JP5242365B2 - Method for producing pharmaceutical composition for papermaking - Google Patents

Description

  The present invention relates to a pharmaceutical composition for papermaking, a method for producing a pharmaceutical composition for papermaking, and a method for producing paper using the composition.

  In recent years, high quality paper with excellent whiteness, opacity, printability, volume, etc. has been demanded, while lightweight paper with low pulp usage is desired for environmental considerations. . In order to solve these problems by the bulkiness of paper, various methods for improving the bulk have been attempted so far, and one of them is the use of a paper quality improver such as a bulking agent.

  For example, Patent Document 1 discloses a monoamine, for the purpose of obtaining a coated paper having a small increase in density even after pressure treatment, high ink absorbability, and excellent color development and water resistance of an ink image. Pulp fiber is a compound obtained by reacting an epihalohydrin or glycidyl ether and / or a compound derived therefrom with a compound having a residue obtained by removing active hydrogen from a polyamine, polyalkyleneimine or a derivative thereof and an acyl group. It is disclosed that low density paper that is attached and imparted with bulkiness is used as a base paper.

  Further, Patent Document 2 discloses a residue obtained by removing active hydrogen from a monoamine, polyamine, polyalkyleneimine or a derivative thereof for the purpose of producing a paper product with high opacity without reducing the strength and size of the paper. A paper opacifying agent characterized by a compound obtained by reacting a compound having a group and an acyl group with epihalohydrin or glycidyl ether and / or a compound derived therefrom is disclosed. And as the manufacture example, tetraethylenepentamine and stearic acid (molar ratio 1/2) are reacted to obtain an intermediate compound, and the intermediate compound is further heated to 90 ° C. to produce epichlorohydrin (molar ratio 1). / 2) is disclosed as a paper opacifier component obtained by dripping.

  Patent Document 3 discloses an aqueous emulsion system in which a polymer compound obtained by reacting a predetermined amide compound with an epihalohydrin in the presence of a cationic polymer and / or an amphoteric polymer is highly concentrated. Is used as an internal additive for paper.

  Patent Document 4 discloses a basic fatty acid amide prepared from a specific fatty acid mixture and a specific amine and quaternized with epichlorohydrin in order to improve the effect of a conventional sizing agent. It is disclosed to use a paper sizing agent comprising an aqueous formulation of the kind and an electrolyte.

  Patent Document 5 discloses a method for producing a pulp sheet having a step of adding a specific papermaking agent for reducing the sizing degree, a cationic surfactant, and an alkyl ketene dimer or alkenyl succinic anhydride to a pulp slurry. It is disclosed.

  Patent Document 6 discloses a paper pharmaceutical composition comprising a nonionic surfactant and two specific types of cationic surfactants. Patent Document 6 describes that components such as a sizing agent are desirably added separately from the paper-making drug composition when paper is produced using the paper-making drug composition.

JP 2005-188001 A JP 2000-273792 A JP 2006-104609 A Japanese Examined Patent Publication No. 63-30439 JP-A-2005-314836 JP 2007-277736 A

  One of the problems in bulky paper production by the bulking agent is that the liquid absorption amount of the coating liquid tends to increase in the step of applying the coating liquid to the surface of the paper immediately after the dryer, such as passing through a predryer. This is thought to be due to an increase in the porosity of the paper when a bulking agent is used. This increase in the amount of liquid absorption increases the drying load after coating, and the papermaking speed cannot be sufficiently increased throughout the production of bulky paper (reduction in papermaking speed). In particular, as a process of applying the coating liquid, liquid absorption in the size press process is a problem. The phenomenon of increasing the liquid absorption amount is noticeable in a two-roll size press where it is difficult to control liquid absorption because of the structure in which paper is passed through the coating liquid.

  An object of this invention is to provide the manufacturing method of the pharmaceutical composition for paper manufacture from which the liquid absorption of a coating liquid can be suppressed and a bulky paper is obtained.

The present invention is represented by a nonionic surfactant (A) [hereinafter referred to as component (A)], alkyl ketene dimer (B) [hereinafter referred to as component (B)], and the following general formula (C-1). A cationic surfactant (C) [hereinafter referred to as component (C)] and water, a method for producing a papermaking pharmaceutical composition comprising:
(A) Component and (B) component are emulsified in water in the presence of component (C) [hereinafter referred to as emulsification step],
The present invention relates to a method for producing a pharmaceutical composition for papermaking.

[Wherein R _{1c to} R _4c are each an alkyl group having 1 to 24 carbon atoms, an alkenyl group having 2 to 24 carbon atoms, a β-hydroxyalkyl group having 1 to 24 carbon atoms, a benzyl group, or a formula: (A ₁ O) n ₁ -Z ₁ (wherein A ₁ O is an oxyalkylene group having 2 to 4 carbon atoms, Z ₁ is a hydrogen atom or an acyl group, and n ₁ is an average addition mole of A ₁ O. X ₁ ⁻ is a counter ion. ]

  Moreover, this invention relates to the pharmaceutical composition for paper manufacture which consists of an emulsion obtained by emulsifying (A) component and (B) component in water in presence of (C) component.

  The present invention also relates to a paper manufacturing method having a size pressing step, wherein the paper pharmaceutical composition of the present invention is added in a step prior to the size pressing step.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the pharmaceutical composition for paper manufacture which can suppress the liquid absorption of the coating liquid at the time of papermaking, and can obtain a bulky paper is provided. Since the liquid absorption of the coating liquid is suppressed by using the papermaking chemical composition produced according to the present invention, the papermaking speed can be increased, and it can be expected that the productivity of bulky paper is improved as compared with the conventional art.

  The pharmaceutical composition for papermaking produced according to the present invention has a reduced volume of paper that is absorbed in the process of applying the coating liquid immediately after the dryer by adding it to the pulp slurry at the time of papermaking and papermaking. The size is improved. Hereinafter, (A) component, (B) component, and (C) component used for this invention are demonstrated.

[(A) component]
The nonionic surfactant (A) of the present invention is preferably selected from those having a water separation degree of 4% or more as defined below from the viewpoint of bulkiness.
Degree of water separation (%) = (α ₀ −α) / α ₀ × 100
α: Moisture content of wet sheet obtained by adding 5 parts by weight of a compound that becomes a nonionic surfactant to 100 parts by weight of pulp α ₀ : Add a compound that becomes a nonionic surfactant to pulp Moisture content of wet sheet obtained without making paper

The measuring method of the water separation degree in this invention is explained in full detail.
[Method of measuring water separation]
(A) Used pulp
A beech-derived hardwood bleached pulp (hereinafter referred to as LBKP) having a Hunter whiteness (JIS P 8123) of 80 ± 5% of a handsheet obtained by the method for preparing a handsheet for pulp test of JIS P8209 is used.

(B) Measurement of degree of water separation (i) LBKP was disintegrated in a certain amount at 25 ± 3 ° C with a beater and beaten to 460 ± 10 ml with Canadian standard freeness (JIS P 8121). Of LBKP slurry.

The pulp slurry was weighed so that the basis weight of the LBKP content of the sheet after papermaking was 80 ± 2 g / m ² , adjusted to pH 4.5 with aluminum sulfate, and then added 1.0 weight of nonionic surfactant. % Ethanol solution is added in an amount of 5 parts by weight (pure content) to 100 parts by weight of pulp, and a wet sheet is obtained by making paper with a 150 mesh wire (area 200 cm ² ) using a round tappi paper machine. Two sheets of filter paper (having a diameter of 185 mm) having a basis weight of 320 ± 20 g / m ² are stacked on the wet sheet, and a coach plate is further stacked thereon to perform coaching, and then the wet sheet is taken out. Next, the wet sheet is sandwiched between the above two filter papers and pressed at a pressure of 340 ± 10 kPa for 5 minutes. After pressing, the weight w (g) of the wet sheet is weighed immediately.

Next, it is dried at 105 ± 3 ° C. for 60 minutes, and the weight W _d (g) of the obtained dried sheet is weighed.
(Ii) The water content α (%) is obtained from the above-obtained W and W _d by the equation (1).
α (%) = (W−W _d ) / W × 100 (1)
Further, a sheet is prepared in the same manner without adding a compound that becomes a nonionic surfactant, and the water content obtained in the same manner is defined as α ₀ .
(Iii) The water separation degree is obtained from the following formula (2) from the moisture contents α and α ₀ obtained above.
Degree of water separation (%) = (α ₀ −α) / α ₀ × 100 (2)

In addition, the nonionic surfactant (A) is preferably one or more nonionic surfactants selected from the following (A _i ) and (A _ii ) from the viewpoint of bulkiness, and in particular, Among them, the water separation degree is preferably 4% or more.

(A _i ) a straight or branched chain having 6 to 22 carbon atoms, a saturated or unsaturated monohydric alcohol, a 2 to 14 polyhydric alcohol having a total carbon number of 2 to 24 which may contain an ether group, and One or more compounds selected from these alkylene oxide adducts having 2 to 4 carbon atoms [hereinafter referred to as (A _i ) component]

(A _ii ) one or more compounds selected from fatty acid esters and adducts thereof having 2 to 4 carbon atoms (hereinafter referred to as AO) [hereinafter referred to as (A _ii ) component]

Among the components (A) of the present invention, the component (A _i ) is a straight or branched chain having 6 to 22 carbon atoms, a saturated or unsaturated monohydric alcohol, and a total carbon number of 2 which may contain an ether group. -24 to 14-valent polyhydric alcohols, and these AO adducts having 2 to 4 carbon atoms. Furthermore, an ether compound in which an alkyl group is bonded to part or all of the terminal of the alcohol or its AO adduct is also included.

  The monohydric alcohol is preferably a linear saturated alcohol having 6 to 22 carbon atoms, more preferably a linear saturated alcohol having 8 to 22 carbon atoms, and further preferably a linear saturated alcohol having 10 to 22 carbon atoms.

  The polyhydric alcohol is preferably a 2- to 12-valent alcohol having 2 to 24 carbon atoms which may contain an ether group, more preferably a 2- to 10-valent alcohol, and even more preferably a 3- to 6-valent alcohol.

  Examples of the dihydric alcohol include those having a total carbon number of 2 to 10 which may contain an ether group, such as propylene glycol, dipropylene glycol, butylene glycol, dibutylene glycol, ethylene glycol, diethylene glycol, and polyethylene glycol.

  As trihydric or higher alcohols, alcohols having a total carbon number of 3 to 24 which may have an ether group, those having a total number of hydroxyl groups / total number of carbons in one molecule = 0.4 to 1, such as glycerin, poly Examples thereof include glycerin (average condensation degree 2 to 5), pentaerythritol, dipentaerythritol, arabitol, sorbitol, stachyose, erythritol, arabit, mannitol, glucose, sucrose, and the like.

  More preferably ethylene glycol, diethylene glycol, propylene glycol, an alcohol having 3 to 12 total carbon atoms which may have an ether group, and having 3 or more valences, wherein the number of hydroxyl groups in one molecule / total number of carbons = 0.5 to 1. It is alcohol. Particularly preferred are glycerin, polyglycerin (average condensation degree 2 to 4), and pentaerythritol.

  AO is ethylene oxide (hereinafter referred to as EO) and / or propylene oxide (hereinafter referred to as PO). When both EO and PO are used, either random addition or block addition may be used. Moreover, 0-200 mol is preferable and, as for each average addition mole number, 0-100 mol is more preferable. PO is preferably 0 to 150 mol, more preferably 0 to 100 mol.

The component (A _ii ) is one or more compounds selected from fatty acid esters and C2-4 AO adducts thereof. Among these, esters of fatty acids and alcohols are preferable, and esters of fatty acids and polyhydric alcohols are more preferable.

Fatty acids used for esters of fatty acids and alcohols include fatty acids having 6 to 24 carbon atoms, preferably 10 to 22 carbon atoms, and may be saturated, unsaturated, linear or branched. preferable. More preferred are lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, and oleic acid, with stearic acid being preferred. Specific examples of the alcohol used in the ester include the monovalent or polyhydric alcohols described in the component (A _i ) and their AO adducts.

As esters of fatty acids and monohydric alcohols, compounds represented by the following general formula (A ′) can also be preferably used.
R′COO (EO) _p (PO) _q R ″ (A ′)
[In the formula, R ′ represents an alkyl group, alkenyl group or β-hydroxyalkyl group having 5 to 23 carbon atoms, and R ″ represents an alkyl group, alkenyl group or β-hydroxyalkyl group having 6 to 22 carbon atoms. . EO is ethylene oxide, PO is propylene oxide, p and q are average addition mole numbers, p is a number of 0 to 20, and q is a number of 1 to 20, respectively. ]

  These esters can be obtained by a known esterification reaction and AO addition reaction. For example, an esterification catalyst is added to a mixture of a fatty acid and a polyhydric alcohol, and an ester is obtained by reacting at 150 to 250 ° C., if necessary. Further, an AO having 2 to 4 carbon atoms in the presence of an alkali catalyst or the like. Is added to obtain an AO-added ester. Further, esterification may be performed after adding AO to fatty acid or polyhydric alcohol. Furthermore, it may be obtained by adding only AO to the fatty acid.

  The average degree of substitution of this ester is preferably 10 to 95 equivalent%, more preferably 10 to 80 equivalent% of OH in the alcohol per mole of polyhydric alcohol, particularly preferably 1 mole. It has 1-2 mol ester groups per monohydric alcohol.

  When using AO addition ester, the average addition mole number of AO is more than 0-10 mol per alcoholic hydroxyl group, and more than 0-5 mol is preferable. In addition, when the polyhydric alcohol which can become AO group like ethylene glycol etc. is used, they are also included in the number of AO groups. AO is preferably EO or PO. These may be EO, PO alone or a mixture of EO and PO. In the present invention, it is particularly preferable to use an ester of a polyhydric alcohol and a fatty acid that does not contain an AO group.

  As the component (A), an ester compound of an alcohol selected from glycerin, polyglycerin (average condensation degree 2 to 4) and pentaerythritol, and a fatty acid selected from palmitic acid and stearic acid is particularly preferable.

  In addition, the component (A) is uniformly transparent when it is maintained at 20 ° C. after being added to and stirred in water so as to have a concentration of 1.0% by weight (may be heated to 100 ° C. or lower during the course). What does not become preferred is preferable. Here, “thing that does not become uniform and transparent” means that the whole system is not uniform (there is no precipitate or suspended matter), or even if it is uniform, 1.0 weight of component (A) at 20 ° C. The transmittance (T%) at an optical path of 10 mm in visible light of 660 nm of a% aqueous solution is 5% or less when water is 100%.

[Component (B)]
The pharmaceutical composition for paper manufacture manufactured by this invention contains the alkyl ketene dimer as (B) component. Examples of the alkyl ketene dimer include those having 12 to 22 carbon atoms, preferably those having 14 to 20 carbon atoms, and more preferably those having 16 or 18 carbon atoms.

[Component (C)]
The pharmaceutical composition for paper manufacture manufactured by this invention contains the cationic surfactant (C) represented by the said general formula (C-1). In General Formula (C-1), R _{1c to} R _4c are preferably an alkyl group having 1 to 24 carbon atoms and an alkenyl group having 2 to 24 carbon atoms, and more preferably an alkyl group having 1 to 20 carbon atoms. The counter ion X ₁ ⁻ is preferably methyl sulfate ion or ethyl sulfate ion.

From the viewpoints of dispersibility and handleability of the component (A) and the component (B), R _{1c to} R _4c are alkyl groups having 1 to 20 carbon atoms, and the counter ion X ₁ ^- is ethyl. It is a compound that is sulfate ion. Furthermore, a compound in which at least one of R _{1c to} R _4c is an alkyl group having 14 to 20 carbon atoms and the remaining is an alkyl group having 1 or 2 carbon atoms is more preferable.

[Method for producing paper-made pharmaceutical composition and paper-made pharmaceutical composition]
The method for producing a pharmaceutical composition for papermaking of the present invention includes a step of emulsifying the component (A) and the component (B) in water in the presence of the component (C) [emulsification step]. The reason why the liquid absorption of the coating liquid is suppressed by the paper pharmaceutical composition of the present invention obtained through such an emulsification step is not clear, but the components (A) and (B) are (C) It is presumed that the efficiency of adsorption to the pulp is improved by emulsification with the components. In the emulsification step, the component (A) and the component (B) can be emulsified in water with the component (C). By the emulsification step, an emulsion containing the component (A), the component (B), the component (C) and water is prepared. In this invention, (A) component and (B) component exist in the state emulsified in water with (C) component.

  In the production method of the present invention, the temperature in the emulsification step is not particularly limited, but preferably the emulsification step is performed at a temperature at which the component (A) and the component (B) are melted. At that time, the component (A), the component (B), the component (C) and water are heated to a temperature equal to or higher than the melting points of the component (A) and the component (B) (that is, the melting point of the component (A) and the component (B). The temperature is higher than both of the melting points of (A) and (B), more preferably at least 10 ° C. higher than the higher melting point of the melting points of the component (A) and the component (B), and more preferably 50 to 100 ° C. preferable. The order of mixing the components (A), (B), (C) and water is not limited, but the emulsion is composed of the three components (A), (B) and (C). Need to be done. If necessary, an emulsifier such as a homomixer, a line mixer, or a high-pressure homogenizer can be used. From the viewpoint of the properties of the emulsion and ease of handling, the solid content concentration in the emulsion is preferably 5 to 50% by weight, more preferably 10 to 40% by weight, and still more preferably 10 to 30% by weight.

  The emulsification time is not particularly limited, but the (A) component, the (B) component, and the (C) component are added to water or warm water, and the entire solution is brought to a temperature equal to or higher than the melting points of the (A) component and the (B) component. It is preferable to carry out for 10 minutes to 3 hours while maintaining, and more preferably for 30 minutes to 2 hours.

  The papermaking pharmaceutical composition of the present invention is obtained from an emulsion obtained by emulsifying the component (A) and the component (B) in water with the component (C), and can be used even in the state of the emulsion. However, from the viewpoint of ease of handling and performance stability, a suspension is preferred. That is, the pharmaceutical composition for papermaking of the present invention has a state of an emulsion containing (A) component, (B) component and (C) component and water in the production process. Any of those other than product and emulsification may be used. The suspension containing the component (A), the component (B), the component (C) and water is obtained by cooling the emulsion obtained in the emulsification step to a temperature below the melting point of the component (A) and the component (B). Can be obtained. Accordingly, the papermaking pharmaceutical composition of the present invention comprises a papermaking pharmaceutical composition comprising an emulsion obtained by emulsifying the component (A) and the component (B) in water in the presence of the component (C), and The pharmaceutical composition for papermaking which consists of a suspension obtained from the emulsion which emulsified (A) component and (B) component in water in presence of (C) component is included.

A method for measuring the melting point of the component (A) and the component (B) will be described. The sample is melted at the lowest possible temperature and sucked up to about 10 mm into a capillary ("ME-18552" manufactured by Mettler (hard glass, length 76 mm, inner diameter 1.3 mm, wall thickness 0.2 mm)). Cool at 10 ° C. or lower for 24 hours or at least 2 hours to solidify the sample in the capillary. The capillary tube is attached to the apparatus shown in FIG. 1, and the temperature rise is started in a place where there is no vibration. The temperature is raised to about 10 ° C. before the expected melting point, and then the temperature is raised at a rate of 1 ° C. per minute. Read the temperature at which the sample began to rise up the capillary (one decimal place) and use it as the melting point. The bath solution uses water. The unit of the numerical values in FIG. 1 is mm. The component (A) preferably has a melting point of 20 to 90 ° C., more preferably 30 to 80 ° C., and the component (B) preferably has a melting point of 40 to 60 ° C., more preferably 45 to 55 ° C.

  In the case of a liquid composition, the pharmaceutical composition for papermaking of the present invention preferably contains 1 to 32% by weight, more preferably 3 to 12% by weight of component (A), and 0.5 to 20% by weight of component (B). %, Further 2 to 12% by weight, and preferably 0.5 to 12% by weight, and more preferably 1 to 4% by weight of component (C). The pH at 20 ° C. (pH of the aqueous phase portion) is preferably 2 to 12, more preferably 4 to 10.

  The pharmaceutical composition for papermaking of the present invention can be added directly into the pulp slurry, and can be further diluted, emulsified, suspended, etc. with water or the like as necessary. From the viewpoint of paper production efficiency, it is preferable to directly add the composition of the present invention consisting of an emulsion or suspension into the pulp slurry.

  The average particle diameter (median diameter) of the emulsified particles or dispersed particles in the emulsion or suspension is preferably from 0.1 to 50 μm, and more preferably from 0.1 to 30 μm. If the average particle size is 0.1 μm or more, the yield is good and efficient, and if it is 50 μm or less, the performance is also good.

<Paper manufacturing method>
The pharmaceutical composition for papermaking of the present invention is added in any step of the papermaking process, and may be added as it is or as a suspension dispersed in water or the like as necessary. Also good.

  The papermaking pharmaceutical composition of the present invention can be widely applied to pulp raw materials such as mechanical pulp such as thermomechanical pulp (TMP), virgin pulp such as chemical pulp such as LBKP, and used paper pulp.

  The pharmaceutical composition for papermaking of the present invention is added in any step prior to the size press step. It is added before the process of forming a paper layer by draining a thin liquid of pulp raw material as it travels over the wire mesh. It is a disintegrator and beater such as a pulper and refiner, a mixing chest, a machine chest, and a head box. May be added to tanks such as water tanks and white water tanks, or pipes connected to these facilities, but it is desirable to add them to the pulp raw material uniformly, such as by adding refiners, mixing chests, machine chests, and head boxes. . The paper-made pharmaceutical composition of the present invention is preferably made as it is after being added to the pulp raw material and remains largely in the paper (pulp sheet). There are no particular limitations on the type of paper machine used to demonstrate the effects of the pharmaceutical composition for papermaking of the present invention. For example, the long net type, the circular net type, the short net type, the twin wire type, and the inclined wire. A formula paper machine. Moreover, about a wire part, a gap former, a hybrid former, etc. are mentioned, for example.

  The method for producing paper using the paper pharmaceutical composition of the present invention can be based on a known method, but from the viewpoint of workability, the paper pharmaceutical composition of the present invention is dissolved or dissolved in water or an aqueous solvent. It is preferable to make paper by adding it to the pulp slurry in a dispersed form. In particular, it is preferable to carry out papermaking by dispersing the pharmaceutical composition for papermaking of the present invention in water having a temperature equal to or higher than its melting point and adding the suspension to the pulp slurry. From the viewpoint of improving paper quality, the addition amount of the pharmaceutical composition for papermaking of the present invention is preferably 0.05 parts by weight or more, more preferably 0.1 parts by weight or more, in terms of solid content, with respect to 100 parts by weight of pulp. 0.2 part by weight or more is more preferable. Further, from the viewpoint of maintaining the original properties of paper, it is preferably 20 parts by weight or less, more preferably 10 parts by weight or less, and still more preferably 2 parts by weight or less. Therefore, from the viewpoint of maintaining the paper quality improvement effect and the original properties of paper, 0.05 to 20 parts by weight is preferable, 0.1 to 10 parts by weight is more preferable, and 0.2 to 2 parts by weight with respect to 100 parts by weight of pulp. Part is more preferred. It is preferable to add the pharmaceutical composition for papermaking of the present invention so as to have this ratio during papermaking.

  In the production of paper in the present invention, a sizing agent, a filler, a yield improver, a drainage improver, a paper strength improver, etc., used in general paper making may be added. In particular, in order for the paper pharmaceutical composition of the present invention to exhibit its function, it is important to fix to pulp, and if necessary, an agent that promotes fixing (hereinafter referred to as a fixing accelerator) is used. Can do. Examples of such agents include aluminum sulfate, cationized starch, compounds having an acrylamide group, polyethyleneimine, and the like. The addition amount of the fixing accelerator is preferably 0.001 to 5 parts by weight and more preferably 0.01 to 2 parts by weight with respect to 100 parts by weight of the pulp. Moreover, it is preferable to use 5-20 weight part with respect to 100 weight part (solid content) of the pharmaceutical composition for paper manufacture of this invention.

  The pharmaceutical composition for papermaking of the present invention is effective in improving the papermaking speed when used in a papermaking machine having a size press facility among coating facilities. That is, in the paper manufacturing method having a size press step, it is preferable to add the papermaking chemical composition of the present invention before the size press step.

  Paper obtained by using the pharmaceutical composition for papermaking of the present invention is known as a pulp sheet, and specifically described in a paper pulp technology manual (issued by the Paper Pulp Technology Association, pages 455 to 460, 1992). Among the above-mentioned item classifications, it is preferably used for paper or paperboard such as newsprint paper, non-coating printing paper, fine coating printing paper, coating printing paper, information paper, cardboard paper, white paperboard, and packaging paper. Particularly, it is suitably used for non-coating printing paper, fine coating printing paper, and coating printing paper used for books and publishing applications.

The following evaluation was performed using the papermaking chemical composition shown in Table 1.
<Method for preparing paper pharmaceutical composition>
(1) Examples 1 to 4 and Comparative Example 4
(A) Component, (B) component, and (C) component are put into warm water so that the total solid content concentration is 10% by weight (total amount: 500 g) in the ratios in the table, and the temperature is increased by stirring until 80 ° C is reached. To do. Stirring is continued for another 60 minutes at 80 ° C., and then emulsification is performed at 8000 rpm for 1 minute in a tabletop homomixer, then cooled to room temperature, and components (A), (B) and (C) are mixed. A pharmaceutical composition for papermaking comprising the suspension contained was obtained.

(2) Comparative Examples 1 and 2
The components (A) and (C) are added in warm water so that the total solid concentration is 10% by weight in the ratio shown in the table (total amount 500 g), and the mixture is heated to 80 ° C. with stirring. Stirring is continued for another 60 minutes after reaching 80 ° C., and then emulsified with a desktop homomixer at 8000 rpm for 1 minute, and then cooled to room temperature to contain the components (A) and (C). A suspension was obtained. In the evaluation described later, in Comparative Example 1, the suspension and the component (B) are separately added to the pulp slurry, and in Comparative Example 2, the component (B) and the suspension are added to the pulp slurry in this order. Added separately.

(3) Comparative Example 3
The components (A) and (C) are added in warm water so that the total solid concentration is 10% by weight in the ratio shown in the table (total amount 500 g), and the mixture is heated to 80 ° C. with stirring. Stirring is continued for another 60 minutes after reaching 80 ° C., and then emulsified with a desktop homomixer at 8000 rpm for 1 minute, and then cooled to room temperature to contain the components (A) and (C). A suspension was obtained. (B) component is mixed with this suspension at the ratio shown in the table at room temperature, and a papermaking agent comprising a suspension containing (A) component, (B) component and (C) component A composition was obtained.

(4) Comparative Example 5
Only the component (B) was used as a papermaking chemical composition.

(5) Comparative Example 6
The components (A) and (C) are added in warm water so that the total solid concentration is 10% by weight in the ratio shown in the table (total amount 500 g), and the mixture is heated to 80 ° C. with stirring. Stirring is continued for another 60 minutes after reaching 80 ° C., and then emulsified with a desktop homomixer at 8000 rpm for 1 minute, and then cooled to room temperature to contain the components (A) and (C). A pharmaceutical composition for papermaking comprising a suspension was obtained.

(6) Comparative Example 7
The pulp sheet by the below-mentioned evaluation was manufactured without adding the chemical composition for papermaking.

<Evaluation>
(1) Tightness and sizing degree (1-1) Papermaking method LBKP was disaggregated and beaten with a beater at room temperature to obtain an LBKP slurry having a pulp concentration of 2.2% by weight. Canadian Standard Freeness was 430ml. The LBKP slurry was weighed so that the basis weight of the sheet after papermaking was 100 g / m ² when it was absolutely dry, and then cationized starch (CATO308, manufactured by NSC Japan) 1.0% (weight basis, vs. pulp, below) The same), industrial sulfuric acid band 0.5%, light calcium carbonate 20%, and the amount of paper-made pharmaceutical composition shown in Table 1 were added with stirring.

After diluting with water so that the pulp concentration becomes 0.5% by weight, and adding 0.03% of a cationic polyacrylamide yield improver (Percoll 47, manufactured by Ciba Specialty Chemicals) with stirring Paper was made with a 150-mesh wire with a round tappi paper machine and coached to obtain wet paper. The wet paper after paper making was pressed with a press at 3.5 kg / cm ² for 2 minutes and dried at 105 ° C. for 2 minutes using a drum dryer to obtain a pulp sheet. The obtained pulp sheet was conditioned at 23 ° C. and a humidity of 50% RH for 1 day, and then the tightness and sizing degree were measured by the following methods. The results are shown in Table 1.

(1-2) Tenacity The basis weight (g / m ² ) and thickness (mm) of the resulting conditioned pulp sheet were measured, and the tenacity (g / cm ³ ) was determined by the following formula.
Calculation formula: (tensity) = (basis weight) / (thickness) × 0.001
The smaller the absolute value, the higher the bulk, and the 0.02 difference in the strength is fully recognized as a significant difference.

(1-3) Sizing degree The degree of sizing of the conditioned pulp sheet obtained by the papermaking method was measured according to JIS-8122.

(2) Dynamic water absorption The same operation as the paper making method was performed up to the press. After pressing, the wet paper is cut into a size of 5 cm × 5 cm and dried at 105 ° C. using a halogen moisture meter manufactured by METTLER TOLEDO Co., Ltd., and the moisture in the paper is estimated to be more than 0 to about 5%. The drying operation is stopped when the weight is reached, and 3 microliters of 60 ° C. warm water is quickly dropped from above using a syringe with the moisture meter set, and the time until the paper completely penetrates into the paper. Was measured. Then, the drying operation was restarted, and the weight was further dried until there was no weight loss, and the weight of moisture in the paper was 0% (absolute dry weight). The moisture in the paper at the time when the penetration time was measured was calculated from the weight when the penetration time was measured and the dry weight. The water content in the paper is the weight of water with respect to the absolute dry weight in%. Measure 5 samples with different moisture in the paper, take the moisture in the paper on the X-axis and the penetration time on the Y-axis, draw a moisture-penetration time curve in the paper, and determine the penetration time at 1% moisture in the paper, Dynamic water absorption was evaluated. The results are shown in Table 1. In this evaluation method, the longer the permeation time, the lower the paper water absorption in the coating process for the paper immediately after the dryer (that is, the dynamic water absorption is suppressed), and the paper making speed is improved.

“Batch” of the addition method means that the components (A) to (C) are added to the pulp slurry as a suspension containing the weight ratios shown in Table 1, and “AKD attachment” It means that (A) component and (C) component were added to the pulp slurry separately. The components in the table are as follows.
A-1: pentaerythritol stearate (ester average substitution degree 45 equivalent%, water separation degree 5.2%, melting point 52 ° C., 1% by weight aqueous solution is separated)
A-2: stearic acid monoglyceride (water separation degree 5.7%, melting point 66 ° C., 1% by weight aqueous solution is separated)
A-3: ethylene glycol monobehenate (water separation degree 5.5%, melting point 64 ° C., 1% by weight aqueous solution is separated)
AKD: Alkyl ketene dimer (melting point 50 ° C., “Syrene S-94” manufactured by Kao Corporation)
ASA: alkenyl succinic anhydride (melting point 20 ° C. or lower, “AS-1532” manufactured by Seiko PMC)

Schematic showing an apparatus for measuring the melting point of (A) component nonionic surfactant and (B) component alkyl ketene dimer

Explanation of symbols

A: Measuring tube B: Cork stopper C: Vent hole D: Thermometer E: Auxiliary thermometer F: Bath solution G: Capillary tube H: Side tube

Claims (7)

Nonionic surfactant (A) [hereinafter referred to as “component (A)”], alkyl ketene dimer (B) [hereinafter referred to as “component (B)”), a cationic represented by the following general formula (C-1) A method for producing a pharmaceutical composition for papermaking containing surfactant (C) [hereinafter referred to as component (C)] and water,
(A) component is 1 or more compounds chosen from fatty acid ester and its C2-C4 alkylene oxide adduct,
(A) and (B) the step of emulsifying in water in the presence of the component (C) component [hereinafter referred to as emulsification step] have a,
The papermaking pharmaceutical composition contains 3 to 12% by weight of component (A), 2 to 12% by weight of component (B), and 1 to 4% by weight of component (C).
A method for producing a pharmaceutical composition for papermaking.

[Wherein R _{1c to} R _4c are each an alkyl group having 1 to 24 carbon atoms, an alkenyl group having 2 to 24 carbon atoms, a β-hydroxyalkyl group having 1 to 24 carbon atoms, a benzyl group, or a formula: (A ₁ O) n ₁ -Z ₁ (wherein A ₁ O is an oxyalkylene group having 2 to 4 carbon atoms, Z ₁ is a hydrogen atom or an acyl group, and n ₁ is an average addition mole of A ₁ O. X ₁ ⁻ is a counter ion. ]   The manufacturing method of the pharmaceutical composition for paper manufacture of Claim 1 which performs an emulsification process at the temperature which (A) component and (B) component fuse | melt. The manufacturing method of the pharmaceutical composition for paper manufacture of Claim 1 or 2 whose (A) component is a 1 or more compound chosen from the polyhydric alcohol and fatty acid ester which do not contain an alkylene oxide group . Nonionic surfactant (A) [hereinafter referred to as component (A)] and alkylketene dimer (B) [hereinafter referred to as component (B)] are represented by the following general formula (C-1) A paper-made pharmaceutical composition comprising an emulsion obtained by emulsifying in water in the presence of the surfactant (C) [hereinafter referred to as component (C)] ,
(A) component is 1 or more compounds chosen from fatty acid ester and its C2-C4 alkylene oxide adduct,
The papermaking pharmaceutical composition contains 3 to 12% by weight of component (A), 2 to 12% by weight of component (B), and 1 to 4% by weight of component (C).
Pharmaceutical composition for papermaking.

[Wherein R _{1c to} R _4c are each an alkyl group having 1 to 24 carbon atoms, an alkenyl group having 2 to 24 carbon atoms, a β-hydroxyalkyl group having 1 to 24 carbon atoms, a benzyl group, or a formula: (A ₁ O) n ₁ -Z ₁ (wherein A ₁ O is an oxyalkylene group having 2 to 4 carbon atoms, Z ₁ is a hydrogen atom or an acyl group, and n ₁ is an average addition mole of A ₁ O. X ₁ ⁻ is a counter ion. ]   The papermaking pharmaceutical composition according to claim 4, comprising a suspension obtained from the emulsion. The papermaking pharmaceutical composition according to claim 4 or 5, wherein the component (A) is one or more compounds selected from a polyhydric alcohol not containing an alkylene oxide group and an ester of a fatty acid .   It is a manufacturing method of the paper which has a size press process, Comprising: The manufacturing method of the paper which adds the chemical | medical agent composition for paper manufacture in any one of Claims 4-6 in the process before a size press process.

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