JP4795077B2 - Pharmaceutical composition for papermaking - Google Patents

Description

  The present invention relates to a specific papermaking pharmaceutical composition used in a papermaking process, a paper production method using the composition, and paper obtained by the production method.

  In the papermaking process, it is known to use various compounds corresponding to nonionic surfactants in order to improve bulkiness (for example, Patent Document 1).

  In addition, it has been reported that a quaternary cationic surfactant is used in a papermaking process in order to soften paper (Patent Document 2).

  Furthermore, in order to obtain a bulky sheet without impairing paper strength, it has been proposed to use a cationic compound, an amine, an amine acid salt, and an amphoteric surfactant as a paper bulking agent (Patent Document 3). .

JP 2001-81687 A JP 2001-271292 A JP-A-11-269799

  An object of the present invention is to make paper making that can suppress excessive foaming in the paper making process, particularly the paper making process, has good fixability of the active ingredient on the paper, and promotes the improvement of the paper characteristics, particularly the paper bulk. It is providing the pharmaceutical composition for use, the manufacturing method of the paper which uses this composition, and the paper obtained by this manufacturing method.

The present invention relates to a nonionic surfactant (A), a cationic surfactant (B ₁ ) represented by the following general formula (1), and a cationic surfactant represented by the following general formula (2). It becomes blended agent (B _2), the ratio of (B ₁₎ and (B ₂₎ the total of the amount of (B ₁₎ is in the range of 50 to 95 wt%, about papermaking pharmaceutical composition.

(In the formula, R _1b is an alkyl group having 16 carbon atoms, an alkenyl group having 16 carbon atoms, or a β-hydroxyalkyl group having 16 carbon atoms, and R _2b is an alkyl group having 1 to 8 carbon atoms, or 1 to 8 carbon atoms. R _3b and R _4b are each an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 1 to 8 carbon atoms, and a β-hydroxy having 1 to 8 carbon atoms. Hydroxyalkyl group, benzyl group, or formula: — (A ₁ O) _n1 —Z ₁ (where A ₁ O is an oxyalkylene group having 2 to 4 carbon atoms, and Z ₁ is a hydrogen atom or 1 to 24 carbon atoms. And n ₁ is an average added mole number and a number of 1 to 50), and X ₁ ⁻ is a counter ion.)

Wherein R _5b is an alkyl group having 18 carbon atoms, an alkenyl group having 18 carbon atoms, or a β-hydroxyalkyl group having 18 carbon atoms, R _6b is an alkyl group having 1 to 8 carbon atoms, or 1 to 8 carbon atoms. R _7b and R _8b are each an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 1 to 8 carbon atoms, and a β-hydroxy having 1 to 8 carbon atoms. Hydroxyalkyl group, benzyl group, or formula: — (A ₂ O) _n2 —Z ₂ (where A ₂ O is an oxyalkylene group having 2 to 4 carbon atoms, and Z ₂ is a hydrogen atom or 1 to 24 carbon atoms. And n ₂ is an average addition mole number and a number of 1 to 50), and X ₂ ⁻ is a counter ion.)

The present invention also includes a nonionic surfactant (A), an amine compound (C ₁ ) represented by the following general formula (3), an amine compound (C ₂ ) represented by the following general formula (4), And a quaternizing agent (D) for the amine compound, wherein (C ₁ ) and (C ₂ ) are quaternized by (D), in the design range ratio is 50 to 95 wt% of the total in the amount of (X) in which C ₁₎ and (quaternized compound according to D) (X) (C ₂₎ of (quaternized compound according to D) (Y) The present invention relates to a certain pharmaceutical composition for papermaking.

(Wherein R _1c is an alkyl group having 16 carbon atoms, an alkenyl group having 16 carbon atoms, or a β-hydroxyalkyl group having 16 carbon atoms, R _2c and R _3c are alkyl groups having 1 to 8 carbon atoms, An alkenyl group having 1 to 8 carbon atoms, a β-hydroxyalkyl group having 1 to 8 carbon atoms, a benzyl group, or a formula: — (A ₃ O) _n3 —Z ₃ (where A ₃ O is an oxyalkylene having 2 to 4 carbon atoms) Z ₃ is a hydrogen atom or an acyl group having 1 to 24 carbon atoms, and n ₃ is an average addition mole number and a number of 1 to 50).

Wherein R _4c is an alkyl group having 18 carbon atoms, an alkenyl group having 18 carbon atoms, or a β-hydroxyalkyl group having 18 carbon atoms, R _5c and R _6c are alkyl groups having 1 to 8 carbon atoms, An alkenyl group having 1 to 8 carbon atoms, a β-hydroxyalkyl group having 1 to 8 carbon atoms, a benzyl group, or a formula: — (A ₄ O) _n4 —Z ₄ (where A ₄ O is an oxyalkylene having 2 to 4 carbon atoms) Z ₄ is a hydrogen atom or an acyl group having 1 to 24 carbon atoms, and n ₄ is an average addition mole number and a number of 1 to 50).

The present invention also provides a nonionic surfactant (A), a cationic surfactant (B ₁ ) represented by the general formula (1), and a cationic compound represented by the general formula (2). surfactants containing (B _2), the ratio of (B ₁₎ and (B ₂₎ the total of the amount of (B ₁₎ is in the range of 50 to 95 wt%, about papermaking pharmaceutical composition.

  The present invention also relates to a paper manufacturing method in which the papermaking pharmaceutical composition of the present invention is added to a pulp slurry, and paper obtained by the paper manufacturing method of the present invention.

  According to the present invention, it is possible to suppress excessive foaming in the papermaking process, particularly in the papermaking process, and the fixing property of the active ingredient to the paper is good, and the papermaking promotes the improvement of the paper characteristics, particularly the paper bulk. The pharmaceutical composition for use, the manufacturing method of paper using the same, and the paper manufactured by the manufacturing method are provided.

  Among the nonionic surfactants used in the papermaking process, particularly in the papermaking process, the present inventors have versatility and excellent bulkiness. The nonionic surfactant of the component (A) of the present invention. On the other hand, the combination of specific cationic surfactants suppresses excessive foaming of the nonionic surfactant, and further expands versatility in the papermaking process of the nonionic surfactant, particularly paper. The present inventors have found that the fixing property to the toner is improved and have completed the present invention.

[(A) component]
The nonionic surfactant 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 is preferably one or more nonionic surfactants selected from the following (A _i ) to (A _iii ) from the viewpoint of bulkiness, and particularly among them. A water separation degree of 4% or more is preferable.

(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]
( _Aii ) Compounds represented by the following general formulas (A-1) to (A-8), and fatty acid amides, fatty acid amide amines derived therefrom, and addition of these alkylene oxides having 2 to 4 carbon atoms One or more compounds selected from products [hereinafter referred to as component (A _ii )]

[Where,
Y ₁ and Y ₂ are the same or different from each other, and are a hydrogen atom, R ₄ , R ₆ CO—, — (AO) _n —COR ₃ or — (AO) _n —H.
AO: alkyleneoxy group Y ₃ C2-4: hydrogen atom or -COR ₆

R ₁ : alkyl group having 8 to 35 carbon atoms, alkenyl group or β-hydroxyalkyl group R ₂ , R ₃ , R ₆ , R ₉ : alkyl group having 7 to 35 carbon atoms, alkenyl group or β-hydroxyalkyl group R ₄ , R ₅ : hydrogen atom or alkyl group having 1 to 3 carbon atoms R ₇ , R ₈ : alkyl group having 1 to 3 carbon atoms R ₁₀ : hydrogen atom or R ₉
n: number of 1 to 20 and average number of moles X ⁻ : anion R ₁₁ : alkyl group, alkenyl group or β-hydroxyalkyl group having 6 to 24 carbon atoms, or — (CH ₂ CH ₂ NH) _{n ′} H ( N 'is 2 or 3)
R _{12 is} an alkyl group, alkenyl group, β-hydroxyalkyl group having 6 to 24 carbon atoms, or a hydrogen atom. ]

One or more compounds selected from (A _iii ) fatty acid esters and C 2-4 alkylene oxide adducts thereof (excluding (A _ii ) component) [hereinafter referred to as (A _iii ) 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 alkylene oxide 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 alkylene oxide 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 particularly 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 particularly 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 include glycerin (average degree of condensation 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.

  The alkylene oxide (AO) is ethylene oxide (EO) and / or propylene oxide (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 ) includes the compounds represented by the above general formulas (A-1) to (A-8), and fatty acid amides, fatty acid amide amines derived therefrom, and alkylenes having 2 to 4 carbon atoms thereof. One or more compounds selected from oxide adducts. In the alkylene oxide adduct having 2 to 4 carbon atoms, the average addition mole number of alkylene oxide is preferably more than 0 to 50.

The component (A _iii ) is one or more compounds selected from fatty acid esters and C 2-4 alkylene oxide adducts thereof, but the component (A _ii ) is excluded from the component (A). Among these, esters of fatty acids and alcohols are preferable, and esters of fatty acids and polyhydric alcohols are particularly preferable.

Fatty acids used in the esters of fatty acids and alcohols include fatty acids having 1 to 24 carbon atoms, preferably 10 to 22 carbon atoms, and may be saturated, unsaturated, linear or branched, and particularly linear fatty acids. preferable. More preferred are lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid and oleic acid, with stearic acid being particularly preferred. Specific examples of the alcohol used for the ester include the monovalent or polyhydric alcohols described in the component (A _i ) and their alkylene oxide adducts.

As esters of fatty acids and monohydric alcohols, compounds represented by the following general formula (B) can also be preferably used.
R _b1 COO (EO) _p (PO) _q R _b2 (B)
[Wherein, R _b1 represents an alkyl group, alkenyl group or β-hydroxyalkyl group having 8 to 35 carbon atoms, and R _b2 represents an alkyl group, alkenyl group or β-hydroxyalkyl group having 1 to 8 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 alkylene oxide addition reaction. For example, if necessary, an esterification catalyst is added to a mixture of fatty acid and polyhydric alcohol and reacted at 150 to 250 ° C. to obtain an ester. Further, an alkylene having 2 to 4 carbon atoms in the presence of an alkali catalyst or the like. By adding an oxide, an alkylene oxide addition ester is obtained. Moreover, you may esterify after adding an alkylene oxide to a fatty acid or a polyhydric alcohol. Furthermore, it may be obtained by adding only an alkylene oxide to a 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 an alkylene oxide addition ester, the average addition mole number of alkylene oxide (AO) is more than 0 to 10 moles per alcoholic hydroxyl group, preferably more than 0 to 5 moles. In addition, when polyhydric alcohols that can be AO groups such as ethylene glycol are used, these are also included in the number of AO groups. The alkylene oxide is preferably ethylene oxide (EO) or propylene oxide (PO). These may be either EO, PO alone or a mixture of EO and PO. In the present invention, it is particularly preferable to use a polyhydric alcohol not containing an AO group and an ester of a fatty acid.

  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. It means that the transmittance (T%) in an optical path of 10% in visible light of 660 nm of a% aqueous solution is 5% or less when water is 100%.

[(B ₁ ), (B ₂ ) component]
The papermaking pharmaceutical composition of the present invention is represented by the compound (B ₁ ) [(B ₁ ) component] selected from the cationic surfactants represented by the above general formula (1) and the above general formula (2). the compound selected from cationic surfactants (B ₂₎ containing [(B ₂₎ component]. The ratio of (B ₁ ) in the total amount of the component (B ₁ ) and the component (B ₂ ) is in the range of 50 to 95% by weight, and the carbon number of R _{1b in} (B ₁ ) (16 carbon atoms). The relation that the carbon number of R _5b (carbon number 18) in (B2) is larger is satisfied.

When (B ₁ ) component R _1b has 16 carbon atoms and (B ₂ ) component R _5b has 18 carbon atoms, the nonionic surfactant has a strong hydrophobic tendency as in the present invention. In addition, excessive foaming in the papermaking process, particularly in the papermaking process, can be suppressed, and both emulsification stability and improvement in fixability of the nonionic surfactant to the pulp can be achieved. Can be improved.

From the viewpoint of improving the properties of the paper such as suppression of foaming and bulkiness, in the general formula (1), R _2b preferably has 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms, still more preferably 1 carbon atoms. -6, more preferably 1-3 alkyl groups are preferred. R _3b and R _4b preferably have 1 to 6 carbon atoms, more preferably 1 to 3 groups, and particularly preferably 1 to 6 carbon atoms, more preferably 1 to 3 alkyl groups. It is.

Further, from the viewpoint of improving the properties of the paper such as suppression of foaming and bulkiness, in the general formula (2), R _6b preferably has 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms, particularly carbon. The number is preferably an alkyl group of 1 to 6, more preferably 1 to 3. R _7b and R _8b are preferably groups having 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms. An alkyl group having 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms is particularly preferable.

[Paper pharmaceutical composition]
Papermaking pharmaceutical compositions of the present invention is formed by blending a component (A), (B ₁₎ component and (B ₂₎ component. The pharmaceutical composition for papermaking of the present invention comprises (A) component, (B ₁ ) component, and (B ₂ ) component at a temperature equal to or higher than the melting point of (A), preferably 50 of the reaction system (reaction solution). After stirring and mixing at ˜100 ° C., a solid composition can be obtained by cooling to a temperature not higher than the melting point of the component (A). When the component (B ₁ ) and the component (B ₂ ) are in a state containing a solvent such as water or alcohol used in the production, after mixing with the component (A), when it does not become solid even after cooling After mixing with the component (A), a solid composition can be obtained through a step of removing the solvent (for example, distillation under reduced pressure, etc.). In addition, (A) component, (B ₁ ) component, (B ₂ ) component are added separately or a mixture of (A) component and (B) component is added to water or warm water, and the melting point of (A) component A liquid (emulsion or suspension) composition can be obtained by stirring and mixing so that the whole is uniform at the above temperature. The component (B ₁ ) and the component (B ₂ ) may be blended separately with the component (A), or those previously mixed at a predetermined ratio may be blended with the component (A).

The present invention also relates to a papermaking pharmaceutical composition comprising the component (A), the component (C ₁ ), the component (C ₂ ), and the component (D) that is a quaternizing agent for the amine compound. The (C ₁ ) component and the (C ₂ ) component are quaternized with the (D) component, and the quaternized products (X) and (C ₂ ) of (C ₁ ) by (D) ( It relates to a pharmaceutical composition for papermaking, wherein the design ratio of (X) in the total amount of quaternized product (Y) according to D) is in the range of 50 to 95% by weight. The quaternized product (X) obtained here corresponds to the component (B ₁ ), and the quaternized product (Y) corresponds to the component (B ₂ ). Hereinafter, the (C ₁ ) component and the (C ₂ ) component are collectively referred to as the (C) component.

Here, the design ratio is a design ratio before the reaction, and by previously setting the ratio (design ratio) of (X) in the total of (X) and (Y), (C ₁ ) component, The charge ratio of the component (C ₂ ) and the component (D) can be calculated.

In this composition, the component (A), the component (C ₁ ) and the component (C ₂ ) are mixed at a temperature equal to or higher than the melting point of the component (A), preferably 50 to 100 ° C. as the temperature of the reaction system (reaction solution). and, wherein this by mixing component (D) (C ₁₎ can be obtained by component and (C ₂₎ manufacturing method comprising the steps of quaternizing the component. Specifically, the component (A), the component (C ₁ ), and the component (C ₂ ) are mixed at a temperature equal to or higher than the melting point of (A) (preferably stirred and mixed), and then the component (D) is mixed ( (It is preferable to drop and mix), and then the solid composition can be obtained by cooling to a temperature not higher than the melting point of the component (A). In addition, after the component (D) is added dropwise and mixed, it is added to water or warm water, and stirred and mixed so that the whole becomes uniform at a temperature equal to or higher than the melting point of the component (A). A suspension) composition can be obtained.

In general formula (3), R _2c and R _3c preferably have 1 to 6 carbon atoms, more preferably 1 to 3 groups, and particularly preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms. It is an alkyl group.

In the general formula (4), R _5c and R _6c are preferably groups having 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms. An alkyl group having 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms is particularly preferable.

Examples of the component (D) include methyl halide (chloride, bromide, etc.), ethyl halide (chloride, bromide, etc.), dialkyl (methyl, ethyl etc.) sulfuric acid, and dialkyl (methyl, ethyl etc.) carbonic acid, preferably Dimethyl sulfate, diethyl sulfate. The component (D) has a molar ratio [(C ₁ ) + (C ₂ )] / (D) of 1 to 1.2 with the total amount of (C ₁ ) and (C ₂ ) and (D). It is preferable to be used.

A suitable papermaking pharmaceutical composition of the present invention comprises (A) component, a mixture containing 80% by weight or more of (B ₁ ) component, and a mixture containing 80% by weight or more of (B ₂ ). It will be. Similarly, the mixture containing (A) component and (C ₁ ) component is preferably 80% by weight or more, more preferably 90% by weight or more, still more preferably 95% by weight or more, and still more preferably 97% by weight or more, and (C ₂₎ a mixture comprising a component 80 wt% or more, the (a) were mixed at a temperature above the melting point of component, the thereto by mixing component (D) (C ₁₎ component and the (C ₂₎ component It was obtained by quaternization. That is, it is preferable to use a mixture having a purity of 80% by weight or more as a blending raw material for the component (B ₁ ), the component (B ₂ ), the component (C ₁ ), and the component (C ₂ ).

The paper pharmaceutical composition of the present invention comprises (A) component, (B ₁ ) component (hereinafter also including (C ₁ ) component quaternized with (D) component), (B ₂ ) component [hereinafter, (D) (including (C ₂ ) component quaternized by component)] is essential, and other components are contained as necessary. Hereinafter, the component (B ₁ ) and the component (B ₂ ) are collectively referred to as the component (B).

  By suppressing excessive foaming due to the component (A) used in the papermaking process and improving the fixability of the surfactant to the paper, the properties of the paper due to the component (A), particularly the high bulkiness of the paper In the composition of the present invention, the weight ratio (A) / (B) of the component (A) and the component (B) is preferably 99/1 to 40/60, more preferably 99 / 1 to 45/55, more preferably 98/2 to 45/55. (C) The design ratio between the component (A) and (X) and (Y) is 99/1 to 40/60 in terms of (A) / [(X) + (Y)] weight ratio. It is preferable to use components.

  Furthermore, from the viewpoint of appropriately ensuring the versatility of the component (A), particularly the bulkiness, the reaction rate of the component (C) is preferably 50% or more, more preferably 80% or more, and more preferably 90% or more. 95% or more is particularly preferable. (C) The measuring method of the reaction rate of a component is based on the method of the below-mentioned Example.

  The content of the component (A) is preferably 1 to 99% by weight, more preferably in the blended raw material of the composition of the present invention, from the viewpoint of appropriately ensuring the versatility of the component (A), particularly the bulkiness. 2 to 99% by weight, more preferably 2 to 98% by weight. When the composition is an emulsion or suspension, it is preferably 1 to 70% by weight, more preferably 2 to 70% by weight, still more preferably. 5 to 70% by weight. When the composition is an emulsion or suspension and is used after being diluted, the content of the component (A) in the blended raw material is preferably 10 to 70% by weight, more preferably 10 to 60% by weight. .

  In the composition of the present invention, from the viewpoint of product handling and product shape stability, an optional component may be contained as necessary. Preferably, the viscosity adjusting component, the melting point adjusting component, the component (A), (B) It contains emulsifying / dispersing agents other than the component. For example, it is preferable to contain a ketone such as distearyl ketone from the viewpoint of increasing the melting point and preventing caking.

  The form of the composition of the present invention may be solid or liquid. In the case of a solid form, considering that it is made into a liquid form, such as an emulsified liquid or a suspension, and added to the papermaking process, flakes, pellets, powders, needles and the like are preferable, and flakes and pellets are more preferable.

  In the case of liquid, it is preferably a melt, emulsion, suspension or the like from the viewpoint of handleability, and is an emulsion or suspension from the viewpoint of improving the dispersion efficiency of the composition in the papermaking process. It is more preferable.

[Paper manufacturing method]
From the viewpoint of improving the properties of the paper obtained, the composition of the present invention is preferably added to the pulp slurry in the pulp preparation process and papermaking process where it can be uniformly blended with the pulp raw material. It is preferable to add.

  More specifically, the composition of the present invention includes a mixing chest, a seed box, and a machine chest before the paper making process in which a diluted liquid of the pulp raw material is filtered from the pulp preparation process while traveling on the wire mesh to form a paper layer. It may be added to tanks such as head boxes and white water tanks, or pipes connected to these facilities (fan pumps, etc.), but is preferably added by mixing chests, seed boxes, machine chests, and fan pumps. .

  When the composition of the present invention is added to the pulp slurry, when the composition is in a solid form, it is diluted with water or the like before addition, emulsified, made into a liquid form such as a suspension, preferably emulsified, made into a suspension, etc. In the case where the composition is an emulsion or suspension, it can be added directly to the pulp slurry. From the viewpoint of paper production efficiency, it is preferable to add the emulsion or suspension of the composition of the present invention directly to the pulp slurry.

  In the paper manufacturing method of the present invention, it is widely used for mechanical pulp such as thermomechanical pulp (TMP), virgin pulp such as chemical pulp such as hardwood bleached pulp (LBKP), pulp raw material such as waste paper pulp and DIP, and mixed raw materials thereof. Applicable.

  In the paper manufacturing method of the present invention, as necessary, the sizing agent, filler, yield improver, freeness improver, paper strength improver, aluminum sulfate, compound having an acrylamide group, component (A) such as polyethyleneimine , (B) component fixing accelerators (pulp fixing accelerators) and the like may be used in combination, but these components may be added separately from the composition of the present invention in the pulp sheet production process. desirable.

  In the paper manufacturing method of the present invention, the amount of the composition of the present invention is such that 100 g of pulp slurry is dried at 105 ° C. for 3 hours with respect to 100 parts by weight of the solid content in the pulp slurry to be added. In addition, the total amount of components (B) (in terms of effective component) is preferably 0.01 to 10 parts by weight, more preferably 0.05 to 10 parts by weight, and still more preferably 0.05 to 7 parts by weight. In particular, from the viewpoint of bulkiness, 0.01 to 10 parts by weight is preferable and 0.05 to 7 parts by weight is more preferable as the total amount of (A) and (B) with respect to 100 parts by weight of the pulp raw material. 0.05 to 5 parts by weight is more preferable.

  The pulp sheet obtained by applying the production method of the present invention is a newspaper web, printing / information in the item classification described in the Paper Pulp Technology Handbook (published by the Paper Pulp Technology Association, pages 455-460, 1992). It is preferably used for paper such as paper, wrapping paper, sanitary paper or paperboard, and particularly preferably used for newspaper winding paper and printing / information paper.

Example 1
The papermaking drug compositions shown in Table 1 were prepared and evaluated as follows. The results are shown in Table 2.

[Preparation of composition]
While the component (A) in Table 1 was being stirred at 80 ° C. in a molten state, the components (B) and (E) were added and mixed for 1 hour, and then left at room temperature up to 25 ° C.

[Emulsification stability]
(1) Low temperature fluidity The composition of Table 1 is stirred and emulsified at 80 ° C. for 1 hour at a solid concentration of 10% by weight to prepare an emulsion. From the preparation, the fluidity at low temperature of the emulsion after storage for a predetermined period shown in Table 2 was evaluated. Low temperature (10 ° C.) fluidity is determined by measuring the viscosity of an emulsion that has been stored in a constant temperature bath at 10 ° C. with a B-type viscometer (12 rpm / 10 ° C.), and the value is 10000 mPa · s or less. Those exceeding 10,000 mPa · s or those for which accurate viscosity cannot be measured due to separation or the like were evaluated as x.
(2) Presence or absence of agglomerates In addition, after storing the emulsion prepared above at 10 ° C. for 30 days, 100 g of the emulsion was filtered with a 100 μm mesh, washed with running water from a tap water for 5 minutes, and the composition on the mesh. Evaluation was made as “◯” when no mark remained, and “X” when the composition remained on the mesh.

[Paper evaluation]
(1) Production conditions of paper 1% by weight of LBKP pulp slurry was weighed so that the basis weight of the sheet after paper making would be 80 g / m ^2, and under stirring, 0.5% by weight of aluminum sulfate (vs. pulp) Cato302 (manufactured by Nippon SC) 0.3% by weight as cationized starch, Cyleen-94 (manufactured by Kao Corporation) 0.2% by weight as alkyl ketene dimer sizing agent, Whiten PC as light calcium carbonate After sequentially adding 15% by weight (manufactured by Shiroishi Kogyo Co., Ltd.), it was diluted to a pulp concentration of 0.5% by weight.

  Further, under stirring, at room temperature (20 to 25 ° C.), the composition of the present invention and the comparative product are added so as to be 0.5% by weight (effective component conversion) with respect to the pulp, and Percoll is used as a yield agent. 47 (made by Ciba Specialty Chemicals) 0.015 wt% was added.

This was made with a round tappy paper machine with a 150 mesh wire to obtain a wet paper, and then two wet papers on each side of Advantech. The sample was sandwiched between 26 round filter papers, pressed at 3.5 kg / cm ² for 5 minutes, and dried at 105 ° C. for 2 minutes using a mirror dryer. The dried sheet was conditioned for 1 day at 23 ° C. and 50% RH.

(2) In-paper fixing rate of component (A) The component (A) is extracted from the humidity-adjusted sheet using a solvent in which the component (A) is dissolved, and quantified by GC (gas chromatography).

(3) Bulk improvement rate Under the above-mentioned paper production conditions, the basis weight (g / m ² ) and thickness (μm) of the sheet obtained in the same manner except that the amount of the composition added was 0.5% by weight of the pulp. And the degree of tension (d) (g / cm ³ ) is determined by the following formula: [(basis weight) / (thickness)]. Further, the tightness (d ₀ ) of a sheet produced in the same manner without adding the composition is obtained. From these tensities d and d ₀ , the bulk improvement rate is calculated from the following formula.
Bulk improvement rate (%) = [(d ₀ −d) / d ₀ ] × 100
d ₀ : Tensile strength of the composition-free sheet d: Tenacity of the sheet obtained by adding the composition

(4) White water bubbling White water bubbling is the amount of foam after 100 g of papermaking filtrate (white water) generated in the above paper production is put into a stoppered graduated cylinder (capacity 250 mL) and stirred vigorously for 30 seconds. It was evaluated in five stages.
Less than 10 mL of foam: 1
Foam volume is 10 mL or more and less than 20 mL: 2
The amount of foam is 20 mL or more and less than 30 mL: 3
The amount of foam is 30 mL or more and less than 40 mL: 4
Bubble volume is 40 mL or more: 5

  In the table, the structure of the component (B) is based on the compound of the following general formula (α).

Further, in the table, in the structure of the component (B), C16 or the like means an alkyl group having the number of carbons next to C. The ratio of the mixed alkyl group is a weight ratio. EtSO ₄ ⁻ is ethyl sulfate ion (C ₂ H ₅ SO ₄ ⁻ ).

  In Table 1, “Separation” in “Appearance of 1% by weight aqueous solution” of component (A) means a state where there are precipitates and suspended matters (the same applies hereinafter).

Example 2
While the component (A) in Table 3 is being stirred in a molten state at 70 ° C., the components (C) [(C-1) and (C-2)] are added and mixed for 1 hour, and then (D ) The components were mixed dropwise over 2 hours and aged for 2 hours. Thereafter, the component (E) was added and mixed at 80 ° C. for 1 hour, and then allowed to stand at room temperature up to 25 ° C. to obtain a papermaking pharmaceutical composition. The same evaluation as in Example 1 was performed using them. The results are shown in Table 4.

  In the table, the structure of the component (C) is based on the compound of the following general formula (β).

  Further, in the table, in the structure of the component (C), C16 or the like means an alkyl group having the number of carbon atoms next to C. The ratio of the mixed alkyl group is a weight ratio.

  In the table, (C-1), (C-2) and (D) charge ratio (% by weight) is determined by setting the design ratio (% by weight) of (X) and (Y) to the value in the table. , (C-1), (C-2) and (D) were determined from the molecular weight and (C) / (D) ratio (molar ratio). The molar ratio (C) / (D) is a ratio of [[number of moles of (C-1)] + [number of moles of (C-2)] / [number of moles of (D)].

Moreover, the reaction rate of (C) was computed by the following (Formula 1).
A = (1- (B + CE (1-F / 100)) / D (1-F / 100)) × 100 Formula 1
A: Reaction rate of (C) (%)
B: Total amine value of composition (mg KOH / g) (analytical value)
C: Acid value (mgKOH / g) of composition (analytical value)
D: Total amine value (mgKOH / g) of composition before blending component (D) (analytical value)
E: Acid value (mgKOH / g) of composition before blending component (D) (analytical value)
F: Charge ratio of component (D) (% by weight)

Here, the acid value and the total amine value are measured by the following methods.
[I] Acid value (I-1) Reagent (I-1-1) mixed solvent Toluene (primary) -ethanol (primary) mixed solution (2 + 1, volume ratio)
A 1% phenolphthalein indicator solution is added to the above mixed solvent and neutralized to a slight red color just before use.

(I-2) Operation (I-2-1) A 10 g sample is weighed into a 200 ml Erlenmeyer flask.
(I-2-2) Add about 30 mL of mixed solvent and dissolve (Note 1).
(I-2-3) Titrate with 0.1 mol / L alcoholic potassium hydroxide standard solution.
The end point is a point where a slight red color lasts for 30 seconds. (Note 1)
(Note 1) If the end point is unclear, obtain by potentiometric titration.

(I-3) Calculation The acid value is determined by the following formula. When the acid value is less than 10, round up to 2 significant figures, and when it is 10 or more, round to 3 significant figures.

A: Amount of alcoholic potassium hydroxide standard solution required for titration (mL)
f: Factor K of alcoholic potassium hydroxide standard solution: 5.611 (0.1 mol / L alcoholic potassium hydroxide standard solution)
28.05 (0.5 mol / L alcoholic potassium hydroxide standard solution)

[II] Total amine number (II-1) Reagent (II-1-1) Bromcresol green indicator solution (BCG indicator solution): 100 mL of ethanol (primary grade) is added to 0.2 g of bromocresol green (special grade) and dissolved. .
(II-1-2) Neutral solvent: 10 mL of BCG indicator solution is added to 1 L of ethanol (first grade) and dissolved. Further neutralize with dilute alcoholic potassium hydroxide or hydrochloric acid.
(II-1-3) 0.2 mol / L alcoholic hydrochloric acid standard solution [Preparation]
Dissolve 17.5 mL of hydrochloric acid (special grade) in ethanol (primary grade) to 1 L, leave it for 4-5 days, and then standardize.
[orientation]
About 0.1 g of sodium carbonate (standard reagent) is weighed into a 100 mL Erlenmeyer flask and dissolved by adding about 30 mL of water. Add 2-3 drops of BPB indicator solution ^* and titrate with 0.2 mol / L alcoholic hydrochloric acid standard solution (sodium carbonate is ignited at 550-650 ° C. for 1 hour).
* Add 90 mL of ethanol to 0.1 g of BPB indicator solution bromophenol blue, and add water to make 100 mL.

(II-2) Operation (1) Weigh 2 g of sample (Note 1) into a 100 mL Erlenmeyer flask.
(2) Add about 30 mL of neutral solvent and dissolve (Note 2).
(3) Titrate with 0.2 mol / L alcoholic hydrochloric acid standard solution. The end point is the point where the color changes from blue to yellow.
(Note 1) Since the sample easily absorbs carbon dioxide in the air, avoid contact with the air as much as possible.
(Note 2) A sample with a high melting point is dissolved by heating. If it is not completely dissolved, dissolve it with toluene.

(II-3) Calculation The total amine value is obtained by the following formula. All amine values are rounded to one decimal place.

A: Amount (mL) of 0.2 mol / L alcoholic hydrochloric acid standard solution required for titration of the sample
f: Factor of 0.2 mol / L alcoholic hydrochloric acid standard solution

Claims (10)

Polyhydric alcohol and fatty acid ester (A) not containing an alkylene oxide group, a cationic surfactant (B ₁ ) represented by the following general formula (1), and a cation represented by the following general formula (2) A surfactant composition (B ₂ ), and the ratio of (B ₁ ) in the total amount of (B ₁ ) and (B ₂ ) is in the range of 50 to 95% by weight. .

(In the formula, R _1b is an alkyl group having 16 carbon atoms, an alkenyl group having 16 carbon atoms, or a β-hydroxyalkyl group having 16 carbon atoms, and R _2b is an alkyl group having 1 to 8 carbon atoms, or 1 to 8 carbon atoms. R _3b and R _4b are each an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 1 to 8 carbon atoms, and a β-hydroxy having 1 to 8 carbon atoms. Hydroxyalkyl group, benzyl group, or formula: — (A ₁ O) _n1 —Z ₁ (where A ₁ O is an oxyalkylene group having 2 to 4 carbon atoms, and Z ₁ is a hydrogen atom or 1 to 24 carbon atoms. And n ₁ is an average added mole number and a number of 1 to 50), and X ₁ ⁻ is a counter ion.)

Wherein R _5b is an alkyl group having 18 carbon atoms, an alkenyl group having 18 carbon atoms, or a β-hydroxyalkyl group having 18 carbon atoms, R _6b is an alkyl group having 1 to 8 carbon atoms, or 1 to 8 carbon atoms. R _7b and R _8b are each an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 1 to 8 carbon atoms, and a β-hydroxy having 1 to 8 carbon atoms. Hydroxyalkyl group, benzyl group, or formula: — (A ₂ O) _n2 —Z ₂ (where A ₂ O is an oxyalkylene group having 2 to 4 carbon atoms, and Z ₂ is a hydrogen atom or 1 to 24 carbon atoms. And n ₂ is an average addition mole number and a number of 1 to 50), and X ₂ ⁻ is a counter ion.) And (A), (B ₁₎ and (B ₂₎ and the weight ratio of (A) / _{[(B 1) + (B 2} ) ] is for papermaking according to claim 1, wherein the 99 / 1-40 / 60 Pharmaceutical composition. Polyhydric alcohol and fatty acid ester (A) not containing an alkylene oxide group, an amine compound (C ₁ ) represented by the following general formula (3), an amine compound (C ₂ ) represented by the following general formula (4) And a quaternizing agent (D) for the amine compound, wherein the (C ₁ ) and (C ₂ ) are quaternized with the (D), The design ratio of (X) in the total amount of the quaternized product (X) according to (D) of (C ₁ ) and the quaternized product (Y) according to (D) of (C ₂ ) is in the range of 50 to 95% by weight. A pharmaceutical composition for papermaking.

(Wherein R _1c is an alkyl group having 16 carbon atoms, an alkenyl group having 16 carbon atoms, or a β-hydroxyalkyl group having 16 carbon atoms, R _2c and R _3c are alkyl groups having 1 to 8 carbon atoms, An alkenyl group having 1 to 8 carbon atoms, a β-hydroxyalkyl group having 1 to 8 carbon atoms, a benzyl group, or a formula: — (A ₃ O) _n3 —Z ₃ (where A ₃ O is an oxyalkylene having 2 to 4 carbon atoms) Z ₃ is a hydrogen atom or an acyl group having 1 to 24 carbon atoms, and n ₃ is an average addition mole number and a number of 1 to 50).

Wherein R _4c is an alkyl group having 18 carbon atoms, an alkenyl group having 18 carbon atoms, or a β-hydroxyalkyl group having 18 carbon atoms, R _5c and R _6c are alkyl groups having 1 to 8 carbon atoms, An alkenyl group having 1 to 8 carbon atoms, a β-hydroxyalkyl group having 1 to 8 carbon atoms, a benzyl group, or a formula: — (A ₄ O) _n4 —Z ₄ (where A ₄ O is an oxyalkylene having 2 to 4 carbon atoms) Z ₄ is a hydrogen atom or an acyl group having 1 to 24 carbon atoms, and n ₄ is an average addition mole number and a number of 1 to 50).   The papermaking machine according to claim 3, wherein the design ratio of (A) to (X) and (Y) is 99/1 to 40/60 by weight ratio (A) / [(X) + (Y)]. Pharmaceutical composition. The pharmaceutical composition for papermaking according to claim 3 or 4, wherein (C ₁ ) and (C ₂ ) are used as a mixture of amine compounds each containing 80% by weight or more thereof. Polyhydric alcohol and fatty acid ester (A) not containing an alkylene oxide group, a cationic surfactant (B ₁ ) represented by the following general formula (1), and a cation represented by the following general formula (2) A paper-made pharmaceutical composition comprising a surfactant (B ₂ ), wherein the ratio of (B ₁ ) in the total amount of (B ₁ ) and (B ₂ ) is in the range of 50 to 95% by weight.

(In the formula, R _1b is an alkyl group having 16 carbon atoms, an alkenyl group having 16 carbon atoms, or a β-hydroxyalkyl group having 16 carbon atoms, and R _2b is an alkyl group having 1 to 8 carbon atoms, or 1 to 8 carbon atoms. R _3b and R _4b are each an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 1 to 8 carbon atoms, and a β-hydroxy having 1 to 8 carbon atoms. Hydroxyalkyl group, benzyl group, or formula: — (A ₁ O) _n1 —Z ₁ (where A ₁ O is an oxyalkylene group having 2 to 4 carbon atoms, and Z ₁ is a hydrogen atom or 1 to 24 carbon atoms. And n ₁ is an average added mole number and a number of 1 to 50), and X ₁ ⁻ is a counter ion.)

Wherein R _5b is an alkyl group having 18 carbon atoms, an alkenyl group having 18 carbon atoms, or a β-hydroxyalkyl group having 18 carbon atoms, R _6b is an alkyl group having 1 to 8 carbon atoms, or 1 to 8 carbon atoms. R _7b and R _8b are each an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 1 to 8 carbon atoms, and a β-hydroxy having 1 to 8 carbon atoms. Hydroxyalkyl group, benzyl group, or formula: — (A ₂ O) _n2 —Z ₂ (where A ₂ O is an oxyalkylene group having 2 to 4 carbon atoms, and Z ₂ is a hydrogen atom or 1 to 24 carbon atoms. And n ₂ is an average addition mole number and a number of 1 to 50), and X ₂ ⁻ is a counter ion.)   The paper composition according to any one of claims 1 to 6, wherein the form is an emulsion or a suspension. The papermaking pharmaceutical composition according to any one of claims 1 to 7, wherein (A) is selected from those having a water separation degree defined below of 4% or more.
Degree of water separation (%) = (α ₀ -Α) / α ₀ × 100
α: Moisture content of a wet sheet obtained by adding 5 parts by weight of the compound (A) to 100 parts by weight of pulp and making paper
α ₀ : Moisture content of wet sheet obtained by making paper without adding compound (A) to pulp The paper manufacturing method which adds the pharmaceutical composition for paper manufacture in any one of Claims 1-8 to a pulp slurry. A paper obtained by the paper manufacturing method according to claim 9 .