JP2516748B2 - Method for producing polyamide polyamine epichlorohydrin resin aqueous solution - Google Patents
Method for producing polyamide polyamine epichlorohydrin resin aqueous solutionInfo
- Publication number
- JP2516748B2 JP2516748B2 JP61213781A JP21378186A JP2516748B2 JP 2516748 B2 JP2516748 B2 JP 2516748B2 JP 61213781 A JP61213781 A JP 61213781A JP 21378186 A JP21378186 A JP 21378186A JP 2516748 B2 JP2516748 B2 JP 2516748B2
- Authority
- JP
- Japan
- Prior art keywords
- polyamide polyamine
- aqueous solution
- epichlorohydrin
- reaction
- viscosity
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 229920000768 polyamine Polymers 0.000 title claims description 102
- 239000004952 Polyamide Substances 0.000 title claims description 92
- 229920002647 polyamide Polymers 0.000 title claims description 92
- 239000007864 aqueous solution Substances 0.000 title claims description 71
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 title claims description 62
- 239000011347 resin Substances 0.000 title claims description 59
- 229920005989 resin Polymers 0.000 title claims description 59
- 238000004519 manufacturing process Methods 0.000 title claims description 28
- 239000007787 solid Substances 0.000 claims description 17
- 238000009833 condensation Methods 0.000 claims description 14
- 230000005494 condensation Effects 0.000 claims description 14
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 12
- 239000012467 final product Substances 0.000 claims description 12
- 125000001931 aliphatic group Chemical group 0.000 claims description 11
- 125000003277 amino group Chemical group 0.000 claims description 11
- 229920001281 polyalkylene Polymers 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 8
- 230000018044 dehydration Effects 0.000 claims description 6
- 238000006297 dehydration reaction Methods 0.000 claims description 6
- 238000005580 one pot reaction Methods 0.000 claims description 5
- 238000000691 measurement method Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 24
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 18
- 239000000123 paper Substances 0.000 description 16
- 239000000047 product Substances 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 11
- 238000001879 gelation Methods 0.000 description 11
- 239000001361 adipic acid Substances 0.000 description 9
- 235000011037 adipic acid Nutrition 0.000 description 9
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 8
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000000034 method Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000007865 diluting Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 238000007039 two-step reaction Methods 0.000 description 3
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000011087 paperboard Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229960001124 trientine Drugs 0.000 description 2
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 1
- YJLUBHOZZTYQIP-UHFFFAOYSA-N 2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CC2=C(CC1)NN=N2 YJLUBHOZZTYQIP-UHFFFAOYSA-N 0.000 description 1
- XYUINKARGUCCQJ-UHFFFAOYSA-N 3-imino-n-propylpropan-1-amine Chemical compound CCCNCCC=N XYUINKARGUCCQJ-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- CONKBQPVFMXDOV-QHCPKHFHSA-N 6-[(5S)-5-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-2-oxo-1,3-oxazolidin-3-yl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C[C@H]1CN(C(O1)=O)C1=CC2=C(NC(O2)=O)C=C1 CONKBQPVFMXDOV-QHCPKHFHSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000013055 pulp slurry Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/54—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen
- D21H17/55—Polyamides; Polyaminoamides; Polyester-amides
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polyamides (AREA)
- Paper (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は、紙、板紙の製造の際に添加して用いるポリ
アミドポリアミンエピクロルヒドリン樹脂水溶液の製造
方法に関する。TECHNICAL FIELD The present invention relates to a method for producing an aqueous solution of a polyamide polyamine epichlorohydrin resin, which is added during the production of paper or paperboard.
（従来の技術） 従来より、紙の製造工程において、ポリアミドポリア
ミンエピクロルヒドリン樹脂は、ティッシュペーパーや
紙タオルのような湿潤紙力を必要とする紙の湿潤紙力剤
として使用されるばかりでなく、印刷ならびに筆記用紙
あるいは板紙においても、アニオン性サイズ剤や填料の
定着率を向上させ、また水性を向上させる目的で広く
使用されている。(Prior Art) Conventionally, in a paper manufacturing process, polyamide polyamine epichlorohydrin resin has been used not only as a wet strength agent for papers requiring wet strength such as tissue paper and paper towel, but also for printing. In addition, it is also widely used in writing paper or paperboard for the purpose of improving the fixing rate of anionic sizing agents and fillers and improving the water resistance.
このようなポリアミドポリアミンエピクロルヒドリン
樹脂水溶液は、製品の固型分濃度が高い場合には、製品
の粘度安定性が悪化し、場合によってはゲル化にまで至
る。また、十分な紙の湿潤紙力を得るためには、該ポリ
アミドポリアミンエピクロルヒドリン樹脂の分子量を増
大させる必要があるが、このような場合には、同様に粘
度安定性が悪化し、同じくゲル化を生じる。Such a polyamide polyamine epichlorohydrin resin aqueous solution deteriorates the viscosity stability of the product when the solid content concentration of the product is high, and even leads to gelation in some cases. Further, in order to obtain sufficient wet paper strength of paper, it is necessary to increase the molecular weight of the polyamide polyamine epichlorohydrin resin, but in such a case, similarly, the viscosity stability is deteriorated and gelation is similarly caused. Occurs.
（発明が解決しようとする課題） 以上のような紙の湿潤紙力向上効果に優れ、かつ製品
の固型分濃度が高く、しかも安定性の優れたポリアミド
ポリアミンエピクロルヒドリン樹脂水溶液は得られなか
った点を改善するために、特開昭56−110727号公報に記
載されているように、脂肪族飽和二塩基酸とポリアルキ
レンポリアミンを所定比で所定粘度になるように110〜2
50℃で反応させ、さらにエピクロルヒドリンを所定比、
所定粘度になるように最初に30〜45℃、ついで50〜90℃
の二段階で反応させ、反応生成物のpHを３〜５に調整し
たポリアミドポリアミンエピクロルヒドリン樹脂水溶液
の製造方法が知られている。(Problems to be Solved by the Invention) An aqueous solution of polyamide polyamine epichlorohydrin resin, which is excellent in the effect of improving the wet strength of paper as described above, has a high solid content of the product, and is excellent in stability, cannot be obtained. In order to improve the above, as described in JP-A-56-110727, an aliphatic saturated dibasic acid and a polyalkylene polyamine are adjusted to have a predetermined viscosity at a predetermined ratio of 110 to 2
Reaction at 50 ℃, epichlorohydrin in a predetermined ratio,
30-45 ° C first, then 50-90 ° C to reach the desired viscosity
A method for producing an aqueous solution of a polyamide polyamine epichlorohydrin resin in which the pH of the reaction product is adjusted to 3 to 5 is known.
しかし、その好ましいものとして実施例に記載されて
いるものは、前者の110〜250℃の温度は180℃あるいは2
00℃であり、最終的に得られるポリアミドポリアミンエ
ピクロルヒドリン樹脂水溶液のpHは高くて4.2であり、
一方比較例ではpHを5.5にするとその最終樹脂溶液はゲ
ル化すること、後者の二段階反応を65℃で一段階反応さ
せると、そのようにして得られた製造直後の最終樹脂粘
度が二段階反応のものより低いにもかかわらず、その樹
脂溶液はゲル化することが記載されているから、結局、
この公報から窺うことができるものは、エピクロルヒド
リンを二段階反応させなければ安定な最終樹脂溶液は得
られないこと、その場合でもpHは4.2、その範囲を大き
くとっても３〜５とならざるを得ないということであ
る。However, what is described in the examples as the preferred one is that the former temperature of 110 to 250 ° C is 180 ° C or 2 ° C.
It is 00 ° C., and the pH of the finally obtained polyamide polyamine epichlorohydrin resin aqueous solution is 4.2 at the highest,
On the other hand, in Comparative Example, when the pH is set to 5.5, the final resin solution gels, and when the latter two-step reaction is carried out in one step at 65 ° C., the final resin viscosity immediately after production thus obtained is two-step. Although it is described that the resin solution gels even though it is lower than that of the reaction, after all,
What can be seen from this publication is that a stable final resin solution cannot be obtained unless the epichlorohydrin is reacted in two steps. In that case, the pH is 4.2, and even if the range is large, it must be 3-5. That's what it means.
このような二段階反応は、ポリアミドポリアミンとエ
ピクロルヒドリンとの反応は発熱反応であり、両者を単
に混合し撹拌するだけで温度が上昇するので、第一段目
の30〜45℃で反応させるためには温度が上がり過ぎない
ように発熱を制御する必要があり、また、その作業が煩
わしい等の生産性が悪いという問題がある。In such a two-step reaction, the reaction between the polyamide polyamine and epichlorohydrin is an exothermic reaction, and the temperature rises only by mixing and stirring the two, so that the reaction at 30 to 45 ° C in the first step is performed. However, there is a problem that it is necessary to control heat generation so that the temperature does not rise too much, and that the work is troublesome and productivity is poor.
（課題を解決するための手段） 本発明は、上記課題を解決するために、ポリアルキレ
ンポリアミンと脂肪族ジカルボン酸を加熱、脱水縮合
し、次いで得られたポリアミドポリアミンを水溶液中で
エピクロルヒドリンと反応させて、ポリアミドポリアミ
ンエピクロルヒドリン樹脂水溶液を製造する方法におい
て、 （ａ）ポリアルキレンポリアミンと脂肪族ジカルボン酸
のモル比が1.0:0.9〜1.1の範囲であって、その脱水縮合
させる際の加熱温度が135℃〜150℃の間であり、 （ｂ）上記（ａ）で得られたポリアミドポリアミンの50
％水溶液のブルックフィールド粘度計による25℃、毎分
60回転における粘度が300〜600センチポイズの間であ
り、 （ｃ）上記（ｂ）のポリアミドポリアミンの20〜50％水
溶液中で、該ポリアミドポリアミン中のアミノ基に対
し、1.2〜2.0当量のエピクロルヒドリンをその最終生成
物の固型分20％水溶液の上記測定法による粘度が30〜20
0センチポイズになるまで50〜80℃で一段階反応させる
こと を特徴とするポリアミドポリアミンエピクロルヒドリン
樹脂水溶液の製造方法を提供するものである。(Means for Solving the Problem) The present invention, in order to solve the above problems, a polyalkylene polyamine and an aliphatic dicarboxylic acid are heated and dehydrated and condensed, and then the obtained polyamide polyamine is reacted with epichlorohydrin in an aqueous solution. In the method for producing the polyamide polyamine epichlorohydrin resin aqueous solution, (a) the molar ratio of the polyalkylene polyamine and the aliphatic dicarboxylic acid is in the range of 1.0: 0.9 to 1.1, and the heating temperature for the dehydration condensation is 135 ° C. To 150 ° C., and (b) 50 of the polyamide polyamine obtained in (a) above.
% Aqueous solution at 25 ° C per minute with Brookfield viscometer
The viscosity at 60 revolutions is between 300 and 600 centipoise, and (c) in a 20 to 50% aqueous solution of the polyamide polyamine of (b) above, 1.2 to 2.0 equivalents of epichlorohydrin is added to the amino groups in the polyamide polyamine. The final product has a solid content of 20% and a viscosity of 30 to 20 by the above measurement method.
The present invention provides a method for producing an aqueous solution of a polyamide polyamine epichlorohydrin resin, which is characterized by carrying out a one-step reaction at 50 to 80 ° C until it reaches 0 centipoise.
本発明で使用するポリアルキレンポリアミンとして
は、ジエチレントリアミン、トリエチレンテトラミン、
テトラエチレンペンタミン、イミノビスプロピルアミン
等が代表的なものであり、これらは一種類のみでも、二
種類以上を併用して使用してもよい事はもちろんであ
る。また、脂肪族ジカルボン酸としては、シュウ酸、マ
ロン酸、コハク酸、グルタル酸、アジピン酸等が挙げら
れるが、これらのうち一種類もしくは二種類以上を併用
して使用することもできる。Examples of the polyalkylene polyamine used in the present invention include diethylene triamine, triethylene tetramine,
Tetraethylenepentamine, iminobispropylamine and the like are typical, and it goes without saying that these may be used alone or in combination of two or more. Further, examples of the aliphatic dicarboxylic acid include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid and the like, and one kind or a combination of two or more kinds of them can be used.
ポリアルキレンポリアミンと脂肪族カルボン酸のモル
比は、1.0:0.9〜1.1の範囲が好ましく、脂肪族ジカルボ
ン酸のモル比がこの範囲より多い場合には、最終生成物
の安定性が悪化する。また、同じく脂肪族ジカルボン酸
のモル比が上記範囲より少ない場合には生成ポリアミド
ポリアミンの粘度が上がりにくく、所定の粘度になるま
で冗長な反応時間が必要となり、生産性が低下する。The molar ratio of the polyalkylene polyamine to the aliphatic carboxylic acid is preferably in the range of 1.0: 0.9 to 1.1, and when the molar ratio of the aliphatic dicarboxylic acid is more than this range, the stability of the final product is deteriorated. Similarly, when the molar ratio of the aliphatic dicarboxylic acid is less than the above range, the viscosity of the produced polyamide polyamine is unlikely to increase, and a redundant reaction time is required until the viscosity reaches a predetermined value, which lowers the productivity.
ポリアルキレンポリアミンと脂肪族ジカルボン酸の縮
合温度を135℃〜150℃の範囲内に限定することが最終生
成物の性能、安定性にとって重要である。すなわち、縮
合温度が150℃より高い場合には、最終生成物の安定性
が著しく阻害される。一方、縮合温度が135℃未満で
は、縮合速度が遅く、所定の粘度に達するまで冗長な時
間が必要となり、生産性が著しく低下し、好ましくな
い。It is important for the performance and stability of the final product to limit the condensation temperature of the polyalkylene polyamine and the aliphatic dicarboxylic acid within the range of 135 ° C to 150 ° C. That is, when the condensation temperature is higher than 150 ° C, the stability of the final product is significantly impaired. On the other hand, if the condensation temperature is lower than 135 ° C., the condensation rate is slow and a long time is required until the viscosity reaches a predetermined value, which is not preferable because the productivity is remarkably reduced.
また、生成ポリアミドポリアミンは、50％水溶液の粘
度が300〜600cps（ブルックフィールド粘度計による25
℃、毎分60回転における粘度（センチポイズ）を示す、
以下同様）の範囲にあることが必要である。すなわち、
粘度が300cps未満では紙への湿潤紙力向上効果が不十分
である。また、粘度が600cpsより高くなるまで縮合を継
続した場合には、縮合温度が150℃以下であっても最終
生成物の安定性が阻害される。In addition, the generated polyamide polyamine has a viscosity of a 50% aqueous solution of 300 to 600 cps (25% by Brookfield viscometer).
Shows viscosity (centipoise) at 60 ° C / min,
The same shall apply hereinafter). That is,
If the viscosity is less than 300 cps, the effect of improving wet paper strength on paper is insufficient. Further, when the condensation is continued until the viscosity becomes higher than 600 cps, the stability of the final product is impaired even if the condensation temperature is 150 ° C or lower.
以上述べたように、ポリアルキレンポリアミンと脂肪
族ジカルボン酸をモル比で1.0:0.9〜1.11の割合にて135
℃〜150℃の温度範囲内で縮合し、生成ポリアミドポリ
アミンの50％水溶液の粘度が300〜600cpsになるまで反
応を行うことが、最終生成物の安定性向上のために必要
となる。As described above, the polyalkylene polyamine and the aliphatic dicarboxylic acid are mixed at a molar ratio of 1.0: 0.9 to 1.11.
In order to improve the stability of the final product, it is necessary to carry out the condensation within a temperature range of ℃ to 150 ℃ and to carry out the reaction until the viscosity of a 50% aqueous solution of the polyamide polyamine is 300 to 600 cps.
次いで、上記のようにして得られたポリアミドポリア
ミンを必要に応じて水で希釈して、20〜50％水溶液と
し、ポリアミドポリアミン中のアミノ基に対し1.2〜2.0
当量のエピクロルヒドリンと反応させる。エピクロルヒ
ドリンのポリアミドポリアミン中のアミノ基に対する反
応割合が1.2当量より少ない場合、反応終了後、最終生
成物の安定性が悪く、40℃にて保存した場合には、数日
経過後ゲル化する。一方、エピクロルヒドリンの反応割
合が2.0当量より多い場合には、十分な湿潤紙力を得る
ことができない。Then, the polyamide polyamine obtained as described above is diluted with water as necessary to give a 20 to 50% aqueous solution, which is 1.2 to 2.0 with respect to the amino groups in the polyamide polyamine.
React with an equivalent amount of epichlorohydrin. When the reaction ratio of epichlorohydrin to the amino group in the polyamide polyamine is less than 1.2 equivalents, the stability of the final product is poor after the reaction is completed, and the gelation occurs after several days when stored at 40 ° C. On the other hand, when the reaction ratio of epichlorohydrin is more than 2.0 equivalents, sufficient wet strength cannot be obtained.
ポリアミドポリアミンとエピクロルヒドリンの反応は
30℃〜80℃の範囲で行うが、最終生成物の20％水溶液の
粘度が30〜200cpsになるまで継続する。20％水溶液の粘
度が30cps未満であると、紙の湿潤紙力向上効果が不十
分であり、また、200cpsより大きいと、最終生成物の安
定性が悪くなるばかりか、抄紙工程においてパルプスラ
リー中に添加した時、発泡を生じさせ好ましくない。こ
のように、最終生成物の20％水溶液の粘度が30〜200cps
になるまで反応させた後、最終生成物の固型分濃度が20
〜40％になるように水で希釈調整し、次いで酸を加えて
pHを３〜６に調整する。ここで使用する酸としては硫
酸、塩酸等の無機酸及び、ギ酸、酢酸等の有機酸が挙げ
られる。The reaction between polyamide polyamine and epichlorohydrin is
Perform in the range of 30 ° C to 80 ° C, but continue until the viscosity of a 20% aqueous solution of the final product reaches 30 to 200 cps. If the viscosity of the 20% aqueous solution is less than 30 cps, the effect of improving the wet strength of paper is insufficient, and if it exceeds 200 cps, not only the stability of the final product deteriorates, but also the pulp slurry in the papermaking process is deteriorated. When added to, unfavorably it causes foaming. Thus, the 20% aqueous solution of the final product has a viscosity of 30-200 cps.
Until the solids concentration of the final product is 20
Dilute with water to adjust to ~ 40%, then add acid
Adjust pH to 3-6. Examples of the acid used here include inorganic acids such as sulfuric acid and hydrochloric acid, and organic acids such as formic acid and acetic acid.
以下に本発明について実施例、比較例及び応用例によ
り説明する。The present invention will be described below with reference to examples, comparative examples and application examples.
（実施例） 実施例 １ １−１ ポリアミドポリアミン樹脂の製造 温度計、冷却管および攪拌棒を備えた四つ口フラスコ
に、ジエチレントリアミン103g（１モル）とアジピン酸
146g（１モル）を仕込み、窒素気流下145℃で脱水しな
がら反応を９時間行った後、水200gを徐々に加え、ポリ
アミドポリアミンの52.4％水溶液を得た。この生成ポリ
アミドポリアミンの50％水溶液の粘度は437cpsであっ
た。(Example) Example 1-1 1-1 Production of Polyamide Polyamine Resin In a four-necked flask equipped with a thermometer, a cooling tube and a stirring rod, 103 g (1 mol) of diethylenetriamine and adipic acid were added.
After charging 146 g (1 mol) and performing the reaction for 9 hours while dehydrating at 145 ° C. under a nitrogen stream, 200 g of water was gradually added to obtain a 52.4% aqueous solution of polyamide polyamine. The viscosity of a 50% aqueous solution of the produced polyamide polyamine was 437 cps.
１−２ ポリアミドポリアミンエピクロルヒドリン樹脂
の製造 実施例１−１と同様の反応容器に、実施例１−１で得
られた固型分濃度52.4％のポリアミドポリアミン122.0g
を仕込み、次いで水148.2gを加えて稀釈後、エピクロル
ヒドリン47.2gを加え、70℃に昇温してそのまま４時間
加熱攪拌した。その後、水22.2g、濃硫酸1.5gを順次加
え、冷却して固型分濃度30.5％、pH5.2のポリアミドポ
リアミンエピクロルヒドリン樹脂水溶液を得た。この物
の20％水溶液の粘度は82cpsであった。なお本反応にお
けるポリアミドポリアミン中のアミノ基１当量に対する
エピクロルヒドリンの当量数は1.70である。この樹脂水
溶液は40℃に保存した場合、一ケ月以上経てもゲル化に
は至らなかった。1-2 Production of Polyamide Polyamine Epichlorohydrin Resin 122.0 g of polyamide polyamine having a solid content concentration of 52.4% obtained in Example 1-1 was placed in the same reaction vessel as in Example 1-1.
Then, 148.2 g of water was added and diluted, 47.2 g of epichlorohydrin was added, the temperature was raised to 70 ° C., and the mixture was heated and stirred for 4 hours. Then, 22.2 g of water and 1.5 g of concentrated sulfuric acid were sequentially added and cooled to obtain a polyamide polyamine epichlorohydrin resin aqueous solution having a solid content concentration of 30.5% and a pH of 5.2. The viscosity of a 20% aqueous solution of this product was 82 cps. In this reaction, the equivalent number of epichlorohydrin is 1.70 with respect to 1 equivalent of the amino group in the polyamide polyamine. When this resin aqueous solution was stored at 40 ° C, gelation did not occur even after one month or more.
実施例 ２ ２−１ ポリアミドポリアミン樹脂の製造 実施例１と同様の反応容器に、ジエチレントリアミン
103g（１モル）とアジピン酸150.4g（1.03モル）を仕込
み、窒素気流下135℃で脱水しながら反応を11時間行っ
た後、水200gを徐々に加え、ポリアミドポリアミンの5
3.8％水溶液を得た。この生成ポリアミドポリアミンの5
0％水溶液の粘度は390cpsであった。Example 22-1 Production of Polyamide Polyamine Resin Diethylenetriamine was placed in the same reaction vessel as in Example 1.
After charging 103 g (1 mol) and 150.4 g (1.03 mol) of adipic acid and performing the reaction for 11 hours while dehydrating under a nitrogen stream at 135 ° C., 200 g of water was gradually added to give 5 parts of polyamide polyamine.
A 3.8% aqueous solution was obtained. 5 of this produced polyamide polyamine
The viscosity of the 0% aqueous solution was 390 cps.
２−２ ポリアミドポリアミンエピクロルヒドリン樹脂
の製造 実施例１と同様の反応容器に、実施例２−１で得られ
た53.8％ポリアミドポリアミン121.2gを仕込み、次いで
水86.5gで稀釈後、エピクロルヒドリン51.3gを加え、65
℃に昇温して、そのまま3.5時間加熱攪拌した。その
後、水50.1g、濃硫酸2.0gを順次加え、冷却して固型分
濃度35.2％、pH5.5のポリアミドポリアミンエピクロル
ヒドリン樹脂水溶液を得た。このものの20％水溶液の粘
度は52cpsであった。なお本反応におけるポリアミドポ
リアミン中のアミノ基１当量に対するエピクロルヒドリ
ンの当量数は1.85である。この樹脂水溶液は40℃に保存
した場合、一ケ月以上経てもゲル化には至らなかった。2-2 Manufacture of Polyamide Polyamine Epichlorohydrin Resin In a reaction vessel similar to that of Example 1, 121.2 g of 53.8% polyamide polyamine obtained in Example 2-1 was charged, and after diluting with 86.5 g of water, 51.3 g of epichlorohydrin was added. , 65
The temperature was raised to ℃ and the mixture was heated and stirred as it was for 3.5 hours. Thereafter, 50.1 g of water and 2.0 g of concentrated sulfuric acid were sequentially added and cooled to obtain a polyamide polyamine epichlorohydrin resin aqueous solution having a solid content concentration of 35.2% and a pH of 5.5. The viscosity of a 20% aqueous solution of this product was 52 cps. The equivalent number of epichlorohydrin to 1 equivalent of amino group in the polyamide polyamine in this reaction is 1.85. When this resin aqueous solution was stored at 40 ° C, gelation did not occur even after one month or more.
実施例 ３ ３−１ ポリアミドポリアミン樹脂の製造 実施例１と同様の反応容器に、ジエチレントリアミン
103g（１モル）とアジピン酸143.1g（0.98モル）を仕込
み、窒素気流下150℃で脱水しながら反応を10時間行っ
た後、水200gを徐々に加え、ポリアミドポリアミンの5
1.7％水溶液を得た。この生成ポリアミドポリアミンの5
0％水溶液の粘度は452cpsであった。Example 3 3-1 Production of Polyamide Polyamine Resin In a reaction vessel similar to that in Example 1, diethylenetriamine was added.
Charge 103 g (1 mol) and adipic acid 143.1 g (0.98 mol), carry out the reaction for 10 hours while dehydrating under a nitrogen stream at 150 ° C., and then gradually add 200 g of water to obtain 5 parts of polyamide polyamine.
A 1.7% aqueous solution was obtained. 5 of this produced polyamide polyamine
The viscosity of the 0% aqueous solution was 452 cps.
３−２ ポリアミドポリアミンエピクロルヒドリン樹脂
の製造 実施例１と同様の反応容器に、実施例３−１で得られ
た51.7％ポリアミドポリアミン122.3gを仕込み、次いで
水130.6gで稀釈後、エピクロルヒドリン50.0gを加え、7
0℃に昇温し、そのまま3.5時間加熱攪拌した。その後、
水44.0g、濃硫酸2.0gを順次加え、冷却して固型分濃度3
0.1％、pH4.6のポリアミドポリアミンエピクロルヒドリ
ン樹脂水溶液を得た。このものの20％水溶液の粘度は74
cpsであった、なお本反応におけるポリアミドポリアミ
ン中のアミノ基１当量に対するエピクロルヒドリンの当
量数は1.80である。この樹脂水溶液は40℃に保存した場
合、一ケ月以上経てもゲル化には至らなかった。3-2 Production of Polyamide Polyamine Epichlorohydrin Resin In a reaction vessel similar to that in Example 1, 122.3 g of 51.7% polyamide polyamine obtained in Example 3-1 was charged, and then diluted with 130.6 g of water, and then 50.0 g of epichlorohydrin was added. , 7
The temperature was raised to 0 ° C., and the mixture was heated and stirred as it was for 3.5 hours. afterwards,
Add 44.0 g of water and 2.0 g of concentrated sulfuric acid in sequence and cool to obtain a solid content of 3
A 0.1% aqueous solution of polyamide polyamine epichlorohydrin resin having a pH of 4.6 was obtained. The viscosity of a 20% aqueous solution of this is 74
It was cps, and the equivalent number of epichlorohydrin to 1 equivalent of amino groups in the polyamide polyamine in this reaction is 1.80. When this resin aqueous solution was stored at 40 ° C, gelation did not occur even after one month or more.
実施例 ４ ４−１ ポリアミドポリアミン樹脂の製造 実施例１と同様の反応容器に、ジエチレントリアミン
103g（１モル）のアジピン酸146g（１モル）を仕込み、
窒素気流下140℃で脱水しながら反応を10時間行った
後、水200gを徐々に加え、ポリアミドポリアミンの52.0
％水溶液を得た。この生成ポリアミドポリアミンの50％
水溶液の粘度は375cpsであった。Example 4 4-1 Production of Polyamide Polyamine Resin In a reaction vessel similar to that in Example 1, diethylenetriamine was added.
Charge 103 g (1 mol) of adipic acid 146 g (1 mol),
After performing the reaction for 10 hours while dehydrating at 140 ° C. under a nitrogen stream, 200 g of water was gradually added, and the polyamide polyamine of 52.0 was added.
% Aqueous solution was obtained. 50% of this produced polyamide polyamine
The viscosity of the aqueous solution was 375 cps.
４−２ ポリアミドポリアミンエピクロルヒドリン樹脂
の製造 実施例１と同様の反応容器に、実施例４−１で得られ
た52.0％ポリアミドポリアミン122.9gを仕込み、次いで
水90.1gで稀釈後、エピクロルヒドリン48.6gを加え、55
℃に昇温して、そのまま2.5時間加熱攪拌した。その
後、水34.4g、濃硫酸2.5gを順次加え、冷却して固型分
濃度36.1％、pH4.1のポリアミドポリアミンエピクロル
ヒドリン樹脂水溶液を得た。このものの20％水溶液の粘
度は42cpsであった。なお本反応におけるポリアミドポ
リアミン中のアミノ基１当量に対するエピクロルヒドリ
ンの当量数は1.75である。この樹脂水溶液は40℃に保存
した場合、一ケ月以上経てもゲル化には至らなかった。4-2 Production of Polyamide Polyamine Epichlorohydrin Resin In a reaction vessel similar to that of Example 1, 122.9 g of 52.0% polyamide polyamine obtained in Example 4-1 was charged, and after diluting with 90.1 g of water, 48.6 g of epichlorohydrin was added. , 55
The temperature was raised to ° C and the mixture was heated and stirred for 2.5 hours as it was. Then, 34.4 g of water and 2.5 g of concentrated sulfuric acid were sequentially added and cooled to obtain a polyamide polyamine epichlorohydrin resin aqueous solution having a solid content concentration of 36.1% and a pH of 4.1. The viscosity of a 20% aqueous solution of this product was 42 cps. In this reaction, the equivalent number of epichlorohydrin is 1.75 with respect to 1 equivalent of amino group in polyamide polyamine. When this resin aqueous solution was stored at 40 ° C, gelation did not occur even after one month or more.
実施例 ５ ５−１ ポリアミドポリアミン樹脂の製造 実施例１と同様の反応容器に、トリエチレンテトラミ
ン144g（１モル）とアジピン酸146g（１モル）を仕込
み、窒素気流下135℃で脱水しながら反応を12時間行っ
た後、水230gを徐々に加え、ポリアミドポリアミンの5
3.1％水溶液を得た。この生成ポリアミドポリアミンの5
0％水溶液の粘度は345cpsであった。Example 5 5-1 Production of Polyamide Polyamine Resin To a reaction vessel similar to that in Example 1, 144 g (1 mol) of triethylenetetramine and 146 g (1 mol) of adipic acid were charged, and the reaction was carried out while dehydrating at 135 ° C. under a nitrogen stream. For 12 hours, gradually add 230 g of water and add 5% of polyamide polyamine.
A 3.1% aqueous solution was obtained. 5 of this produced polyamide polyamine
The viscosity of the 0% aqueous solution was 345 cps.
５−２ ポリアミドポリアミンエピクロルヒドリン樹脂
の製造 実施例１と同様の反応容器に、実施例５−１で得られ
た53.1％ポリアミドポリアミン71.8gを仕込み、次いで
水123.9gで稀釈後、エピクロルヒドリン50.0gを加え、6
0℃に昇温して、そのまま４時間加熱攪拌した。その
後、水60.9g、濃硫酸2.0gを順次加え、冷却して固型分
濃度25.8％、pH4.9のポリアミドポリアミンエピクロル
ヒドリン樹脂水溶液を得た。このものの20％水溶液の粘
度は91cpsであった。なお本反応におけるポリアミドポ
リアミン中のアミノ基１当量に対するエピクロルヒドリ
ンの当量数は1.80である。この樹脂水溶液は40℃に保存
した場合、一ケ月以上経てもゲル化には至らなかった。5-2 Production of Polyamide Polyamine Epichlorohydrin Resin A reaction vessel similar to that of Example 1 was charged with 71.8 g of 53.1% polyamide polyamine obtained in Example 5-1 and then diluted with 123.9 g of water, and then 50.0 g of epichlorohydrin was added. , 6
The temperature was raised to 0 ° C., and the mixture was heated and stirred as it was for 4 hours. Then, 60.9 g of water and 2.0 g of concentrated sulfuric acid were sequentially added and cooled to obtain a polyamide polyamine epichlorohydrin resin aqueous solution having a solid content concentration of 25.8% and a pH of 4.9. The viscosity of a 20% aqueous solution of this product was 91 cps. In this reaction, the equivalent number of epichlorohydrin is 1.80 with respect to 1 equivalent of amino group in the polyamide polyamine. When this resin aqueous solution was stored at 40 ° C, gelation did not occur even after one month or more.
実施例 ６ ６−１ ポリアミドポリアミン樹脂の製造 実施例１と同様の反応容器に、ジエチレントリアミン
103g（１モル）とアジピン酸148.9g（1.02モル）を仕込
み、窒素気流下150℃で脱水しながら反応を12時間行っ
た後、水200gを徐々に加え、ポリアミドポリアミンの5
1.7％水溶液を得た。この生成ポリアミドポリアミンの5
0％水溶液の粘度は530cpsであった。Example 6 6-1 Production of Polyamide Polyamine Resin In a reaction vessel similar to that in Example 1, diethylenetriamine was added.
103 g (1 mol) and 148.9 g (1.02 mol) of adipic acid were charged, the reaction was carried out for 12 hours while dehydrating at 150 ° C under a nitrogen stream, and then 200 g of water was gradually added to the polyamide polyamine 5
A 1.7% aqueous solution was obtained. 5 of this produced polyamide polyamine
The viscosity of the 0% aqueous solution was 530 cps.
６−２ ポリアミドポリアミンエピクロルヒドリン樹脂
の製造 実施例１と同様の反応容器に、実施例６−１で得られ
た51.7％ポリアミドポリアミン125.3gを仕込み、次いで
水133.8gで稀釈後、エピクロルヒドリン50.0gを加え、6
0℃に昇温して、そのまま3.5時間加熱攪拌した。その
後、水105.7g、濃硫酸1.5gを順次加え、冷却して固型分
濃度24.9％、pH4.7のポリアミドポリアミンエピクロル
ヒドリン樹脂水溶液を得た。このものの20％水溶液の粘
度は105cpsであった。なお本反応におけるポリアミドポ
リアミン中のアミノ基１当量に対するエピクロルヒドリ
ンの当量数は1.80である。この樹脂水溶液は40℃に保存
した場合、一ケ月以上経てもゲル化には至らなかった。6-2 Production of Polyamide Polyamine Epichlorohydrin Resin In a reaction vessel similar to that of Example 1, 125.3 g of 51.7% polyamide polyamine obtained in Example 6-1 was charged, and after diluting with 133.8 g of water, 50.0 g of epichlorohydrin was added. , 6
The temperature was raised to 0 ° C., and the mixture was heated and stirred for 3.5 hours as it was. Then, 105.7 g of water and 1.5 g of concentrated sulfuric acid were sequentially added and cooled to obtain a polyamide polyamine epichlorohydrin resin aqueous solution having a solid content concentration of 24.9% and a pH of 4.7. The viscosity of this 20% aqueous solution was 105 cps. In this reaction, the equivalent number of epichlorohydrin is 1.80 with respect to 1 equivalent of amino group in the polyamide polyamine. When this resin aqueous solution was stored at 40 ° C, gelation did not occur even after one month or more.
比較例 １〜３ 比較例 １ １−１ ポリアミドポリアミン樹脂の製造 ジエチレントリアミンとアジピン酸の脱水縮合反応を
165℃で４時間行ったほかは、実施例１−１と同様の反
応を行い、ポリアミドポリアミンの51.6％水溶液を得
た。この生成ポリアミドポリアミンの50％水溶液の粘度
は445cpsであった。Comparative Examples 1 to 3 Comparative Example 1 1-1 Production of Polyamide Polyamine Resin The dehydration condensation reaction of diethylenetriamine and adipic acid was conducted.
The same reaction as in Example 1-1 was carried out except that the reaction was carried out at 165 ° C. for 4 hours to obtain a 51.6% aqueous solution of polyamidepolyamine. The viscosity of a 50% aqueous solution of the produced polyamide polyamine was 445 cps.
１−２ ポリアミドポリアミンエピクロルヒドリン樹脂
の製造 比較例１−１で得られたポリアミドポリアミンを用い
たほかは、実施例１−２と同様の反応を行い、固型分濃
度30.2％、pH5.4のポリアミドポリアミンエピクロルヒ
ドリン樹脂水溶液を得た。このものの20％水溶液の粘度
は88cpsであった。この樹脂水溶液は40℃にて保存した
場合、三日でゲル化した。1-2 Production of Polyamide Polyamine Epichlorohydrin Resin A polyamide having a solid content concentration of 30.2% and a pH of 5.4 was prepared by the same reaction as in Example 1-2 except that the polyamide polyamine obtained in Comparative Example 1-1 was used. An aqueous solution of polyamine epichlorohydrin resin was obtained. The viscosity of a 20% aqueous solution of this product was 88 cps. When this resin aqueous solution was stored at 40 ° C., it gelled in 3 days.
比較例 ２ ２−１ ポリアミドポリアミン樹脂の製造 ジエチレントリアミンとアジピン酸の脱水縮合反応を
125℃で24時間行ったほかは、実施例１−１と同様の反
応を行い、ポリアミドポリアミンの52.8％水溶液を得
た。この生成ポリアミドポリアミンの50％水溶液の粘度
は225cpsであった。Comparative Example 22-1 Production of Polyamide Polyamine Resin A dehydration condensation reaction of diethylenetriamine and adipic acid was conducted.
The same reaction as in Example 1-1 was carried out except that the reaction was carried out at 125 ° C. for 24 hours to obtain a 52.8% aqueous solution of polyamidepolyamine. The viscosity of a 50% aqueous solution of the produced polyamide polyamine was 225 cps.
２−２ ポリアミドポリアミンエピクロルヒドリン樹脂
の製造 比較例２−１で得られたポリアミドポリアミンを用い
たほかは、実施例１−２と同様の反応を行い、固型分濃
度30.9％、pH5.6のポリアミドポリアミンエピクロルヒ
ドリン樹脂水溶液を得た。このものの20％水溶液の粘度
は76cpsであった。この樹脂水溶液は40℃にて保存した
場合、二日でゲル化した。2-2 Production of Polyamide Polyamine Epichlorohydrin Resin Polyamide having a solid content concentration of 30.9% and a pH of 5.6 except that the polyamide polyamine obtained in Comparative Example 2-1 was used. An aqueous solution of polyamine epichlorohydrin resin was obtained. The viscosity of a 20% aqueous solution of this product was 76 cps. When this resin aqueous solution was stored at 40 ° C, it gelled in 2 days.
比較例 ３ ポリアミドポリアミンエピクロルヒドリン樹脂の製造 実施例１−１と同様の反応容器に比較例２−１で得ら
れた52.8％ポリアミドポリアミン121.0gを仕込み、次い
で水155.3gで稀釈後、エピクロルヒドリン50.5gを加
え、70℃に昇温して、そのまま4.5時間加熱攪拌した。
その後、水22.2g、濃硫酸1.5gを順次加え、冷却して固
型分濃度30.1％、pH5.3のポリアミドポリアミンエピク
ロルヒドリン樹脂水溶液を得た。このものの20％水溶液
の粘度は74cpsであった。なお本反応におけるポリアミ
ドポリアミン中のアミノ基１当量に対するエピクロルヒ
ドリンの当量数は1.82である。この樹脂水溶液は40℃に
保存した場合、一ケ月以上経てもゲル化には至らなかっ
た。Comparative Example 3 Preparation of Polyamide Polyamine Epichlorohydrin Resin 121.0 g of 52.8% polyamide polyamine obtained in Comparative Example 2-1 was charged in the same reaction vessel as in Example 1-1, and then diluted with 155.3 g of water, and then 50.5 g of epichlorohydrin was added. In addition, the temperature was raised to 70 ° C., and the mixture was heated and stirred as it was for 4.5 hours.
Then, 22.2 g of water and 1.5 g of concentrated sulfuric acid were sequentially added and cooled to obtain a polyamide polyamine epichlorohydrin resin aqueous solution having a solid content concentration of 30.1% and a pH of 5.3. The viscosity of a 20% aqueous solution of this product was 74 cps. The equivalent number of epichlorohydrin to 1.8 equivalents of amino groups in the polyamide polyamine in this reaction is 1.82. When this resin aqueous solution was stored at 40 ° C, gelation did not occur even after one month or more.
応用例 実施例１−６及び比較例３で得られたポリアミドポリ
アミンエピクロルヒドリン樹脂を下記に示す条件の抄紙
試験に供し、得られた手抄き紙の紙力をJIS法により測
定した。その結果を次表に示す。Application Example The polyamide polyamine epichlorohydrin resins obtained in Examples 1-6 and Comparative Example 3 were subjected to a papermaking test under the conditions shown below, and the paper strength of the obtained handmade paper was measured by the JIS method. The results are shown in the table below.
以上の結果からは、実施例中pHの一番高い実施例２の
pH5.5のポリアミドポリアミンエピクロルヒドリン樹脂
水溶液は安定であり、一方比較例１のものはポリアミド
ポリアミン樹脂製造時の縮合温度が165℃と高いため、
最終的に得られるpH5.4のポリアミドポリアミンエピク
ロルヒドリン樹脂水溶液は不安定であることが分り、ま
た、比較例２からはその縮合温度が125℃と低いと、反
応時間が24時間にもなり、これは実施例のうち一番反応
時間の長い実施例６のその時間が12時間であるのと比べ
ると２倍にもなり、生産性が悪いことが分かる。From the above results, it can be seen that in Example 2 having the highest pH among the Examples.
The polyamide polyamine epichlorohydrin resin aqueous solution having a pH of 5.5 is stable, while the one of Comparative Example 1 has a high condensation temperature of 165 ° C. during the production of the polyamide polyamine resin,
It was found that the finally obtained aqueous solution of the polyamide polyamine epichlorohydrin resin of pH 5.4 was unstable, and from Comparative Example 2, when the condensation temperature was as low as 125 ° C., the reaction time was as long as 24 hours. In comparison with Example 6, which has the longest reaction time among Examples, the time is 12 hours, which is twice that of Example 6, and it can be seen that productivity is poor.
抄紙条件 抄紙機：ノーブル アンド ウッド式抄紙試験機 使用パルプ:LBKP/NBKP＝1/1 フリーネス:465ml 用水pH:7.0 樹脂添加量:0.3％（対パルプ固型分比） 乾燥条件:100℃×１分（回転式ドライヤー） （発明の効果） 本発明の方法に従い製造されたポリアミドポリアミン
エピクロルヒドリン樹脂水溶液は、従来より市販されて
いるポリアミドポリアミンエピクロルヒドリン樹脂水溶
液に比較して、優れた湿潤紙力向上効果を有し、かつ製
品の固型分濃度が高い場合でもその保存性に優れてい
る。 Papermaking machine Papermaking machine: Noble and Wood type papermaking machine Pulp used: LBKP / NBKP = 1/1 Freeness: 465 ml Water pH: 7.0 Resin addition amount: 0.3% (ratio to pulp solids) Drying condition: 100 ℃ × 1 Minute (rotary dryer) (Effect of the invention) The polyamide polyamine epichlorohydrin resin aqueous solution produced according to the method of the present invention has an excellent wet paper strength improving effect as compared with conventionally commercially available polyamide polyamine epichlorohydrin resin aqueous solutions. It has excellent storage stability even when it has a high solid content of the product.
また、本発明においては、上記（ａ）のポリアルキレ
ンポリアミンと脂肪族ジカルボン酸の脱水縮合におい
て、その加熱温度を135〜150℃とし、かつ上記（ｃ）の
ポリアミドポリアミンとエピクロルヒドリンとの反応を
50〜80℃で一段階反応させたので、従来は前者の加熱温
度を例えば180℃と高くし、そのように高くすると後者
の反応を一段階反応させる場合その生成物の樹脂水溶液
はゲル化し易いので、後者を低温と高温の二段階反応と
することによってその危険を回避せざるを得ず、その結
果後者の反応を行わせる際には低温時の反応でポリアミ
ドポリアミンとエピクロルヒドリンとの発熱反応を制御
して温度が上がり過ぎないように所定の低温に維持しな
ければならないということや、作業が煩わしい等の生産
性の点で問題があり、一方上記の加熱温度の180℃を例
えば120℃のように低くすると反応をさせる作業能率が
悪く、いずれも改善する必要があった点を、前者の脱水
縮合のための加熱温度を180℃よりはかなり低く、しか
もその反応をさせる作業能率を害さない最適範囲に抑え
ることにより後者の一段階反応を行った場合でもそのゲ
ル化を回避することができ、これにより作業性を向上さ
せ、製造時間を短縮し、生産性を向上させることができ
る。Further, in the present invention, in the dehydration condensation of the polyalkylene polyamine of (a) and the aliphatic dicarboxylic acid, the heating temperature is set to 135 to 150 ° C., and the reaction of the polyamide polyamine of (c) with epichlorohydrin is carried out.
Since the one-step reaction was carried out at 50 to 80 ° C, the heating temperature of the former was conventionally increased to 180 ° C, and when such a reaction was carried out in the one-step reaction of the latter, the resin aqueous solution of the product was easily gelled. Therefore, there is no choice but to avoid the danger by making the latter a two-step reaction of low temperature and high temperature, and as a result, when carrying out the latter reaction, the exothermic reaction between polyamide polyamine and epichlorohydrin is caused by the reaction at low temperature. There is a problem in terms of productivity that the temperature must be controlled and maintained at a predetermined low temperature so that the temperature does not rise too much, and the work is troublesome. On the other hand, the above-mentioned heating temperature of 180 ° C is, for example, 120 ° C. The lower the heating temperature for the dehydration condensation of the former is considerably lower than 180 ° C, and the work efficiency of the reaction is low, the work efficiency of the reaction is poor when the temperature is low. The gelation can be avoided even when the latter one-step reaction is carried out by suppressing it to the optimum range that does not damage the workability, which improves the workability, shortens the production time, and improves the productivity. it can.
このように、前者の加熱温度を低い水準に限定する
と、後者の反応により得られる生成物の樹脂水溶液はpH
を３〜６の範囲でゲル化するようなことを回避すことが
できるため、その樹脂水溶液の安定性を維持でき、これ
によりその樹脂水溶液の保存性を高めることができ、上
記の従来のものがpHを３〜５の範囲内で安定であるとさ
れているのにくらべ、その安定性、保存性をpHの高い範
囲まで拡大することができる結果、例えばタンク等の容
器、配管の腐食が抑制され、また、硫酸バンドを減らし
て中性領域で抄紙しようとする中性抄紙方法の抄紙系pH
を苛性ソーダ等の添加により調整する操作や管理（低い
pHの添加剤を添加すると抄紙系pHを低下させることがあ
る）を簡単にできるという効果を有することができる。Thus, if the heating temperature of the former is limited to a low level, the aqueous resin solution of the product obtained by the latter reaction will have a pH
Since it is possible to avoid gelling in the range of 3 to 6, the stability of the resin aqueous solution can be maintained, and thus the storage stability of the resin aqueous solution can be improved. Is stable within a pH range of 3 to 5, its stability and storage stability can be expanded to a high pH range, resulting in corrosion of vessels such as tanks and piping. The pH of the papermaking system of the neutral papermaking method that is suppressed and tries to make paper in the neutral region by reducing the sulfuric acid band.
Operation and control (low)
(Adding a pH additive may lower the pH of the papermaking system).
Claims (1)
ボン酸を加熱、脱水縮合し、次いで得られたポリアミド
ポリアミンを水溶液中でエピクロルヒドリンと反応させ
て、ポリアミドポリアミンエピクロルヒドリン樹脂水溶
液を製造する方法において、 （ａ）ポリアルキレンポリアミンと脂肪族ジカルボン酸
のモル比が1.0:0.9〜1.1の範囲であって、その脱水縮合
させる際の加熱温度が135℃〜150℃の間であり、 （ｂ）上記（ａ）で得られたポリアミドポリアミンの50
％水溶液のブルックフィールド粘度計による25℃、毎分
60回転における粘度が300〜600センチポイズの間であ
り、 （ｃ）上記（ｂ）のポリアミドポリアミンの20〜50％水
溶液中で、該ポリアミドポリアミン中のアミノ基に対
し、1.2〜2.0当量のエピクロルヒドリンをその最終生成
物の固型分20％水溶液の上記測定法による粘度が30〜20
0センチポイズになるまで50〜80℃で一段階反応させる
こと を特徴とするポリアミドポリアミンエピクロルヒドリン
樹脂水溶液の製造方法。1. A method for producing an aqueous solution of a polyamide polyamine epichlorohydrin resin by heating and dehydrating condensation of a polyalkylene polyamine and an aliphatic dicarboxylic acid, and then reacting the obtained polyamide polyamine with epichlorohydrin, wherein (a) The molar ratio of the polyalkylene polyamine to the aliphatic dicarboxylic acid is in the range of 1.0: 0.9 to 1.1, and the heating temperature for the dehydration condensation is between 135 ° C and 150 ° C, (b) in (a) above. 50 of the obtained polyamide polyamine
% Aqueous solution at 25 ° C per minute with Brookfield viscometer
The viscosity at 60 revolutions is between 300 and 600 centipoise, and (c) in a 20 to 50% aqueous solution of the polyamide polyamine of (b) above, 1.2 to 2.0 equivalents of epichlorohydrin is added to the amino groups in the polyamide polyamine. The final product has a solid content of 20% and a viscosity of 30 to 20 by the above measurement method.
A method for producing an aqueous solution of a polyamide polyamine epichlorohydrin resin, which comprises carrying out a one-step reaction at 50 to 80 ° C. until it reaches 0 centipoise.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61213781A JP2516748B2 (en) | 1986-09-12 | 1986-09-12 | Method for producing polyamide polyamine epichlorohydrin resin aqueous solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61213781A JP2516748B2 (en) | 1986-09-12 | 1986-09-12 | Method for producing polyamide polyamine epichlorohydrin resin aqueous solution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6369826A JPS6369826A (en) | 1988-03-29 |
| JP2516748B2 true JP2516748B2 (en) | 1996-07-24 |
Family
ID=16644932
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61213781A Expired - Fee Related JP2516748B2 (en) | 1986-09-12 | 1986-09-12 | Method for producing polyamide polyamine epichlorohydrin resin aqueous solution |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2516748B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2969636B2 (en) * | 1988-12-23 | 1999-11-02 | 住友化学工業株式会社 | Method for producing aqueous solution of cationic thermosetting resin |
| WO2010000696A1 (en) * | 2008-07-01 | 2010-01-07 | Akzo Nobel N.V. | Resin precursor |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56110727A (en) * | 1980-02-07 | 1981-09-02 | Takeda Chem Ind Ltd | Preparation of aqueous solution of cationic thermo-setting resin |
-
1986
- 1986-09-12 JP JP61213781A patent/JP2516748B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6369826A (en) | 1988-03-29 |
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