JP2014070292A - Method for producing fibrillated pulp and fiber reinforced plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing fibrillated pulp, which can produce fibrillated pulp having excellent quality.SOLUTION: When fibrillating a pulp sheet by using a crusher, the method for producing the fibrillated pulp treats the pulp sheet by using a fibrillating agent that contains at least one of a following (a) component and a (b) component. The (a) component is an amide compound or a salt thereof obtained by reaction of aliphatic acid and polyamine, and the (b) component is an ester compound of an alkylene oxide adduct of aliphatic amine and aliphatic acid.

Description

  TECHNICAL FIELD The present invention relates to a method for producing pulverized pulp that can be used for industrial products such as filled pulp for heat insulating materials, diapers and other sanitary products and ceramic boards, and a fiber reinforced plate using the same.

  Conventionally, a pulverized pulp is obtained by pulverizing (defibrating) a pulp sheet, and this is blended as a reinforcing fiber in a building material such as a ceramic board. In producing the pulverized pulp, the pulp sheet is often mechanically dry pulverized, and a pulverizer type, a hammer mill type, a dry beating machine, etc. are employed as the pulverization method.

  However, in the above method, since the pulp sheet is pulverized only by mechanical shear, it is difficult to separate the pulp fibers one by one, which may cause lumps (pulp fiber lump). In addition, in order to suppress the occurrence of lumps, if a mechanically strong share is applied, the pulp fiber may be damaged or cut, which may reduce the quality of the secondary product containing the pulverized pulp. . In addition, since a very large amount of energy is required to pulverize the pulp sheet, not only does the power cost of the pulverizer increase, but noise problems may occur and the life of the apparatus may be shortened. there were. Therefore, there is a problem that it is difficult to obtain a high-quality pulp sheet only by mechanical share.

  Therefore, it has been proposed to facilitate the pulverization using a drug. For example, Patent Document 1 describes that cellulose fibers are defibrated in a solution containing a dispersant.

Japanese Patent No. 4384411

  However, a pulverized pulp having better quality than the above conventional example has been desired.

  The present invention has been made in view of the above points, and an object of the present invention is to provide a method for producing a pulverized pulp from which a pulverized pulp having good quality such as improved defibration and suppression of water absorption can be obtained. . Another object of the present invention is to provide a fiber reinforced plate using the above pulverized pulp.

In the method for producing pulverized pulp according to the present invention, when the pulp sheet is pulverized by a pulverizer, the pulp sheet is treated with a defibrating agent containing at least one of the following components (a) and (b): It is characterized by.
(A) An amide compound or a salt thereof obtained by reacting a fatty acid with a polyamine.
(B) An ester compound of an alkylene oxide adduct of an aliphatic amine and a fatty acid.

  In this invention, the said (a) component may contain the urea condensate produced | generated by the deammonium reaction of the said amide compound or its salt, and urea.

  In the present invention, it is preferable to use a defibrating agent in which the content ratio of the component (a) and the component (b) is in the range of 60:40 to 99: 1 by mass ratio.

  The fiber reinforcing plate according to the present invention is characterized by containing the pulverized pulp as reinforcing fibers.

  The method for producing pulverized pulp according to the present invention pulverizes a pulp sheet after being treated with a defibrating agent, so that the pulp sheet may be pulverized in a state where the bond between pulp fibers of the pulp sheet is weakened with the defibrating agent. It is possible to obtain pulverized pulp with less occurrence of lumps, and it is not necessary to pulverize with a strong share by a pulverizer, so that each pulp fiber can be made without damaging or cutting the pulp fiber. It can be separated and pulverized. Further, the power cost of the pulverizer can be reduced, noise problems can be reduced, and the lifetime of the apparatus can be extended. Moreover, since the pulp sheet is treated with a defibrating agent containing at least one of the component (a) and the component (b), a pulverized pulp with good quality such as improved defibration and reduced water absorption can be obtained. It is something that can be done.

  The fiber reinforced board according to the present invention is less damped, can be reinforced with pulverized pulp with less damage and cutting of fibers, and can improve physical properties such as bending strength.

  Hereinafter, modes for carrying out the present invention will be described.

  The method for producing pulverized pulp of the present invention is to pulverize a pulp sheet after being treated with a defibrating agent by a pulverizer. As the defibrant, (a) component which is an amide compound obtained by reacting a fatty acid and a polyamine or a salt thereof, and (b) component which is an ester compound of an alkylene oxide adduct of an aliphatic amine and a fatty acid Any one or both of these are contained.

  As the fatty acid used in the component (a), a carboxylic acid having 8 to 30 carbon atoms is preferable, and a carboxylic acid having 12 to 26 carbon atoms is more preferable. Specifically, caprylic acid, capric acid, Lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, oleic acid, linoleic acid, linolenic acid, erucic acid, 21-triacontenoic acid, 12-hydroxystearic acid, ricinoleic acid, isononanoic acid , Isodecanoic acid, isotridecanoic acid, isomyristic acid, isopalmitic acid, isostearic acid, tall oil fatty acid, beef tallow fatty acid, coconut fatty acid, castor fatty acid, and hardened fatty acids thereof can be used.

  Examples of the polyamine used in component (a) include polyamines represented by the general formula [1], polyamines having an alkanol group such as aminoethylethanolamine, and melamine.

_{H 2 N - ((CH 2} ) n -NH) m -H ... [1]
In general formula [1], m is an integer of 1 to 7, and n is an integer of 1 to 6. Examples of the amine represented by the general formula [1] include alkyldiamines such as ethylenediamine, propylenediamine, and hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, Mention may be made of polyalkylene polyamines such as heptaethyleneoctamine, dipropylenetriamine, tripropylenetetramine. Moreover, you may use the industrial polyamine which contains these as a main component. Examples of industrial polyamines include ethyleneamines manufactured and sold by Sumitomo Seika, Tosoh and Kanto Denka Kogyo.

  The reaction between the fatty acid and the polyamine can be carried out at 150 to 250 ° C. for 30 minutes to 6 hours after blending the fatty acid and the polyamine. Moreover, the mixture ratio of a fatty acid and a polyamine can make a polyamine 0.5-2 times mole with respect to 1 mol of fatty acids. This reaction is preferably carried out until a reaction product (amide compound) having an acid value of 5 to 1 mg KOH / g, a total amine value of 500 to 50, and a tertiary amine value of 300 to 10 is obtained. A part of the amide compound may form an imidazoline structure. Moreover, the salt of the amide compound obtained by making a fatty acid and a polyamine react can be obtained by neutralizing said amide compound which is a reaction material of a fatty acid and a polyamine with an acid. Thus, by using a salt of an amide compound, which is a reaction product of a fatty acid and a polyamine, as a defibrating agent, the emulsifiability in water can be improved and the defibrating property can be improved. Can be obtained, which is preferable. Acids used to form amide compound salts include organic acids such as formic acid, acetic acid, propionic acid, butanoic acid, lauric acid, stearic acid, oleic acid, lactic acid, glycolic acid, malic acid, citric acid, and hydrochloric acid And inorganic acids such as sulfuric acid, phosphoric acid and phosphorous acid.

  The component (a) may contain a urea condensate in addition to the amide compound or a salt thereof. This urea condensate is preferably produced by a deammonium reaction between the amide compound or a salt thereof and urea. In this case, 0.01 to 0.5-fold moles of urea can be blended and reacted with 1 mole of polyamine used in the formation of the amide compound or a salt thereof. Moreover, the reaction conditions of an amide compound or its salt and urea can be made into 30 minutes-6 hours at 100-200 degreeC. The reaction is preferably carried out until a reaction product (amide compound containing a urea condensate) having a total amine value of 400 to 10 and a tertiary amine value of 300 to 10 is obtained. The urea condensate thus obtained can suppress freezing of the defibrating agent at −5 ° C. and can be used by emulsifying the defibrating agent in water as it is even at low temperatures. The urea condensate is preferably contained in the component (a) in an amount of 0 to 20 mol%, and the remainder is preferably an amide compound or a salt thereof.

  As the alkylene oxide adduct of the aliphatic amine used in the component (b), the number of added moles of alkylene oxide is preferably 1 to 100, and the number of added moles is more preferably 2 to 20. When the added mole number is within this range, the emulsifiability with respect to water becomes good and the defibration property can be improved. As the aliphatic amine, a saturated or unsaturated primary amine or secondary amine having 8 to 36 carbon atoms can be used. Specifically, octylamine, 2-ethylhexylamine, nonylamine, laurylamine, myristylamine, cetylamine, stearylamine, isostearylamine, oleylamine, behenylamine, coconutamine, 12-hydroxystearylamine, dilaurylamine, distearyl Examples include amines, dioleylamines, and other synthetic amines. As said alkylene oxide, a C2-C4 thing is preferable, More preferably, ethylene oxide (EO) independent or the block or random adduct of ethylene oxide and propylene oxide (PO) can be used. . When ethylene oxide and propylene oxide are used in combination, it is preferable that 20 mol% or more of the added moles of alkylene oxide is ethylene oxide. The fatty acid used in component (b) is preferably a saturated or unsaturated monocarboxylic acid having 8 to 36 carbon atoms. Specifically, caprylic acid, capric acid, lauric acid, myristic acid , Palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, oleic acid, linoleic acid, linolenic acid, erucic acid, 21-triacontenoic acid, 12-hydroxystearic acid, ricinoleic acid, isononanoic acid, isodecanoic acid, isotridecane Examples include acids, isomyristic acid, isopalmitic acid, isostearic acid, dimer acid in which fatty acids are doubled, tall oil fatty acid, beef tallow fatty acid, palm fatty acid, castor fatty acid, and hardened fatty acids thereof. And in producing | generating the ester compound of (b) component, after adding an alkylene oxide to an aliphatic amine, Preferably it is 1-2 mol of a fatty acid with respect to 1 mol of alkylene oxide adducts of an aliphatic amine. Try to react at a ratio. The reaction conditions can be 30 to 280 ° C. for 30 minutes to 6 hours.

  The above-described defibrating agent only needs to contain at least one of the component (a) and the component (b), but when the component (a) and the component (b) are used in combination, the blending ratio is a mass ratio. Component (a): component (b) is preferably in the range of 60:40 to 99: 1, more preferably component (a): component (b) = 80: 20 to 95: 5. When the component (a) and the component (b) are used in combination within the above range, the defibration can be further improved.

  In the method for producing pulverized pulp of the present invention, a pulp sheet is treated with the above defibrant and then pulverized by a pulverizer. The pulp sheet is obtained by solidifying pulp fibers into a sheet by a papermaking method or the like, and may be provided in a state of being wound in a roll. When the pulp sheet is treated with the defibrating agent, the treatment method is not particularly limited as long as the defibrating agent is supplied substantially uniformly throughout the pulp sheet. For example, the treatment can be performed by blending and diluting a defibrating agent with water, alcohol or a mixture thereof and impregnating the pulp sheet by spraying or dipping. Moreover, it is preferable to dry the pulp sheet impregnated with the diluent with a dryer or the like. It is preferable to treat the defibrating agent so that the solid content mass is 0.05 to 5.0 mass% with respect to the total mass of the pulp sheet. The pulp sheet treated with the defibrating agent becomes bulky and becomes a soft and soft sheet. This phenomenon is because the bond between pulp fibers is weakened due to the effect of the defibrating agent, the entanglement of the pulp fibers is reduced, and a gap is formed between the pulp fibers.

  The pulverized pulp can be obtained by pulverizing (defibrating) the pulp sheet treated as described above with a pulverizer (defibner) such as a hammer mill method. And in said method, a pulp sheet can be grind | pulverized in the state which weakened the coupling | bonding between the pulp fibers of a pulp sheet with a defibrating agent, and a pulverized pulp with little generation | occurrence | production of a dama can be obtained. Further, it is not necessary to pulverize with a strong share by a pulverizer, and the pulp fibers can be separated and pulverized one by one without damaging or cutting the pulp fibers. Furthermore, the power cost of the crushing device can be reduced, noise problems can be reduced, and the life of the device can be extended.

  The fiber reinforced board of the present invention contains the above pulverized pulp as a reinforcing material. When the fiber reinforced board is formed as a cement board such as a building material, examples of components other than pulverized pulp include cement, quartzite powder, and aggregate. And, when the above pulverized pulp is used, there is little pulp fiber lumps, so that the part that becomes a defect in the reinforcing fiber board can be reduced, and the physical properties such as the bending strength of the fiber reinforcing board are not easily lowered. It is.

  Hereinafter, the present invention will be specifically described by way of examples.

Example 1
In a four-necked flask equipped with a thermometer and a nitrogen gas blowing tube, 578 g (2.0 mol) of tall oil fatty acid is taken, heated gradually with a mantle heater while blowing nitrogen gas, and diethylenetriamine at 100 to 110 ° C. 103 g (1 mol) was added dropwise over 1 hour. Thereafter, the temperature was further gradually raised, and a dehydration reaction was performed at 240 to 250 ° C. for 3 hours. The acid value of the obtained reaction product (amide compound) was 1, the total amine value was 88, and the tertiary amine value was 75.

  Next, the reaction product was cooled, 9 g (0.2 mol) of urea was added at 120 ° C., and deammonia reaction was performed at 170 to 180 ° C. to obtain a urea condensate. The urea condensation product obtained had a total amine value of 78 and a tertiary amine value of 75. The urea condensate was neutralized with 99% by mass acetic acid to obtain a neutralized product. This neutralized product was used as component (a). The neutralized product is a neutralized product of a mixture of diethylenetriamine tall fatty acid amide (0.85 mol) and its urea condensate (0.07 mol).

  The “total amine value” was determined by accurately weighing about 1 g of a sample in 30 mL of glacial acetic acid previously neutralized with 0.1 mol / L perchloric acid, and using a potentiometric titrator. Evaluation was carried out by titration with mol / L perchloric acid. In addition, the “tertiary amine value” is obtained by accurately weighing approximately 1 g of a sample in 30 mL of a mixed solution of acetic anhydride: glacial acetic acid (3: 7, mass ratio) and heating at 100 ° C. for 30 minutes. After acetylation of the secondary amine and secondary amine, the tertiary amine was evaluated by titrating with 0.1 mol / L perchloric acid using a potentiometric titrator.

  The component (a) was used as a defibrating agent. As the pulp sheet, product number intercontinental manufactured by Canfor was used. When treating the pulp sheet with a defibrating agent, dilute the defibrating agent with water and supply the diluent to the pulp sheet so that the defibrating agent is 1.0% by mass with respect to the total mass of the pulp sheet. And impregnated substantially uniformly. Next, the treated pulp sheet was pulverized using a hammer mill type pulverizer (Hammer Mill H manufactured by Hosokawa Micron Corporation). Thus, the knot ratio of the pulverized pulp obtained by pulverization was measured. The knot ratio is an evaluation index of the defibration properties of pulp fibers, and is expressed as a sieve residue (mass ratio,%) per 1 g of pulp fibers. Specifically, the pulverized pulp was conveyed by an air flow, and the undefined rate was calculated from the remaining part of the 80 mesh sieve (mesh hole 850 μm sieve according to ISO 3310/1) to obtain the knot rate. It can be said that the smaller the knot ratio, the finer the pulverized pulp and the better the pulp defibration.

  A fiber-reinforced cement board was prepared using the above pulverized pulp. In this case, first, 50 parts by mass of the above pulverized pulp, 400 parts by mass of cement, 300 parts by mass of silica powder, and 250 parts by mass of aggregate are mixed and then mixed with 200 parts by mass of water. Thus, a molding material was prepared. Next, this molding material was molded on a mat and then pressed into a plate shape by pressing at a surface pressure of 20 MPa. Next, the molded plate was cured in an atmosphere of 40 ° C. for 1 day, and then cured at 170 ° C. for 24 hours. In this way, a fiber reinforced cement board was obtained by curing the cement.

(Example 2)
269 g (1 mol) of stearylamine is charged into a pressure-resistant reaction vessel, the inside is replaced with nitrogen gas, the temperature is raised to 130 ° C., and 88 g (2 mol) of ethylene oxide is blown into the pressure-resistant reaction vessel at a reaction temperature of 140 to 150 ° C. The addition reaction was carried out. Next, 1.0 g of sodium hydroxide was added as a catalyst, and 358 g (6 mol) of propylene oxide was blown to cause an addition reaction. Next, 354 g (8 mol) of ethylene oxide was blown to cause addition reaction. 983 g (1 mol) of the obtained stearylamine alkylene oxide adduct, 578 g (2 mol) of tall oil fatty acid and 1 g of paratoluenesulfonic acid as a catalyst were charged into a four-necked flask, and the temperature was 180 to 240 under a nitrogen gas stream. The dehydration esterification reaction was carried out at 5 ° C. for about 5 hours. This ester compound was used as component (b).

  A pulverized pulp was obtained in the same manner as in Example 1 except that the component (b) was used as a defibrating agent, and a fiber-reinforced cement board was formed using the pulverized pulp.

(Example 3)
The component (a) of Example 1 and the component (b) of Example 2 were mixed at a mass ratio of 60:40 to obtain a mixture. A ground pulp was obtained in the same manner as in Example 1 except that this mixture was used as a defibrating agent, and a fiber-reinforced cement board was formed using this ground pulp.

Example 4
The component (a) of Example 1 and the component (b) of Example 2 were mixed at a mass ratio of 90:10 to obtain a mixture. A ground pulp was obtained in the same manner as in Example 1 except that this mixture was used as a defibrating agent, and a fiber-reinforced cement board was formed using this ground pulp.

(Comparative Example 1)
A pulverized pulp was obtained in the same manner as in Example 1 without using a defibrating agent, and a fiber reinforced cement board was formed using the pulverized pulp.

(Comparative Example 2)
A pulverized pulp was obtained in the same manner as in Example 1 except that dioleyldimethylammonium chloride, which is a cationic quaternary amine compound, was used as a defibrating agent, and a fiber reinforced cement board was formed using the pulverized pulp.

  About said Example and comparative example, the three-point bending strength (JIS A 1106: 2006) of the fiber reinforced cement board and the water absorption after 24 hours in water were measured. The results are shown in Table 1.

  When pulverized pulp having a high knot ratio (a lot of fiber lumps) is used, defects are likely to occur inside the fiber-reinforced cement board, and the three-point bending strength is reduced (Comparative Examples 1 and 2). In the case of the examples, a uniform fiber-reinforced cement board with high strength development and little variation can be obtained. Moreover, in Example 1, the water absorption rate of the fiber reinforced cement board fell. This is because the water absorption of the pulverized pulp was reduced by the treatment with the defibrating agent, and as a result, improvement in the dimensional stability and durability of the fiber-reinforced cement board is expected.

Claims (4)

In pulverizing a pulp sheet with a pulverizer, the pulp sheet is treated with a defibrating agent containing at least one of the following components (a) and (b):
(A) An amide compound or a salt thereof obtained by reacting a fatty acid with a polyamine.
(B) An ester compound of an alkylene oxide adduct of an aliphatic amine and a fatty acid.   The said (a) component contains the urea condensate produced | generated by the deammonium reaction of the said amide compound or its salt, and urea, The manufacturing method of the ground pulp of Claim 1 characterized by the above-mentioned.   The pulverized pulp according to claim 1 or 2, wherein a defibrating agent in which the content ratio of the component (a) and the component (b) is in a range of 60:40 to 99: 1 by mass ratio is used. Production method. A fiber-reinforced plate comprising the pulverized pulp according to any one of claims 1 to 3 as a reinforcing fiber.