JP3690509B2 - Cationic thermosetting resin aqueous solution and paper obtained by paper making using the cationic thermosetting resin aqueous solution - Google Patents

Description

【００２５】
実施例または比較例で得られたポリアミドポリアミン−エピクロロヒドリン樹脂溶液について、以下の評価を行った。
【００２６】
（１）貼り付き性試験
パルプ（Ｌ−ＢＫＰ）を離解したパルプスラリーに、実施例または比較例で得られた樹脂水溶液を対パルプ固形分比固形分で０．３％加えた。こうして得られたパルプスラリーについて、ＴＡＰＰＩスタンダードシートマシン（角型）にて坪量１００ｇ／ｍ^２となるように抄紙した。得られた湿紙は、樹脂板と重ね自動プレス機にて圧着し、湿紙を引張試験機にて剥がし、樹脂板に残った紙粉を採取し、乾燥させ、紙粉の重量を測定した。結果を表２に示す。
【００２７】
（２）湿潤紙力強度
パルプ（Ｌ−ＢＫＰ）を離解したパルプスラリーに、実施例または比較例で得られた樹脂水溶液を対パルプ固形分比固形分で０．３％加えた。こうして得られたパルプスラリーについて、ＴＡＰＰＩスタンダードシートマシン（角型）にて坪量１００ｇ／ｍ^２となるように抄紙した。得られた湿紙を、ロールプレスにて線圧１５ｋｇ／ｃｍでプレス脱水した。次いで、回転型乾燥機で１１０℃において４分間乾燥し、２３℃、５０％Ｒ．Ｈ．の条件下に２４時間調湿して、手抄きシートを作成した。得られた手抄きシートの湿潤紙力強度をＪＩＳ Ｐ８１３５に準じて測定した。結果を表２に示す。
【００２８】
【表２】

＊樹脂板へ貼り付いた紙粉量は、少ない方が貼り付き性良好。
【００２９】
表２から、ポリアミドポリアミン−エピハロヒドリン樹脂の組成として、疎水性カルボン酸類を含むことにより、湿潤紙力強度を得つつ、湿紙の貼り付き性を低減できていることが認められる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a wet paper strength enhancer comprising a cationic thermosetting resin aqueous solution, and a paper containing the wet paper strength enhancer . Wet strength agent obtained by the present invention is a perforated in the manufacture of paper dimensional stability and wet strength strength is required.
[0002]
[Prior art]
In recent years, the mounting density of electrical components has increased due to the reduction in the thickness and size of electrical products, and the conductor patterns of printed wiring boards have become thinner. Therefore, various performances such as processability, dimensional stability, and punchability have been required for laminated boards used as printed wiring boards.
[0003]
In general, a laminate is produced by impregnating a laminate base paper with a thermosetting resin such as phenol resin or epoxy resin, heating and drying it to form a semi-cured resin prepreg, laminating this prepreg, and thermoforming it. . Therefore, the laminated board base paper needs to be excellent in dimensional stability and high in strength, and a wet paper strength enhancer is used to achieve this purpose.
[0004]
As the wet paper strength enhancer, those having an affinity for these thermosetting resins are preferable, and melamine formalin resin has been widely used. Melamine formalin resin has a narrow papermaking pH range, and has a wet paper strength effect. There was a problem that it was not sufficient and contained harmful formalin. For this reason, in recent years, studies have been made to use polyamide polyamine-epihalohydrin resin instead of melamine formalin resin.
[0005]
[Problems to be solved by the invention]
However, when paper is produced using a polyamide polyamine-epihalohydrin resin, there is a problem that in the papermaking process, the press roll is easily wrinkled with wet paper, and in severe cases, paper breakage occurs and the productivity is lowered. . The present invention relates to a cationic thermosetting resin that reduces the occurrence of wrinkle of wet paper on a press roll and has excellent dimensional stability, and particularly provides sufficient wet paper strength when used in a laminated board base paper. An object of the present invention is to provide a wet paper strength enhancer comprising an aqueous solution, and further to provide a paper having excellent dimensional stability and sufficient wet strength by using the wet paper strength enhancer.
[0006]
[Means for Solving the Problems]
As a result of intensive studies to solve the above problems, the present inventor has found that the above problems can be solved by using a cationic thermosetting resin aqueous solution in which a hydrophobic carboxylic acid is reacted.
[0007]
That is, the present invention relates to (A) an aliphatic dibase that is at least one selected from the group consisting of (A) malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and esters thereof. Acids, (B) polyalkylene polyamine and (C) a compound obtained by reacting maleic anhydride with an alkene having 10 or more carbon atoms, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, aliphatic having 8 or more carbon atoms At least one hydrophobic carboxylic acid selected from the group consisting of monobasic acids and esters thereof is used as follows: (C) Hydrophobic carboxylic acids: (A) Use amount of aliphatic dibasic acid (weight) 0.5: 99. 5-10: in an aqueous solution containing a polyamide polyamine obtained by reacting with 90, obtained by reacting (D) epihalohydrins positive It relates wet strength agent consisting on thermosetting resin solution, to a paper obtained by addition to the paper making by use of the wet strength agent.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
The polyamide polyamine used in the present invention is (A) an aliphatic which is at least one selected from the group consisting of malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid and esters thereof Dibasic acids (hereinafter referred to as component (A)) , (B) polyalkylene polyamine and (C) a compound obtained by reacting maleic anhydride with an alkene having 10 or more carbon atoms, phthalic acid, phthalic anhydride, isophthalic acid And terephthalic acid, an aliphatic monobasic acid having 8 or more carbon atoms, and at least one hydrophobic carboxylic acid selected from the group consisting of these esters . Examples of ( B) polyalkylene polyamine (hereinafter referred to as component (B)) include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, iminobispropylamine and the like. (C) a compound obtained by reacting maleic anhydride with an alkene having 10 or more carbon atoms, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, an aliphatic monobasic acid having 8 or more carbon atoms and esters thereof Examples of at least one hydrophobic carboxylic acid selected from the group (hereinafter referred to as component (C)) include stearic acid, palmitic acid, and esters thereof, and water-insoluble dibasic acids include carbon. Examples thereof include compounds obtained by reacting maleic anhydride with several tens or more alkenes. The aromatic carboxylic acids are not particularly limited, and examples thereof include phthalic acid, isophthalic acid, terephthalic acid and esters thereof, and phthalic anhydride. The ester is not particularly limited, and known ones can be used. Usually, however, the alkyl ester of the hydrophobic carboxylic acid is used because of reactivity and availability. In the case of an ester of a dibasic acid, either a monoester in which one is an ester or both carboxylic acids may be in an ester. Among these, compounds obtained by reacting maleic anhydride with alkenes having 10 or more carbon atoms, phthalic acid, isophthalic acid, terephthalic acid, aliphatic monobasic acids having 8 or more carbon atoms, and esters thereof are used as press rolls. Since the sticking property of can be improved, it is preferable.
[0009]
The polyamide polyamine preferably has a viscosity of a 50% by weight aqueous solution at 25 ° C. of about 100 to 1000 mPa · s. When the aqueous solution viscosity of the polyamide polyamine is lower than 100 mPa · s, the final product polyamide polyamine-epihalohydrin resin does not have sufficient wet paper strength effect. When the polyamide polyamine is higher than 1000 mPa · s, the final product polyamidopolyamine-epihalohydrin resin is insufficient. The storage stability tends to be insufficient.
[0010]
The reaction of component (A), component (B) and component (C) is usually carried out in the presence or absence of a catalyst such as sulfuric acid, benzenesulfonic acid, paratoluenesulfonic acid and the like at a reaction temperature of 110 to 250 ° C. About 2 to 24 hours. Moreover, in order to adjust the aqueous solution viscosity of the obtained polyamidopolyamine within the above range, the molar ratio of the component (A) and the component (C) to the component (B) is set to 1: 0.9 to 1. It is preferable to use in the range of about 2. In addition, the usage-amount of (C) component needs to be about 0.5: 99.5-10: 90 by weight ratio of (C) component: (A) component. Component (C): By setting the component (A) to 0.5: 99.5 or more, the sticking property of the wet paper to the press roll can be suppressed, and by setting it to 10:90 or less, the wet paper strength Ru can prevent a reduction in strength.
[0011]
In the cationic thermosetting resin aqueous solution of the present invention, examples of (D) epihalohydrins (hereinafter referred to as (D) component) include epichlorohydrin, epibromohydrin, methyl epichlorohydrin, and the like. A mixture of two or more types can be used. Of these epihalohydrins, epichlorohydrin is most preferred.
[0012]
Water is added to the obtained polyamide polyamine to form an aqueous solution, which is then reacted with the component (D) to form a cationic thermosetting resin aqueous solution, which reacts with the components (A), (B) and (C). The polyamide polyamine thus prepared may be mixed with the polyamide polyamine reacted only with the component (A) and the component (B) and reacted with the component (D). Further, when the epihalohydrin is reacted with the polyamide polyamine, a component (B) may be newly added. The ratio of the component (D) to the polyamide polyamine is not particularly limited. However, since the amount of the low-molecular organic halogen compound is small, usually the secondary amino group of the polyamide polyamine and the epoxy group of the component (D) are used. It is preferably used so that the equivalent ratio (epoxy group / secondary amino group) is in the range of 0.8 to 2.0. In order to reduce the amount of low-molecular organic halogen compound produced, the equivalent ratio is more preferably 1.7 or less, and the storage stability of the polyamidopolyamine-epihalohydrin resin aqueous solution, the wet paper strength effect, and the like are taken into consideration. For example, the equivalent ratio is more preferably 0.9 or more.
[0013]
The reaction between the polyamide polyamine and the epihalohydrin includes a step of adding an epihalohydrin to the polyamide polyamine and a step of increasing the viscosity by crosslinking. The reaction temperature of such a reaction is usually preferably about 5 to 80 ° C., and the reaction solution is usually preferably about 20 to 70% by weight. Such reaction conditions can be adjusted as appropriate, but it is easy to suppress by-product formation of low-molecular-weight organic halogen compounds and the reaction can be easily controlled. Therefore, the reaction temperature is the temperature at which epihalohydrin is added to polyamide polyamine ( It is preferable to set it in two stages of 5 to 40 ° C .: primary insulation) and a temperature for further thickening (40 to 80 ° C .: secondary insulation). When the reaction temperature is set in two stages, it is preferable that the concentration of the reaction solution is equal to or lower than the concentration of the secondary temperature compared to the concentration of the primary temperature. The concentration of the reaction solution is preferably adjusted to, for example, about 30 to 70% by weight for the primary heat retention and about 20 to 40% by weight for the second heat retention.
[0014]
The reaction between the polyamide polyamine and the epihalohydrin is preferably carried out so that the viscosity of a 25 wt% aqueous solution of the finally obtained polyamide polyamine-epihalohydrin resin aqueous solution at 25 ° C. is in the range of about 10 to 500 mPa · s. . From the viewpoint of the performance of the final product as a wet paper strength agent, the viscosity of the aqueous solution is more preferably 10 mPa · s or more, and from the viewpoint of storage stability of the final product, it is preferably 500 mPa · s or less. From the standpoint of improving stickiness, it is more preferably 50 mPa · s or less. In order to adjust the viscosity of the polyamide polyamine-epihalohydrin resin aqueous solution to the above range, it is usually preferable to react for about 3 to 20 hours. In particular, when the reaction temperature is set in two stages, it is preferable that the primary heat retention time is about 1 to 10 hours, and the secondary heat retention time is about 0.5 to 10 hours.
[0015]
The wet paper strength enhancer comprising the polyamide polyamine-epichlorohydrin resin aqueous solution of the present invention thus obtained is adjusted to a concentration of the aqueous solution to about 10 to 30% by weight by adding water as necessary, for example, by a generally known method. , sulfuric acid, nitric acid, inorganic acids such as phosphoric acid, formic acid, Ru 2-4 about the tone pollock the pH of the aqueous solution by adding an organic acid such as acetic acid.
[0016]
The wet paper strength enhancer thus obtained is added to the pulp and can be made into paper by a generally known method. It should be noted that the amount of wet paper strength enhancer used varies depending on the use of the paper, and therefore it is necessary to determine it appropriately according to the use, but it is generally 0.05-1. About 0 parts by weight is appropriate.
[0017]
【The invention's effect】
The wet paper strength enhancer comprising the cationic thermosetting resin aqueous solution of the present invention has a wet paper strength enhancing effect. By using the wet paper strength enhancer of the present invention, generation of wet paper wrinkles in the press roll can be reduced in the paper making process without significantly reducing the wet strength, and the dimensional stability is excellent and sufficient wetness is achieved. Paper having paper strength can be produced. Further, unlike melamine formalin resin, since it does not contain formalin, it is preferable from the viewpoint of sanitary environment.
[0018]
【Example】
The present invention will be described more specifically with reference to the following examples, but the present invention is not limited to these examples. In each example, “%” is based on weight.
[0019]
Example 1
A flask equipped with a thermometer, a condenser, a stirrer and a nitrogen inlet tube was charged with 693.5 g (4.75 mol) of adipic acid, 62.1 g (0.25 mol) of stearic acid and 516 g (5 mol) of diethylenetriamine, The temperature was raised while excluding generated water from the system, and after reacting at 120 to 200 ° C. for 8 hours, 1100 g of water was gradually added to a polyamide polyamine aqueous solution having a solid content concentration of 50% and a viscosity of 300 mPa · s (25 ° C.). Got.
[0020]
In a flask equipped with a thermometer, a cooler and a stirrer, 238 g of water was added to 400 g of the polyamide polyamine aqueous solution obtained in Example 1 so that the concentration of the reaction solution was 40%, and epichlorohydrin 92 g (equivalent amount) at 15 ° C. Ratio (epoxy group of epichlorohydrin: secondary amino group of polyamide polyamine) = 1.1: 1) was added dropwise over 2 hours, then kept at 30 ° C. for 5 hours, and further 90 g of water was added. The temperature was raised to 60 ° C. and kept at that temperature for 2 hours. Subsequently, 360 g of water and 50 g of 62.5% sulfuric acid were added and cooled to obtain a polyamide polyamine-epichlorohydrin resin aqueous solution having a solid content concentration of 25%, a viscosity of 50 mPa · s (25 ° C.), and a pH of 3.0. . This is resin a.
[0021]
Examples 2-4
In Example 1, except that the hydrophobic carboxylic acids were changed as shown in Table 1, the same reaction as in Example 1 was performed to obtain a polyamide polyamine-epichlorohydrin resin solution having the same properties. These are designated as resins b, c, and d.
[0022]
Comparative Example 1
In Example 1, except that the composition of adipic acid, stearic acid and diethylenetriamine was changed as shown in Table 1, the same reaction as in Example 1 was performed to obtain a polyamide polyamine-epichlorohydrin resin solution having the same properties. It was. This is resin e.
[0023]
Comparative Example 2
In Example 1, except that the hydrophobic carboxylic acids were not used, the same reaction as in Example 1 was carried out with the composition shown in Table 1 to obtain a polyamide polyamine-epichlorohydrin resin solution having the same properties. This is resin f.
[0024]
[Table 1]

[0025]
The following evaluation was performed about the polyamide polyamine-epichlorohydrin resin solution obtained by the Example or the comparative example.
[0026]
(1) Stickability test To the pulp slurry from which the pulp (L-BKP) was disaggregated, 0.3% of the aqueous resin solution obtained in Examples or Comparative Examples was added in terms of solid content to pulp solid content. The pulp slurry thus obtained was paper-made with a TAPPI standard sheet machine (square) so as to have a basis weight of 100 g / m ² . The obtained wet paper was pressure-bonded with a resin plate with an automatic press machine, the wet paper was peeled off with a tensile tester, the paper powder remaining on the resin plate was collected, dried, and the weight of the paper powder was measured. . The results are shown in Table 2.
[0027]
(2) The aqueous resin solution obtained in Examples or Comparative Examples was added to the pulp slurry obtained by breaking up wet paper strength strength pulp (L-BKP) with a solid content ratio of 0.3% to pulp solid content. The pulp slurry thus obtained was paper-made with a TAPPI standard sheet machine (square) so as to have a basis weight of 100 g / m ² . The obtained wet paper was press dehydrated with a roll press at a linear pressure of 15 kg / cm. Subsequently, it dried for 4 minutes at 110 degreeC with a rotary dryer, and 23 degreeC and 50% R. H. The hand-sheet was prepared by adjusting the humidity for 24 hours under the above conditions. The wet paper strength of the obtained handsheet was measured according to JIS P8135. The results are shown in Table 2.
[0028]
[Table 2]

* The smaller the amount of paper dust stuck to the resin plate, the better the sticking property.
[0029]
From Table 2, it can be seen that, as a composition of the polyamide polyamine-epihalohydrin resin, by including hydrophobic carboxylic acids, wet paper strength can be reduced while wet paper strength is reduced.

Claims (3)

(A) Aliphatic dibasic acids which are at least one selected from the group consisting of malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid and esters thereof , (B) poly (C) compounds obtained by reacting maleic anhydride with (C) alkenes having 10 or more carbon atoms, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, aliphatic monobasic acids having 8 or more carbon atoms, and these At least one hydrophobic carboxylic acid selected from the group consisting of esters is (C) hydrophobic carboxylic acids: (A) aliphatic dibasic acid used (weight) of 0.5: 99.5 to 10:90 using an aqueous solution containing a polyamide polyamine obtained by reacting, (D) a cationic thermosetting resin obtained by reacting epihalohydrins Wet strength agent consisting of a solution. 2. The wet paper strength enhancer according to claim 1, wherein the viscosity of the 25% by weight aqueous solution at 25 ° C. is 10 to 500 mPa · s. A paper obtained by paper making using the wet paper strength enhancer according to claim 1 or 2 .