JPH062995B2 - Deinking agent for recycled waste paper - Google Patents

Description

TECHNICAL FIELD The present invention relates to a deinking agent used for recycling printed waste paper such as newspapers, magazines and leaflets. More specifically, the present invention relates to a deinking agent capable of obtaining a deinked pulp having high whiteness and less residual ink when the deinking treatment of newspapers, magazines and the like is carried out by the flotation method, and the foaming property and the ink collecting property are enhanced.

(Prior Art) Recycling of newspapers, magazines, etc. has been carried out for a long time, but recently, due to the protection of forest resources and the expanded use of deinked pulp, the effective use of recycled paper has become more important. There is.

In order to recycle printed waste paper, the printed waste paper is usually placed in a disintegrator and an alkaline chemical such as caustic soda or sodium silicate and a deinking agent, and if necessary, a bleaching agent such as hydrogen peroxide or hyposulfite, E
Disaggregate with sequestering agents such as DTA and PTPA,
A method in which ink is desorbed from the pulp and the desorbed ink is separated from the pulp by a water washing treatment or a flotation treatment is widely adopted.

The de-blackening agent is roughly classified into a dispersion-type de-blackening agent, which is intended to remove the desorbed ink in a finely dispersed state, and a de-inking agent which is separated from the system to a certain extent. There are cohesive deinking agents for the purpose of removing the coagulant deinking agent, and among them, cohesive deinking agents, which can increase the whiteness of recycled pulp, are widely used.

Dehydrating ink agents include anionic activators such as alkylbenzene sulfonates, higher alcohol sulfates, α-orphine sulfonates, non-ionic activators such as polyoxyalkylene alkyl ethers, polyoxyalkylene alkyl allyl ethers, and fatty acid alkanol amides. Agents or higher fatty acids have been blended alone or in combination of two or more. However, although the higher fatty acid type has a high ink aggregation effect, it has a problem that it cannot penetrate into the pulp, the ink peeling effect and the foamability are low, and a sufficient deinking effect cannot be obtained.

Therefore, a deinking agent for recycling used paper, which is obtained by adding an alkylene oxide to a monovalent higher fatty acid (JP-A-53-130309).
No.), a deinking agent obtained by adding an alkylene oxide to a fatty acid (JP-A-58-109696), and a deinking agent for recycling used paper obtained by adding an ethylene oxide and a mixed alkylene oxide to a monovalent higher fatty acid (JP-A-59). -130400
No.), a deinking agent containing a polyoxyalkylene glycol ester as a main component, which is obtained by adding alkylene oxide to rosin which is also a monovalent carboxylic acid (JP-A-63-
No. 303190), a deinking agent for recycling used paper containing an addition reaction product of a natural oil and fat, a polyhydric alcohol and an alkylene oxide (Japanese Patent Laid-Open No. 1111086) has been proposed, and these polyoxyalkylene alkyl ethers and other alkylene oxides have been proposed. The adduct system has a high effect of penetrating into the pulp and a peeling and dispersing effect of the ink, but since the affinity with the ink is poor, the aggregating effect of the ink is not yet sufficient.

(Problems to be solved by the invention) In particular, recently used paper has improved printing technology, and in particular, the ink composition changes due to offsetting of printing ink, and a drying oil or a thermosetting resin is used. Was hardened, and it was difficult to remove the ink from the conventional deinking agent and separate it from the pulp, and it was not possible to obtain a high quality deinked pulp.

Further, as the use of deinked pulp expands, there is a demand for deinked pulp with higher whiteness and less residual ink.

Therefore, the present invention aims to resist a deinking agent capable of easily performing high deinking even on waste paper that has become difficult to be desorbed and separated. Considering that it is necessary to be a deinking agent that has a large effect and a large ink aggregation effect and foaming property at the same time, as a result of intensive research,
In particular, it was found that a dimer acid of a higher unsaturated fatty acid or a polymer acid to which an alkylene oxide is added has the above-mentioned necessary physical properties, and the present invention has been completed. By the way, as a method for binding polyoxyalkylene to the dimer acid and polymer acid of the higher unsaturated fatty acid, there are roughly classified into an esterification method through polyoxyalkylene glycol and an addition polymerization method in which alkylene oxide is directly addition-polymerized. The former esterification method is suitable for producing an addition polymer in which a polyoxyalkylene is bonded to a part of a carboxyl group to partially leave a fatty acid group, but the production cost is high and it is not suitable for industrial products. On the other hand, in the latter addition polymerization method, all of the carboxyl group polyoxyalkylenes are added to leave no fatty acid, but it is suitable for mass production, affords an addition polymerization product, and can be obtained by the esterification method. It was found that it has deinking performance comparable to that of the product.

(Means for Solving the Problems) That is, the present invention provides at least one of dimer acid and polymer acid of a higher unsaturated fatty acid having 16 to 20 carbon atoms,
The deinking agent for recycling used paper is characterized in that the main component is a copolymer having no residual carboxyl group obtained by addition-polymerizing one or more alkylene oxides having 2 to 4 carbon atoms in an amount of 300 mol or less.

The dimer acid and polymer acid of the higher unsaturated fatty acid having 16 to 20 carbon atoms used in the present invention can be obtained by polymerizing higher fatty acid monoenoic acid or dienoic acid.
Examples include those obtained by thermal polymerization of unsaturated fatty acid monomers such as oleic acid, linoleic acid, and linolenic acid, or by other methods.Currently commercially available and easily available are those of oleic acid and linoleic acid. Polymerized dimer acid having 36 carbon atoms and trimer acid having 54 carbon atoms, or a mixture thereof. Its molecular production is not clear, and it is industrially provided as a mixture of various isomers, such as halidimer obtained by polymerization of tall oil fatty acid (manufactured by Harima Kasei Kogyo), that obtained by polymerization of soybean oil fatty acid, etc. This is a suitable example. The present invention does not limit the incorporation of small amounts of monomeric acid.

Examples of the alkylene oxide used in the present invention include ethylene oxide, propylene oxide and butylene oxide, and one kind or two or more kinds may be added.
The addition of one or more species can be carried out by random addition or block addition, with random addition being the most preferred combination of ethylene oxide and propylene oxide. The number of moles of alkylene oxide added is 300 moles or less, and when it is 300 moles or more, the foamability in the flotation step during deinking is deteriorated, and the cohesiveness of the peeled ink is impaired, and high quality recycled pulp cannot be obtained. . The number of added moles of alkylene oxide is particularly preferably 10 to 200 moles. The addition reaction is not particularly limited, and for example,
By adding an alkaline substance as a catalyst to the above-mentioned dimer acid and / or polymer acid, 100-200 ° C., 1-5 Kg
Blowing alkylene oxide at / cm ² and reacting for several hours,
Addition products can be obtained.

The place where the deinking agent of the present invention is added is preferably the step before the pulper or the aging tower, but the deinking agent can also be added and used in the floatator. Although the present deinking agent is sufficiently effective alone, other deinking agents such as anionic activators, nonionic activators such as polyoxyalkylene alkyl ethers, and higher fatty acids may be used in combination.

(Effect) Since the deinking agent of the present invention has an alkylene oxide added to a dimer acid of a higher unsaturated fatty acid or a polymer acid, it not only has excellent penetrability into ink and releasability, but also foamability and aggregation of ink. Since the properties are extremely excellent as compared with conventional deinking agents, it is possible to easily obtain high quality recycled pulp with high whiteness and less residual ink.

(Examples) Hereinafter, the present invention will be specifically described based on Examples.

Example 1 Dimer acid 79 obtained by polymerization of tall oil fatty acid
%, Trimer acid 18%, monomer acid 3% and acid value 193,
484 g of Haridimer 250 (manufactured by Harima Kasei Kogyo Co., Ltd.) having an average molecular weight of 605 was placed in a pressure resistant reaction vessel, 2.4 g of caustic potash was added, and the mixture was heated to 170 ° C. and deaerated, and nitrogen gas was sealed therein. Blowing reaction was carried out at 5 kg / cm ² for 3 hours to obtain a deinking agent containing 6 mol of ethylene oxide.

[Example 2] The reaction conditions were 2 of Haridimer 250 (manufactured by Harima Chemicals).
A deinking agent containing 40 mol of ethylene oxide was obtained in the same manner as in Example 1 except that 42 g, caustic potassium 1.2 g and ethylene oxide 704.8 g were used.

Example 3 Dimer acid 79 obtained by polymerization of tall oil fatty acid
%, Trimer acid 18%, monomer acid 3% and acid value 193,
121 g of Haridimer 250 (manufactured by Harima Kasei Co., Ltd.) having an average molecular weight of 605 was placed in a pressure resistant reaction vessel, 0.6 g of caustic potash was added, degassed by heating to 170 ° C., and nitrogen gas was sealed therein. / Cm ² for 3 hours, followed by blowing propylene oxide (232.3 g) at 1-5 kg / cm ² for 3 hours to obtain a deinking agent containing 20 mol of ethylene oxide and 20 mol of propylene oxide.

[Example 4] A deinking agent containing 40 mol of ethylene oxide and 10 mol of butylene oxide was obtained in the same manner as in Example 3 except that 352.4 g of ethylene oxide and 144.2 g of butylene oxide were used as the alkylene oxide.

[Example 5] A deinking agent containing 40 mol of ethylene oxide and 20 mol of propylene oxide was obtained in the same manner as in Example 3 except that 352.4 g of ethylene oxide and 232.3 g of propylene oxide were used as the alkylene oxide.

[Example 6] A deinking agent containing 40 mol of ethylene oxide and 40 mol of propylene oxide in the same manner as in Example 3 except that 352.4 g of ethylene oxide and 464.6 g of propylene oxide were used as the alkylene oxide and blowing of propylene oxide was performed for 4 hours. Got

[Example 7] As the alkylene oxide, 352.4 g of ethylene oxide and 464.6 g of propylene oxide were used, and 40 mol of ethylene oxide and 40 mol of ethylene oxide were used in the same manner as in the reaction conditions except that ethylene oxide and propylene oxide were simultaneously blown in and the reaction time was 6 hours. A random adduct deinking agent containing 40 mol of propylene oxide was obtained.

[Example 8] 40 mol of ethylene oxide and propylene oxide were carried out in the same manner as in Example 6 except that 352.4 g of ethylene oxide and 464.6 g of propylene oxide were used as the alkylene oxide, and the reaction conditions were that propylene oxide was blown in and then ethylene oxide was blown in and reacted. A deinking agent with a 40 mol adduct was obtained.

[Example 9] A deinking agent containing 40 mol of ethylene oxide and 80 mol of propylene oxide was obtained in the same manner as in Example 6 except that 352.4 g of ethylene oxide and 929.3 g of propylene oxide were used as the alkylene oxide.

Example 10 Ethylene oxide 1 was used in the same manner as in Example 3 except that 881.0 g of ethylene oxide and 1161.6 g of propylene oxide were used as the alkylene oxide, and the blowing of ethylene oxide was 4 hours and the blowing of propylene oxide was 5 hours.
A deinking agent having an addition amount of 00 mol and 100 mol of propylene oxide was obtained.

Example 11 Dimer acid 97 obtained by polymerization of tall oil fatty acid
%, Trimeric acid 2%, monomeric acid 1%, acid value 195, and average molecular weight 566, Haridimer 300 (manufactured by Harima Kasei Co., Ltd.) were used, except that 376.7 g of ethylene oxide and 496.7 g of propylene oxide were used as alkylene oxides. Similarly, an adduct of 40 mol of ethylene oxide and 40 mol of propylene oxide was obtained.

Example 12 Acid value 19 consisting of 25% dimer acid and 75% trimer acid
Haridimer 500 with an average molecular weight of 774 (manufactured by Harima Chemicals) ethylene oxide 413.2 g, propylene oxide
An adduct of 600 mol of ethylene oxide and 60 mol of propylene oxide was obtained in the same manner as in Example 11 except that 544.8 g was used.

Example 13 Ethylene oxide 9 was prepared in the same manner as in Example 12 except that 619.8 g of ethylene oxide and 272.4 g of propylene oxide were used.
An adduct of 0 mol and 30 mol of propylene oxide was obtained.

[Comparative Examples 2 to 5] Oleic acid, stearic acid and lauryl alcohol were used in place of the above tall oil fatty acid polymers, and oleic acid (EO) ₂₀ (PO) ₁₀ and oleic acid were prepared by the same reaction as in the examples.
(EO) ₂₀ (PO) ₂₀ , stearic acid (EO) ₂₀ (PO) ₂₀ , and lauryl alcohol (EO) ₂₀ (PO) ₂₀ were obtained.

[Deinking test example]

J. TAPP paper pulp test method No. According to 39-82, raw waste paper consisting of 80% offset printed newspaper and 20% leaflet is shredded into 3 × 3 cm pieces, a certain amount of which is put in a pulp disintegrator, warm water is added, and caustic soda 1 is added to the weight of used paper. 0.5%, No. 3 sodium silicate 3.0%, 30% hydrogen peroxide 3.0%, 0.3% of each deinking agent shown in Table 1, pulp concentration 4.0%, 30 separate solutions at 50 ° C And then at 50 ℃ 1
Aged for hours. Thereafter, water was added to dilute the pulp to 1.0%, and a flotation treatment was performed at 30 ° C. for 10 minutes. The pulp slurry after flotation is dehydrated with an 80 mesh wire and concentrated to 5%, and then water is added to dilute it to a pulp concentration of 1.0%.
A g / m ² pulp sheet was prepared.

The whiteness of the obtained pulp sheet was measured by a Hunter white altimeter according to JIS P8123.

The residual carbon is indicated by a simple method for measuring carbon in deinked pulp. The obtained pulp sheet is crushed with a household mixer, and 100 mg of this is put into an acetyl bromide / acetic acid (1/3 volume ratio) mixture. Cellulose was dissolved at 65 to 70 ° C. for 2 hours and filtered through an Advantech Toyo glass fiber filter (GS25, diameter 55 mm). The filter was air-dried and then measured with a color difference meter. The smaller the residual ink of the obtained recycled pulp sheet, the larger the residual carbon L value.

The results are also shown in Table 1.

Claims (2)

[Claims] 1. At least one dimer acid or polymer acid of a higher unsaturated fatty acid having 16 to 20 carbon atoms and 3 or more of one or more alkylene oxides having 2 to 4 carbon atoms.
A deinking agent for recycling used paper, which comprises, as a main component, a copolymer having no residual carboxyl group which has been addition-polymerized in an amount of not more than 00 mol. 2. The deinking agent for recycling used paper according to claim 1, wherein the alkylene oxide is ethylene oxide and propylene oxide, and is formed by random addition polymerization with respect to the dimer acid and the polymer acid.