JP5445203B2 - Additive for paper - Google Patents

Description

  The present invention relates to a paper additive. More specifically, the present invention relates to a paper additive capable of simultaneously imparting sufficient size and good flexibility to paper in a well-balanced manner.

  With the progress of visualization and colorization of printed matter, there is a demand for a printing paper having higher flexibility from the viewpoint of improving printability. In addition, more flexible printing paper is required from the viewpoint of easy turning of pages of printed materials such as books.

  As a method for improving the flexibility of paper, a quaternary ammonium salt, a fatty acid having 8 to 24 carbon atoms or a salt thereof, and an esterified product of a fatty acid having 10 to 24 carbon atoms and pentaerythritol have been used at a predetermined weight ratio. A method using a softener contained in (Patent Document 1), a method using an amidated product obtained from a polyalkylene polyamine and a carboxylic acid or a salt thereof (Patent Document 2), and the like are known. However, although these softening agents are effective in improving flexibility, they may inhibit the effect of the sizing agent added to prevent bleeding during printing.

  A method using both a softening agent having a melting point of 50 ° C. or less and an HLB value of 8 or less and a sizing agent that is an ester compound of a polyhydric alcohol and a saturated fatty acid (patented) Reference 3), a method of using an amidated product obtained by reacting a carboxylic acid having 14 to 24 carbon atoms and an iodine value of 50 or less with a polyalkylene polyamine and an alkyl ketene dimer in a predetermined weight ratio (patent) Document 4) is known. However, there is a need for a method of imparting sufficient sizing properties and a superior flexibility improvement effect without using a sizing agent.

JP 7-189171 A JP 2002-275786 A JP 2004-324024 A JP 2004-11058 A

  An object of this invention is to provide the paper additive which can provide sufficient size property and favorable softness | flexibility to paper simultaneously with sufficient balance in view of the said situation.

  As a result of intensive studies to solve the above problems, the present inventors have obtained an object of the present invention to provide an amidoamine compound obtained by reacting a specific polyamine mixture and a specific fatty acid at a predetermined ratio and having a predetermined amine value. Found to achieve.

  That is, the paper additive of the present invention is based on 1 mol of a polyamine mixture composed of 10 to 40 mol% of the polyamine compound A represented by the formula (1) and 60 to 90 mol% of the polyamine compound B represented by the formula (2). It is obtained by reacting 2 to 5 moles of an aliphatic monocarboxylic acid having 12 to 24 carbon atoms and is composed of an amidoamine compound having an amine value of 40 to 280 mgKOH / g.

  (In the formula, x + y is an integer of 0 to 2.)

  (In the formula, z is an integer of 3 to 5.)

  The paper additive of the present invention is composed of an amidoamine compound that can be imparted to paper with both size and flexibility, so that sufficient sizing and good for paper can be obtained without using a sizing agent and a softening agent in combination. Flexibility can be imparted at the same time in a well-balanced manner.

  The paper additive of the present invention comprises an amidoamine compound obtained by reacting a specific polyamine mixture and a specific fatty acid in a specific ratio. Hereinafter, each component for producing this amidoamine compound will be described.

[Polyamine mixture]
The polyamine mixture used in the present invention contains 10 to 40 mol%, preferably 20 to 35 mol% of the polyamine compound A represented by the formula (1), and 60 to 90 mol of the polyamine compound B represented by the formula (2). Mol%, preferably 65 to 80 mol%. If the content ratios of the polyamine compound A and the polyamine compound B exceed these ranges, there is a possibility that sufficient size properties cannot be obtained.

[Polyamine Compound A]
The polyamine compound A used in the present invention is a polyethylene polyamine having a branched skeleton as represented by the formula (1).

  In the formula, x + y is an integer of 0-2. In this invention, the 1 type (s) or 2 or more types of polyamine compound A represented by Formula (1) can be used.

[Polyamine Compound B]
The polyamine compound B used in the present invention is a linear polyethylene polyamine as represented by the formula (2).

  In the formula, z is an integer of 3 to 5. In the present invention, one or more polyamine compounds B represented by the formula (2) can be used.

[Aliphatic monocarboxylic acid]
The aliphatic monocarboxylic acid used in the present invention is a fatty acid having 12 to 24 carbon atoms. Specific examples include lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, arachidic acid, behenic acid, erucic acid, and lignoceric acid. Of these, saturated fatty acids having 16 to 20 carbon atoms are preferred. These aliphatic monocarboxylic acids may be used alone or in a mixture.

[Amidamine compound]
The amidoamine compound used in the present invention is obtained by subjecting 1 mol of the polyamine mixture to a condensation reaction of 2 to 5 mol of the aliphatic monocarboxylic acid. If the number of moles of the aliphatic monocarboxylic acid to be reacted with respect to 1 mole of the polyamine mixture is less than 2 moles, sufficient size may not be obtained. In addition, the number of moles of the aliphatic monocarboxylic acid to be reacted with 1 mole of the polyamine mixture is hereinafter also referred to as a reaction mole ratio.

The amidoamine compound used in the present invention has an amine value of 40 to 280 mg KOH / g. If the amine value is less than 40 mg KOH / g, good flexibility may not be obtained, and if it exceeds 280 mg KOH / g, sufficient size may not be obtained. The amine value of the amidoamine compound is determined by a known method such as Tf of American Oil Chemists' Society (AOCS).
It can be measured according to 1b-64 (indicator method).

  The amidoamine compound used in the present invention is prepared by mixing the polyamine mixture and the aliphatic monocarboxylic acid without solvent and raising the temperature to 160 to 230 ° C. while stirring in an inert gas atmosphere such as nitrogen gas. It can manufacture by making it react, removing the produced water byproduced out of a reaction system.

  The amine value of the amidoamine compound used in the present invention can be adjusted by changing the number of amino groups per mole of the polyamine mixture, the reaction molar ratio of the aliphatic carboxylic acid, and the carbon number of the aliphatic monocarboxylic acid. . For example, the amine value can be increased by using a polyamine mixture having many amino groups per mole, reducing the reaction molar ratio, or using an aliphatic monocarboxylic acid having a small number of carbon atoms.

[Additives for paper]
Typically, the paper additive of the present invention comprising the above-mentioned amidoamine compound can be used as a dispersion by dispersing the above-mentioned amidoamine compound in a dispersion medium. Note that water is preferable as the dispersion medium.

  When the paper additive of the present invention is used as a dispersion, it is preferable to neutralize the amidoamine compound with an acid to make a salt in order to facilitate the preparation of the dispersion. Examples of the acid used in this case include various inorganic acids or organic acids. Specifically, hydrochloric acid, sulfuric acid, carbonic acid, nitric acid, phosphoric acid, formic acid, acetic acid, propionic acid, butyric acid, glycolic acid, lactic acid, Examples include gluconic acid, salicylic acid, hydroxyvaleric acid, aspartic acid, glutamic acid, taurine, sulfamic acid, and the like. Formic acid, acetic acid, glycolic acid, lactic acid and gluconic acid are preferred. When an acid is used to form a salt, the amine value of the obtained amidoamine compound is measured, and the amount of acid added to give an acid value approximately equivalent to the measured amine value is calculated and added to the amidoamine compound. It is preferable to use a salt of

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention concretely, this invention is not limited at all by these Examples.

[Synthesis of Amidoamine Compound]
The polyamine mixtures (1 to 4) listed in Tables 1 and 2 and the aliphatic monocarboxylic acids listed in Table 2 were subjected to a condensation reaction at the reaction molar ratios listed in Table 2 (to 1 mole of the polyamine mixture) (Synthesis Examples 1 to 4). Comparative Synthesis Examples 1 to 3) and amidoamine compounds (AA-1 to AA-4, AA′-1 to AA′-3) were obtained.

[Measurement of amine value]
For each of the amidoamine compounds (AA-1 to AA-4, AA′-1 to AA′-3) listed in Table 2, the amine value was measured according to AOCS Tf 1b-64 (indicator method). did.

[Examples 1-4 and Comparative Examples 1-3]
Dispersions (1-7) of the amidoamine compounds (AA-1 to AA-4, AA′-1 to AA′-3) listed in Table 2 were prepared, and Examples 1 to 4 and Comparative Example 1 were sequentially prepared. It was set to ~ 3. In preparing the dispersion, acetic acid equivalent to 1 equivalent of the amine value of each amidoamine compound is added to ion-exchanged water, and the amidoamine compound is dispersed so as to be 1.0 mass% as an acetate salt of the amidoamine compound. It was.

[Evaluation of paper additives]
Handsheets were produced as follows using the paper additive dispersions (Examples 1-4 and Comparative Examples 1-3) obtained above. The obtained handsheet was evaluated for size and flexibility (bending stiffness).

(1) Preparation of handsheet A pulp slurry containing 1% by mass of LBKP (hardwood bleached pulp) having a freeness of 430 ml was prepared. 400 g of this pulp slurry (pulp amount 4 g) is taken in a beaker, and 1.0% by mass of the above-mentioned amidoamine compound is obtained using 1.0% by mass of the above-mentioned amidoamine compound as an effective component of pregelatinized cationized starch (manufactured by Oji Cornstarch Co., Ltd .: Ace K-100). 0.5% by mass of pulp was added as an effective component of the dispersion and stirred for 1 minute with a turbine blade. Using 100 g of this stirred pulp slurry, a paper is made with a TAPPI standard sheet machine (manufactured by Yasuda Seiki Co., Ltd.), pressed with a hydraulic press machine (manufactured by Yasuda Seiki Co., Ltd.) for 0.35 MPa, and then drum-type. Drying was performed at 105 ° C. for 2 minutes using a dryer (manufactured by Yasuda Seiki Co., Ltd.) to prepare three handsheets having a basis weight of 50 g / m ² . The handsheet was conditioned for 17 hours in a constant temperature and humidity chamber (temperature 23 ° C., humidity 50%).

(2) Evaluation of sizing properties In accordance with JIS P8122: 2004, the squeecht sizing degree of the handsheets was measured 6 times in each example, the total sizing degree was determined, and listed in Table 3. Furthermore, the sizing properties were evaluated according to the following criteria, and the evaluations are also summarized in Table 3.

(Evaluation criteria) Total size is 60 seconds or more: Good size
Total size is less than 60 seconds: Size is insufficient ×

(3) Evaluation of flexibility The bending stiffness of the moisture-controlled handsheet was measured with a pure bending tester (manufactured by Kato Tech Co., Ltd .: KES-FB2). Each example was measured six times, and the average value of bending stiffness was obtained and summarized in Table 3. Furthermore, the flexibility was evaluated according to the following criteria, and the evaluation is also summarized in Table 3.

(Evaluation criteria) Less than 3.5 × 10 ⁻⁵ N · m ² / m: Good flexibility ○
3.5 × 10 ⁻⁵ N · m ² / m or more: Insufficient flexibility ×

In Examples 1 to 4 using the paper softener of the present invention, the sizing degree is 60 seconds or more and the bending stiffness is less than 3.5 × 10 ⁻⁵ N · m ² / m, which is sufficient for paper. Size and good flexibility were obtained.

  On the other hand, since Comparative Example 1 uses an amidoamine compound (AA′-1) that does not contain amine compound A, the flexibility is the same as in Examples 1 to 4 of the present invention. Sex was insufficient. In Comparative Example 2, the amine value of the amidoamine compound exceeded the upper limit specified in the present invention, so that the size and flexibility were insufficient. Furthermore, since Comparative Example 3 used capric acid, which is an aliphatic monocarboxylic acid having 10 carbon atoms, when synthesizing the amidoamine compound (AA′-3), the size property was insufficient.

  The paper additive of the present invention can impart sufficient size and good flexibility to paper at the same time in a well-balanced manner, so bookbinding paper, newsprint paper, printing / information paper, cardboard paper, paperboard, tissue paper, It can be widely used for various papers such as toilet paper and kitchen towels.

Claims (1)

Aliphatic monocarboxylic acid having 12 to 24 carbon atoms with respect to 1 mol of polyamine compound A comprising 10 to 40 mol% of polyamine compound A represented by formula (1) and 60 to 90 mol% of polyamine compound B represented by formula (2) A paper additive comprising an amidoamine compound obtained by reacting 2 to 5 moles of an acid and having an amine value of 40 to 280 mg KOH / g.

(In the formula, x + y is an integer of 0 to 2.)

(In the formula, z is an integer of 3 to 5.)