitch formation suppression. If it exceeds 15.0% by weight, there is an effect of improving dispersibility in the papermaking system and suppressing pitch formation, but the dispersed particles become too fine, and the adhesion to the pulp is low, which is not preferable in terms of yield. There is also a risk of causing foaming and adversely affecting operations. Therefore, when blending a fatty acid and / or a salt thereof, blending so that the ratio in the paper density adjusting agent composition is 1.0 to 10.0% by weight is preferable for obtaining a better effect. The effect of the addition of this fatty acid and / or salt thereof is particularly problematic when making paper from neutral to alkaline using cheap fillers such as raw paper pulp and mechanical pulp, calcium carbonate, and the like. It is exhibited in a system in which a large amount of negatively charged anionic trash such as additive chemicals, resin pitch, and eluted lignin is generated. The fatty acid and / or salt thereof suppresses complex formation between the compound (A) and anion trash, prevents contamination in the system due to generation of coarse particles, and further imparts appropriate dispersibility into the papermaking system. It is considered a thing.

  The paper density adjuster composition of the present invention has an appropriate pH of 4.5 to 11.0 in terms of 1% by weight aqueous dispersion, taking into consideration various process chemicals and operating equipment conditions that are normally used. It is preferable that the pH is close to the pH of the pulp slurry in the system. In order to adjust the pH, a pH adjusting agent can be blended. As the pH adjusting agent, organic acids such as formic acid, acetic acid and lactic acid are preferable from the viewpoint of solubility and storage stability. If present, caustic potash, caustic soda, and alkylolamines are preferable.

  The effect of improving the bulk of the paper in the paper density adjusting composition of the present invention is considered to be mainly due to the compound (A) represented by the general formulas (a) and (b), but improves the bulk of the paper. This effect is thought to be due to the fact that these compounds adhere to the pulp and inhibit the hydrogen bonding between the pulps due to the hydrophobic effect, thereby preventing aggregation between the pulps. In order to express this performance effectively, uniform adhesion of the paper density adjusting agent to the pulp surface is required. As a result of working together by adding an alkylolamide compound and further a fatty acid and / or salt thereof, moderate dispersibility is imparted, resulting in improved uniform dispersion effect in papermaking system and uniform adhesion to pulp It is presumed that the effect of giving higher bulk to papers is exhibited.

  In order to obtain low density papers using the paper density adjusting composition of the present invention, it is necessary to control the dispersibility of the paper density adjusting composition in the system. If the dispersibility index here is mentioned, the particle diameter of the dispersed particles of the paper density adjusting agent composition is optimal. Many of the papermaking processes are operated at a pulp slurry temperature of 15 to 40 ° C. and a pH of 4.5 to 11.0. In order for the paper density adjuster composition to function effectively under these conditions, a paper density adjuster is required. When the particle size (median diameter) of the dispersed particles in the 1% by weight aqueous dispersion of the composition is in the range of 0.5 μm to 200 μm, the dispersibility in the papermaking system is good, and the dispersed particles are aggregated and installed. It is preferable at the point which suppresses adhesion of this. If it is less than 0.5 μm, it is desirable in terms of excellent dispersibility in the system and prevention of contamination due to aggregation of dispersed particles and adhesion to equipment or the like. However, since the particle size is too fine, the yield to the pulp decreases. In other words, since the adhesiveness to the pulp is lowered and the effect becomes poor, there is a problem that a large amount of the paper density adjusting agent composition needs to be added to the papermaking system and the cost is increased. In addition, when it exceeds 200 μm, the dispersed particles in the system are likely to become coarse particles, the uniform adhesion to the pulp is low, and when the particles are aggregated and adhere to equipment, contamination is likely to occur. It becomes a problem. In particular, when the particle diameter of the dispersed particles is in the range of 10 μm to 150 μm, it is excellent in moderate dispersibility in the system, suppression of the generation of deposits in the system, uniform adhesion to pulp, and the yield is also improved. As a result, the effect of increasing the bulk of the paper is more preferable. Here, in order to control and index the dispersibility of the paper density adjuster composition, the paper density adjuster composition is physically affected by the pulp slurry pH, physical shear force, and particularly the pulp slurry temperature in actual operation. Therefore, it is preferable to consider the following contents. The pH tends to be slightly smaller as the acidity or alkalinity increases with pH 7 as the center. The paper density adjuster composition of the present invention is not particularly problematic as long as it is in the range of pH 4.5 to 11.0 during normal operation, and is adjusted within the range with a pH adjuster as required, more preferably the pulp. Approximate to slurry pH. Alternatively, it is one method to reduce the blending ratio of the (B) alkylolamide compound in the paper density adjuster composition, and further the fatty acid and fatty acid salt added as necessary. The physical shearing force is attributed to the process equipment related to stirring, transfer, circulation, etc., and generally tends to be a smaller particle size when the shearing force is high and a larger particle size when the shearing force is low. The paper density adjuster composition of the present invention is intended to improve dispersibility in the system and suppress the aggregation of dispersed particles, so there is no effect when the shearing force is low or in process equipment that is normally operated. In particular, it is necessary to pay attention only to equipment having a high shearing force. In this case, the blending ratio of (B) alkylolamide compound, fatty acid, fatty acid salt in the paper density adjuster composition is reduced, or the speed of stirring, circulation, etc. is controlled based on the specifications of the process equipment, Adjust the shear force appropriately. Alternatively, it is one method to appropriately select the addition location of the paper density adjusting agent composition based on the specifications of the process equipment. By avoiding the influence on the dispersibility due to pH and physical shearing force in this way, a uniform dispersion effect of the paper density modifier composition and uniform adhesion to the pulp can be obtained, resulting in a bulky and reduced paper strength. In addition, it is possible to obtain low-density papers that suppress a decrease in printability. On the other hand, the pulp slurry temperature is usually in the range of 15 to 40 ° C., and the temperature characteristics of the paper density adjuster composition are larger on the high temperature side than on the particle size of the dispersed particles at 25 ° C. Then, since it has the characteristic which becomes a smaller particle diameter, it is preferable to make the particle diameter of the dispersion particle in this temperature into the range of 0.5 micrometer-200 micrometers. In this case, for example, the above general formulas (a) and (b) are used in order to achieve a hydrophilic or hydrophobic balance in which the paper density adjusting composition is more hydrophilic on the high temperature side and more hydrophobic on the low temperature side. The (A) compound, (B) alkylolamide compound, fatty acid, fatty acid salt and the blending ratio thereof are appropriately adjusted so that the particle size of the dispersed particles at the pulp slurry temperature is 0.5 μm to 200 μm. By maintaining the range, the compound (A) represented by the above general formulas (a) and (b) is inherently stable in the papermaking system without impairing the effect of giving high bulk to the paper. The effect can be continuously expressed. The particle diameter (median diameter) of the dispersed particles is a value measured under the following conditions.

Dispersion particle diameter (median diameter) measurement conditions:
The paper density adjuster composition of the present invention is adjusted to a pH range of 4.5 to 11.0 with a pH adjuster as necessary so that the paper density adjuster composition is 1% by weight, and tap water at the same temperature as the pulp slurry in the system. The mixture was stirred and dispersed for 3 minutes at a rotational speed of 250 rpm using a stirrer having three propeller blades (Three-one motor type 1200G: manufactured by Shinto Kagaku Co., Ltd.). A value (median diameter, relative refractive index) measured by a laser diffraction / scattering type particle size distribution measuring apparatus LA-910, manufactured by Horiba, Ltd., as a particle diameter in a 1% by weight aqueous dispersion of this paper density adjusting composition. : 1.30, particle diameter standard: volume).

  The paper density adjuster composition of the present invention is, for example, a high-concentration chest, a mixing chest, a machine chest, or an approach part type seed box in which pulp slurry before paper making is stirred, a white water in a fan pump or a closed paper making process. By directly adding to a wire pit for circulation as a stock solution or an aqueous dispersion, it can be added uniformly to the pulp and the bulk of the paper can be increased. When adding the paper density regulator composition of this invention in a pulp slurry, the addition amount of 0.01-2 weight% of a pulp raw material dry weight is preferable. As the pulp raw material, any of softwood pulp, hardwood pulp, chemical pulping pulp, semi-chemical pulp, mechanical pulp, waste paper pulp and the like can be used. The paper density modifier composition of the present invention exhibits an excellent bulky effect for both virgin pulp and waste paper pulp, and is used in a closed papermaking process or in an open papermaking process. Although an excellent bulkiness effect is exhibited, an excellent bulkiness imparting effect is also exhibited in a closed papermaking process including waste paper pulp, which is difficult to impart bulkiness with a conventional paper density adjusting agent. In the paper density adjuster composition of the present invention, a nonionic surfactant, an anionic surfactant, a positive surfactant is added as necessary for the purpose of imparting flexibility, bulkiness and the like within a range that does not inhibit the effect. Other surfactants such as ionic surfactants, amphoteric surfactants, and polymeric surfactants can be added. In addition, commonly used papermaking chemicals such as sizing agents such as alkyl ketene dimers, rosin, starch, paper strength enhancers, freeness improvers, yield improvers, fillers, scale inhibitors, antifoaming agents, etc. It can also be used together. Furthermore, the paper density adjusting agent composition of the present invention is appropriately selected according to other characteristics such as printing characteristics other than bulkiness required in use environment characteristics and paper applications, or two or more kinds are blended. Can also be used.

  Hereinafter, the present invention will be described in more detail with reference to examples. The compounds (A) used in Examples and Comparative Examples are as shown in Table 1. In Table 1, an oxyalkylene group (a type of alkylene oxide having 2 to 4 carbon atoms) represents an oxypropylene group as PO and an oxyethylene group as EO. The order of addition of the block adducts of oxyalkylene groups is as described.

The (B) alkylolamide compounds used in Examples and Comparative Examples are as follows.
Amide A: Polyoxyethylene (10 mol) coconut oil fatty acid monoethanolamide amide B: Polyoxypropylene (2 mol) Polyoxyethylene (12 mol) Beef tallow fatty acid monoethanolamide amide C: Polyoxyethylene (2 mol) coconut fatty acid Monoethanolamide

The fatty acids used in Examples and Comparative Examples are as follows.
Fatty acid A: oleic acid 73%, linoleic acid 16%, linoleic acid 1%, saturated fatty acid having 12 to 18 carbon atoms at room temperature, liquid fatty acid B: oleic acid 68%, linoleic acid 23%, linolenic acid 4 %, Mixed fatty acid of normal temperature liquid of 5 to 16% saturated fatty acid having 16 to 18 carbon atoms

Examples 1-11, Comparative Examples 1-10
Test 1 (used paper deinked pulp: DIP, neutral and acidic papermaking)
As a pulp raw material, a paper sheet having a basis weight of 60 g / m ² is obtained by using approximately 3% waste paper pulp slurry (slurry pH: 5.3) containing a process chemical provided by a paper manufacturer adopting a closed paper making process. Adjusted to obtain. While stirring this pulp slurry at a rotational speed of 250 rpm with a stirrer having a propeller type three blades at 25 ° C. (Three-one motor type 1200G: manufactured by Shinto Kagaku Co., Ltd.), with respect to the pulp raw material dry weight in the pulp slurry, 1% by weight aqueous dispersion shown in Table 2 corresponding to 0.6% by weight of the paper density adjusting agent composition, 1.0% by weight of a sizing agent (alkyl ketene dimer system) was added and stirred for 3 minutes, and then 120 mesh wire. A test paper was prepared using a square tappi paper machine equipped with squeezed paper, pressed, then sandwiched between 100 mesh filter cloths, and dried at 105 ° C. for 3 minutes using a mirror dryer. The dried paper sheet is conditioned for 24 hours under the conditions of 25 ° C. and humidity 40%, and then the paper density (bulkyness), paper strength remaining rate (paper strength), anion trash dispersibility, and surface paper strength are measured. The state of the test paper was confirmed by the following method. The measured values of bulkiness and paper residual ratio are 10 measurements, and the confirmation of anion trash dispersibility and surface paper strength is an average evaluation of 5 measurements. The results are shown in Table 3. Table 2 also shows the results of evaluating the pH, median diameter, and dispersion state of a 1% by weight aqueous dispersion of the paper density adjuster composition as follows.

Dispersion state of 1 wt% aqueous dispersion:
If the dispersibility of the drug in the papermaking system is low, the adhesion to the pulp will be biased, leading to a decrease in bulk performance and an oil spot. Moreover, even if the dispersibility is too high, the yield and the performance expression are lowered. For this reason, the dispersion state of the 1% by weight aqueous dispersion of the paper density adjusting agent composition used in Examples and Comparative Examples was visually confirmed, and the results were classified as follows.
A: A particle having a median diameter of 10 μm to 150 μm and maintaining stable particles even when allowed to stand.
○: Some oil floating occurs when the median diameter is 10 μm to 150 μm.
(Triangle | delta): The thing which can maintain a dispersion state for 10 minutes or more after standing by median diameter less than 10 micrometers or 150-200 micrometers.
X: Solubilization, or median diameter exceeding 200 μm, or separation occurring within 10 minutes upon standing.

Paper density (bulkyness) (g / cm ³ ):
Based on JIS P8118-1998 “Testing method for thickness and density of paper and paperboard”, the basis weight (g / m ² ) of the paper sheet after humidity control and the automatic elevating paper thickness meter TM-600 (Kumaya Riki Kogyo ( The thickness (mm) was measured by the following formula (1), and the density (g / cm ³ ) was determined by the following formula (1). The thickness was measured at 24 points for each paper sheet, and an average value was used. The smaller the density, the higher the bulk.
(Equation 1)
Paper density = basis weight ÷ thickness × 0.001 (1)

Bulkiness rate (%)
The bulkiness ratio was calculated from the obtained paper density by the following formula (2). The bulk factor of the blank (made with no chemicals used) is set to 100.
(Equation 2)
Bulkiness factor = paper density of test paper ÷ paper density of blank × 100 (2)

Paper strength remaining rate (%):
Ten test pieces having a size of 2.5 cm × 10 cm were cut out from the paper sheet after humidity control, and the paper strength (tensile strength) was measured with a Unitron tensile tester (Ueshima Seisakusho Co., Ltd.). The average value for 10 samples was obtained as the average paper strength, and the paper strength of blanks (made without using any chemicals) was set to 100, and the residual strength was calculated from the following formula (3).
(Equation 3)
Paper strength remaining rate = average paper strength of the test piece ÷ average paper strength of the blank × 100 (3)

Anion trash dispersibility:
If the anion trash dispersibility is poor, the color difference of the paper sheet decreases, so a test piece of 20 cm x 20 cm is cut out from the paper sheet after humidity control, and is folded four times to a size of 5 cm x 5 cm. Lightness, whiteness, and yellowness were measured by Denshoku Industries Co., Ltd., and were evaluated comprehensively from the average value of each 5 sheets as follows.
A: Brightness 74 or more, whiteness 45 or more, yellowness 28 or less.
○: Lightness 72 or more and less than 74, whiteness 43 or more and less than 45, yellowness 28 or more and less than 30.
(Triangle | delta): Lightness 70-72, Whiteness 41-43, Yellowness 30-32.
X: Lightness less than 70, whiteness less than 41, yellowness of 32 or more

Surface paper strength:
If the uniform adhesion performance of the medicine is low, the amount of the medicine attached becomes darker during papermaking, leading to an oil spot and a local decrease in paper strength. Further, during printing, the portion swells and tears, and the paper is peeled off to hinder the printability. Therefore, JAPAN TAPPI paper pulp test method no. The wax pick test was performed based on 1: 2000 “Paper and paperboard—surface strength test method using wax”. Place the paper sheet after humidity control on 10 sheets of paper on a flat table, place a wax stick melted with an alcohol lamp on the surface of the paper sheet, cool it for 15 minutes, and then remove the paper around the wax. It was pressed with a presser plate and the wax was peeled off vertically. The tip of the peeled wax and the paper sheet were examined, and the highest wax number at which the paper sheet surface did not swell, tear, or peeled off was recorded, and was evaluated comprehensively as follows. In addition, five sheets were tested for each paper sheet to which each chemical was added, and the wax number was written for the blank.
◎: No change at the same wax number as the blank ○: Same wax number as the blank but slightly fuzzy △: One wax number lower than the blank ×: Slightly lower wax number than the blank That cause fluffing or less

Test paper condition:
The properties of the paper sheet after humidity control were evaluated as follows from the paper thickness measurement and visual judgment.
A: Uniform when measuring paper thickness (measurement width of paper thickness is within ± 5% of average value)
○: The paper thickness is almost uniform when measuring the paper thickness (the measured width of the paper thickness is within ± 10% of the average value)
Δ: Local deviation of paper thickness is observed (measurement width of paper thickness is ± 11% or more of average value)
X: An oil spot is generated.

Test 2 (used paper deinked pulp: DIP / alkaline papermaking)
Using about 3% waste paper pulp slurry (slurry pH: 10.0) containing a process chemical provided by a paper manufacturer using a closed paper making process as the pulp material, paper is made in the same manner as in Test 1 and dried. After the humidity control, measurement and evaluation were performed. The results are shown in Table 4.

Test 3 (Hardwood Bleached Kraft Pulp: LBKP)
Using about 3% LBKP pulp slurry (slurry pH: 5.5) containing a process chemical provided by a paper manufacturer as a pulp raw material, paper was made in the same manner as in Test 1, and after drying and humidity control, The density (bulkyness), paper strength remaining rate (paper strength), surface paper strength measurement, and confirmation of the state of the test paper were performed in the same manner as in Test 1. The results are shown in Table 5.

Claims (6)

(A) 2 to 100 mol of alkylene oxide having 2 to 4 carbon atoms is added to hydroxyamine derivative in which alkylene oxide having 10 to 22 carbon atoms is added to nitrogen of primary or secondary alkylolamine. One or more of the compounds represented by formulas (a) and (b) and (B) alkylolamide-based compound in terms of weight ratio, (A) :( B) = 99.9: 0.1-80 A paper density adjuster composition characterized by containing it in a ratio of 0.0: 20.0.

The compound represented by the general formulas (a) and (b) is a hydroxyamine derivative in which an alkylene oxide having 10 to 22 carbon atoms is added to nitrogen of a primary or secondary alkylolamine, and 2 to 50 mol of propylene oxide. The paper density adjuster composition according to claim 1, which is an added compound. The compound represented by the general formulas (a) and (b) is a hydroxyamine derivative in which an alkylene oxide having 10 to 22 carbon atoms is added to nitrogen of a primary or secondary alkylolamine, to 2 to 10 mol of ethylene oxide, The paper density adjuster composition according to claim 1, wherein 15 to 40 moles of propylene oxide are random or block-added compounds. The paper density adjuster composition according to any one of claims 1 to 3, wherein the alkylolamide compound is a compound represented by the following general formula (c).

Furthermore, the paper density regulator composition in any one of Claims 1-4 which contains a fatty acid and / or its salt 0.1 to 15.0 weight% in a composition. The paper density according to any one of claims 1 to 5, wherein the particle size (median diameter) of the dispersed particles of the 1 wt% aqueous dispersion is in the range of 0.5 µm to 200 µm at the same temperature as the slurry temperature in the papermaking system. Conditioner composition.