JPH03163124A - Aqueous formaldehyde-urea solution - Google Patents
Aqueous formaldehyde-urea solutionInfo
- Publication number
- JPH03163124A JPH03163124A JP30381789A JP30381789A JPH03163124A JP H03163124 A JPH03163124 A JP H03163124A JP 30381789 A JP30381789 A JP 30381789A JP 30381789 A JP30381789 A JP 30381789A JP H03163124 A JPH03163124 A JP H03163124A
- Authority
- JP
- Japan
- Prior art keywords
- formaldehyde
- urea
- formalin
- aqueous solution
- soln
- 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.)
- Granted
Links
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 title claims description 23
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 267
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 48
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000004202 carbamide Substances 0.000 claims abstract description 33
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 23
- 239000007864 aqueous solution Substances 0.000 claims description 35
- 238000003756 stirring Methods 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 4
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 19
- 229920003180 amino resin Polymers 0.000 abstract description 16
- 238000013329 compounding Methods 0.000 abstract 1
- 235000019256 formaldehyde Nutrition 0.000 description 51
- 239000003381 stabilizer Substances 0.000 description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- 229920005989 resin Polymers 0.000 description 10
- 239000011347 resin Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 239000004480 active ingredient Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- VGGLHLAESQEWCR-UHFFFAOYSA-N N-(hydroxymethyl)urea Chemical compound NC(=O)NCO VGGLHLAESQEWCR-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 229920000877 Melamine resin Polymers 0.000 description 4
- 229930040373 Paraformaldehyde Natural products 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 229920001807 Urea-formaldehyde Polymers 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000005484 gravity Effects 0.000 description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 4
- 229920002866 paraformaldehyde Polymers 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- CKFGINPQOCXMAZ-UHFFFAOYSA-N methanediol Chemical compound OCO CKFGINPQOCXMAZ-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000011120 plywood Substances 0.000 description 2
- 229920006324 polyoxymethylene Polymers 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- JZLWSRCQCPAUDP-UHFFFAOYSA-N 1,3,5-triazine-2,4,6-triamine;urea Chemical compound NC(N)=O.NC1=NC(N)=NC(N)=N1 JZLWSRCQCPAUDP-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
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- XGEGHDBEHXKFPX-UHFFFAOYSA-N N-methylthiourea Natural products CNC(N)=O XGEGHDBEHXKFPX-UHFFFAOYSA-N 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- XGEGHDBEHXKFPX-NJFSPNSNSA-N methylurea Chemical compound [14CH3]NC(N)=O XGEGHDBEHXKFPX-NJFSPNSNSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000002485 urinary effect Effects 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
Description
【発明の詳細な説明】
（産朶上の利用分野〉
本発明は、新規なアミノ樹脂製造用の原料ホルムアルデ
ヒドに供されるホルムアルデヒド−ｖＡ素水溶液に関す
る。さらに詳しくは、ａｌ１度ホルマリンに尿素を添加
し予備縮合した溶液とホルマリン安定剤とからなる、常
温下保存『＋Ｊ能なホルムアルデヒド−尿累水溶液に関
する。Detailed Description of the Invention (Field of Application in Production) The present invention relates to a formaldehyde-VA aqueous solution that is used as a raw material formaldehyde for producing a novel amino resin. This invention relates to a formaldehyde-urine aqueous solution that can be stored at room temperature and is composed of a precondensed solution and a formalin stabilizer.
合板、パーティクルボード等の木質系製品に使用する接
着剤は、アミノ樹脂と称されるものであり、尿素とホル
ムアルｆヒドを縮合した尿素樹脂、尿素とメラミンとホ
ルムアルデヒドとを縮合した尿索−メラミン樹脂は、廉
価で製法が容易で、かつ木質材料に適した接着特性を有
することから大量に使用されている。Adhesives used for wood products such as plywood and particle board are called amino resins, such as urea resin, which is a condensation of urea and formal f-hyde, and urea resin, which is a condensation of urea, melamine, and formaldehyde. Resins are used in large quantities because they are inexpensive, easy to manufacture, and have adhesive properties suitable for wood materials.
本発明のホルムアルデヒド−尿累水溶液は、このアミノ
樹脂の製法に適した高濃度のボルムアルデヒド水溶液で
あり、常温で貯蔵可能なことから格別に有利に使用する
ことができるものである。The formaldehyde-urine aqueous solution of the present invention is a high-concentration formaldehyde aqueous solution suitable for this amino resin production method, and can be used particularly advantageously because it can be stored at room temperature.
（従来の技術）
アミノ樹脂製造用のホルマリンは、ホルムアルデヒドｌ
Ｉａ度が３７重星％でメタノール含ｈ椿が８重吊％以下
のホルマリン（以下３７％ホルマリンという）が、温度
２０℃以■の常温で安定に貯蔵できることから専ら使用
されてきた。(Prior art) Formalin for producing amino resin is formaldehyde l.
Formalin with an Ia degree of 37% and a methanol content of 8% or less (hereinafter referred to as 37% formalin) has been exclusively used because it can be stored stably at room temperature below 20°C.
しかし、３７％ホルマリンはメタノール含イｆ晴が多く
ホルムアルデヒド濃度が低いために、高い樹脂固形分を
有するアミノ樹脂を製造ずる工程では、多損の水、メタ
ノールを除去するため、メタノール分の屓失があり、さ
らには廃水による公害の発生を防止するための処Ｉ！［
！設備が必要となる欠点がある。However, 37% formalin contains a lot of methanol and has a low formaldehyde concentration, so in the process of producing amino resins with a high resin solid content, a large amount of water and methanol are removed, and the methanol content is lost. In addition, there are measures to prevent pollution caused by wastewater. [
! The disadvantage is that it requires equipment.
このため、近年高溌度ホルマリンと称するホルムアルデ
ヒド濃度が約５０〜５５！ｆ！ｌｆｉ％でメタノール？
有６１が３重］ＩＸ％以下のホルマリン（以下に高濃度
ホルマリンという〉が使用されている。For this reason, in recent years, the formaldehyde concentration, which is called high-permeability formalin, is about 50 to 55! f! Methanol in lfi%?
Formalin containing less than 61% (triple) IX% (hereinafter referred to as high-concentration formalin) is used.
この高濃度ホルマリン（よメタノール含も眼が低く、ホ
ルムアルデヒド濃度が高いため、アミン樹脂製造に際し
て生産性にａ３いて有利なものであるが、貯蔵と輸送に
際して温度５０〜６０℃に保持しなければならない。ざ
らに（よ、『ｒ蔵タンクｊ：り反応缶に輸送した後の空
のパイプラインや、輸送した後の空のローリーが常温に
冷即されるとき、固体のバラホルムアルデヒドが析出し
、ラインを閉鎖づるので、温水で洗浄する必要がある。This highly concentrated formalin (methanol content is low and formaldehyde concentration is high, so it is advantageous in terms of productivity when producing amine resins, but it must be kept at a temperature of 50 to 60°C during storage and transportation. When the empty pipeline after being transported to the reaction tank or the empty lorry after being transported is cooled down to room temperature, solid formaldehyde precipitates out. Since the line is closed, it must be flushed with warm water.
すなわち，ホルムアルデヒドは水溶液中では、ホルムア
ルデヒド［Ｃ口２ｏ１とメチレングリ」一ル［Ｃ口 （
Ｏ■）２］、低級ボリＡキシメチ２
レングリコール［１１０（Ｃ｝１■０）。Ｈ］等の平衡
状態にあり、常温下ではこの平衡状態が不安定であり、
低級ポリオキシメヂレングリコールがさらに重合してバ
ラホルムアルデヒドを析出して、ホルマリンが白濁し、
沈殿するからである。That is, in an aqueous solution, formaldehyde [C2O1 and methylene glycol][C2O1]
O■)2], lower polyA ximethylene glycol [110(C}1■0). H], etc., and this equilibrium state is unstable at room temperature,
Lower polyoxymethylene glycol further polymerizes and precipitates formaldehyde, making formalin cloudy.
This is because it precipitates.
一方、高濃度ホルマリンを濃縮して常温で固体であるパ
ラホルムアルデヒドもアミノ樹脂ｙＪ造に供されるが、
バラホルムアルデヒドは、臭気、吸湿のため完全密閉型
の取扱を必要とし、運搬と計損に多大な労力を要し、か
つ水に溶解するのにかなりの時間を要する欠点がある。On the other hand, paraformaldehyde, which is solid at room temperature by concentrating highly concentrated formalin, is also used in the production of amino resin yJ.
Rose formaldehyde has the disadvantages that it must be handled in a completely sealed container due to its odor and moisture absorption, that it requires a great deal of labor to transport and store, and that it takes a considerable amount of time to dissolve in water.
さらに、高濃度ホルマリンに尿素を加えて弱アルカリ性
Ｆ、加温熟成した後、減圧脱水ぬ縮して製造する尿素，
−ホルムアルデヒド液（以下ＩＪＦ液という）があげら
れる。Furthermore, urea is produced by adding urea to high-concentration formalin, heating and aging it, and then dehydrating it under reduced pressure.
-Formaldehyde liquid (hereinafter referred to as IJF liquid) is mentioned.
ＵＦ液は、アミノ樹脂の製造に供する場合、遊離のホル
ムアルデヒドとメチロール尿素として存在するメチロー
ル態ホルムアルデヒドとの合計出をホルムアルデヒド有
効成分とｂなし、メチロール尿素として存在する尿素を
も右効成分として原料に使用する。When the UF liquid is used for the production of amino resin, the total amount of free formaldehyde and methylol formaldehyde present as methylol urea is treated as formaldehyde active ingredient, and urea present as methylol urea is also used as a raw material as an active ingredient. use.
このｔＪＦ液として、例えば、ホルムアルデヒド対尿素
のモル比が４．８対１であり、ホルムアルデヒド有効成
分が５０重吊％、尿素有効成分が２１重量％のＵＦ−７
０をあげることができる。As this tJF liquid, for example, UF-7 has a molar ratio of formaldehyde to urea of 4.8:1, and contains 50% by weight of formaldehyde active ingredient and 21% by weight of urea active ingredient.
You can give 0.
しかし、このようなＵＦ液は、常温で貯蔵することは可
能であるが、ＵＦ液を製造する工程で多昂の廃水処理を
必要とする欠点があげられる。However, although such UF liquids can be stored at room temperature, they have the disadvantage that extensive wastewater treatment is required in the process of producing the UF liquid.
（発明が解決しようとずる問題点）
かくて、上記のようなアミノ樹脂製造に供されている様
々なホルマリンの欠点である廃水処理、高温貯蔵性、固
体であるための取扱の不便さなどを排除して、高濃度ホ
ルマリンのようにメタノール含量を少なくして、高いホ
ルムアルデヒド含有社による利益を維持しつつ、ホルム
アルデヒドの水溶液状で、３７％ホルマリンのように常
温で貯蔵しうる新規なホルムアルデヒド原料を間発する
ことが当業界から要望されていた。(Problems to be Solved by the Invention) In this way, the disadvantages of various formalins used in the production of amino resins, such as wastewater treatment, high temperature storage, and inconvenience in handling because they are solid, can be solved. A new formaldehyde raw material that is in the form of an aqueous solution of formaldehyde and can be stored at room temperature, such as 37% formalin, while maintaining the benefits of high formaldehyde content by reducing the methanol content like high-concentration formalin. It has been requested by the industry that intermittent generation be achieved.
（問題点を解決するための手段〉
本発明者らは、上記の問題点を解決することを目的とし
て検討した結果、高濃度ホルマリンに卓越した安定効果
を示すホルマリン安定剤であるポリビニルホルマールを
微量添加し、ホルマリンの貯ｍｍａをより低下させ、さ
らに少懇の尿素を添加し、゛ホルマリン中で安定に存在
できるメチロール尿素を加温下、予備縮合して生威させ
ることにより、アミノ＠脂製造のホルマリン原料となり
うるホルムアルデヒド−尿素水溶液が得られることを見
出し本発明を完成した。(Means for Solving the Problems) As a result of studies aimed at solving the above problems, the present inventors discovered that polyvinyl formal, a formalin stabilizer that exhibits an outstanding stabilizing effect on high-concentration formalin, was added in small amounts to By adding a small amount of urea and precondensing methylol urea, which can stably exist in formalin, under heating, amino@ fat production is possible. The present invention was completed by discovering that an aqueous formaldehyde-urea solution that can be used as a raw material for formalin can be obtained.
すなわち本発明のホルムアルデヒド−尿素水溶液はホル
ムアルデヒド濃度が５０〜５５重吊％、メタノール含有
量が３重量％以下であるホルマリンに、尿素をホルムア
ルデヒド対尿素のモル比が６〜１６対１になるように添
加しその混合溶液のＤＨを８〜９の範囲に調整し、温度
６５〜７５℃で１５〜６０分問撹拌して予備縮合するこ
とにより得られた溶液と数平均分子量が１５００〜５０
００、ホルマール化度が６５〜７５モル％であるポリビ
ニルホルマール５〜３０９ＥＣＩとからなる粘度５〜１
０ボイズ、遊離ホルムアルデヒドが２０〜４０重ＩＩ％
のホルムアルデヒド−尿素水溶液である。That is, the formaldehyde-urea aqueous solution of the present invention is prepared by adding urea to formalin having a formaldehyde concentration of 50 to 55% by weight and a methanol content of 3% by weight or less so that the molar ratio of formaldehyde to urea is 6 to 16:1. The DH of the mixed solution was adjusted to a range of 8 to 9, and the number average molecular weight was 1500 to 50.
00, polyvinyl formal having a degree of formalization of 65 to 75 mol% and a viscosity of 5 to 1, consisting of 5 to 309 ECI
0 voids, 20-40% free formaldehyde
This is an aqueous formaldehyde-urea solution.
高濃度ホルマリンとしては、ホルムアルデビドＩｌ度が
、５０〜５５重母％でメタノール含有敏が３重量％以下
の貯蔵温度が５０℃以上の工業用ホルマリンが使用され
る。As the high-concentration formalin, industrial formalin having a formaldehyde level of 50 to 55% by weight, a methanol content of 3% by weight or less, and a storage temperature of 50° C. or higher is used.
本発明に使用されるポリビニルホルマールはホルマリン
安定剤として使用されゲルパーミエイシヨンク０マトグ
ラフィー法（ＧＰＣ法）で測定した数平均分子社が、１
５００〜ｓｏｏｏ （ボリ１ヂレングリコール換算〉、
化学分析によるホルマール化度が、６５〜７，５モル％
であるポリビニルホルマールぐ、ホルマリンに易溶解性
を有するものであればよく、好ましくは、固形分含量が
５〜１０重量％のメタノールー水混合溶液が適当である
。The polyvinyl formal used in the present invention is used as a formalin stabilizer and has a number average molecular weight of 1 as measured by gel permeation chromatography (GPC method).
500~sooo (converted to 1 ethylene glycol),
The degree of formalization according to chemical analysis is 65 to 7.5 mol%
Any polyvinyl formal may be used as long as it is easily soluble in formalin, and preferably a methanol-water mixed solution having a solid content of 5 to 10% by weight is suitable.
このようなホルマリン安定剤の製法として、例えば酢酸
ビニルモノマーから直接合或する方法があげられる。（
特開［６１−３６３０５号公報）。つぎに、本発明の尿
素とホルムアルデヒドの予備縮合溶液の製法を説明する
。An example of a method for producing such a formalin stabilizer is a method in which it is directly synthesized from vinyl acetate monomers. (
JP-A [61-36305]. Next, a method for producing a precondensation solution of urea and formaldehyde according to the present invention will be explained.
高１度ホルマリンに３０ｆｆｌ ｆｉ１％の水酸化ナト
リウム水溶液をｐＦ］が８〜９のアルカリ性になる迄添
加する。その後ホルムアルデヒド対尿素のモル比が６〜
１６対１になるように尿素を添加し、撹拌下、温度６５
〜７５℃で１５〜６０分間、予備縮合したのち３５℃以
下の室温に冷却する。Add 30 ffl fi 1% aqueous sodium hydroxide solution to high 1 degree formalin until it becomes alkaline with pF] of 8 to 9. Then the molar ratio of formaldehyde to urea is 6~
Add urea in a ratio of 16 to 1 and reduce the temperature to 65°C under stirring.
After precondensation at ~75°C for 15-60 minutes, it is cooled to room temperature below 35°C.
本発明のホルムアルデヒド−尿素水溶液はこのようにし
て得られた予備縮合溶液と上述のポリビニルホルマール
５〜３０ｐｐ−とからなる。ボリビニルホルマールは予
備縮合時に反応系中に添加しておいてもよいし、予備縮
合終了後に添加してもよい。The formaldehyde-urea aqueous solution of the present invention consists of the precondensation solution thus obtained and 5 to 30 pp of the above-mentioned polyvinyl formal. Borivinyl formal may be added into the reaction system during precondensation, or may be added after completion of precondensation.
ホルムアルデヒド−尿素水溶液のホルムアルデヒドと尿
素のモル比の範囲｛６〜１６：１｝と、ホルマリン安定
剤添加昂の範囲（５〜３０ｐｐｍ）との関係は、貯ｊｉ
ｌｉ１１度を−５〜２０℃とした場合、貯蔵温度が低く
なれば、該モル比を低く、かつホルマリン安定剤添加量
が増加する関係にある。The relationship between the formaldehyde to urea molar ratio range {6 to 16:1} in the formaldehyde-urea aqueous solution and the formalin stabilizer addition range (5 to 30 ppm) is
When the li11 degree is -5 to 20 degrees Celsius, the lower the storage temperature, the lower the molar ratio and the greater the amount of formalin stabilizer added.
すなわち、ホルムアルデヒドと尿素のモル比が１０〜１
２：１であれば、ホルマリン安定剤添加社が１０〜２０
ｐｐｌで貯ｊｉ１度がＯ〜５℃であり、該モル比が１２
〜１６：１であれば、ホルマリン安定剤添加社が２０〜
３Ｏｐｐ−で貯蔵温度が５〜１５℃とすることが可能で
ある。That is, the molar ratio of formaldehyde and urea is 10 to 1.
If it is 2:1, formalin stabilizer addition company is 10-20
The storage temperature in ppl is 0~5℃, and the molar ratio is 12
~16:1, formalin stabilizer addition company is 20~
At 3Opp- it is possible to have a storage temperature of 5-15°C.
ホルムアルデヒド対尿素のモル比が５：１であれば、ホ
ルマリン安定剤無添加でも０℃で貯蔵できるが、ホルム
アルデヒド−尿索水溶液中の有効尿素成分が多くなり、
アミノ樹脂製造処方の設計に制限をうけ原料ホルムアル
デヒドとして不適当となる。また該モル比が１７：１以
上となればホルマリン安定剤を３０ｐｐｍ以上に増やし
ても２０℃で３０日以上保存できなくなり本発明の目的
を達成することができない。また、ボルマリン安定剤で
あるポリビニルホルマール量は３０ｐｐｍ以上添加して
も、ホルムアルデヒド−尿素水溶液の貯蔵安定性を向上
しないので３０ｐｐｍ以上添加することは好ましくない
。If the molar ratio of formaldehyde to urea is 5:1, it can be stored at 0°C without adding a formalin stabilizer, but the effective urea component in the formaldehyde-urea solution increases.
Due to limitations in the design of the amino resin manufacturing recipe, it is unsuitable as a raw material formaldehyde. Further, if the molar ratio is 17:1 or more, even if the formalin stabilizer is increased to 30 ppm or more, the product cannot be stored at 20° C. for more than 30 days, and the object of the present invention cannot be achieved. Furthermore, it is not preferable to add polyvinyl formal, which is a bomarin stabilizer, in an amount of 30 ppm or more because the storage stability of the formaldehyde-urea aqueous solution is not improved even if the amount is added.
ホルムアルデヒド−尿素予備縮合水溶液の製造でｐＨを
８〜９、予備縮合温度を６５〜７５℃としたのは、この
範囲条件の組合せにより、全Φの尿素とホルムアルデヒ
ドとが反応してメチロール尿素のみを生成させるからで
ある。この範囲からはずれた場合、予備縮合潟度が低く
、ｐＨが低いときもよ、メチＯ−ル尿素の生或が少なく
、′ＴＬ離のホルムアルデヒドが多くなることから、バ
ラホルムアルデヒドが生じ易くなる。また、予備縮合濡
度が高く、反応時間が長いときは、樹脂状の水不溶の綜
合物が生成し、貯蔵中短期間で白濁や沈殿を生じたりす
るので、いずれの場合も好ましくない。The reason why the pH was set to 8 to 9 and the precondensation temperature was set to 65 to 75°C in the production of the formaldehyde-urea precondensation aqueous solution is that due to the combination of these range conditions, all Φ of urea and formaldehyde react to form only methylol urea. This is because it generates. If it deviates from this range, even when the degree of precondensation lag is low and the pH is low, the production of methyl O-lurea is small and formaldehyde separated from 'TL is large, so that paraformaldehyde is more likely to be produced. Furthermore, when the precondensation wetness is high and the reaction time is long, a water-insoluble resinous composite is formed, which may become cloudy or precipitate within a short period of time during storage, which is not preferable in either case.
このようにして製造したホルムアルデヒド−尿素水溶液
の２５℃での物性は、外？ＪＡＪｌＩｔ色透明、比重１
．１〜１．２書手、枯度５〜１０センチボイズ、（Ｂ型
回転粘度計で測定）、ｐＨ約６．５〜７で、ホルムアル
デヒド有効成分含１５０〜５５重徂％のうら、遊離のホ
ルムアルデヒド含有迅が２０〜４０重吊％と高いもので
ある。What are the physical properties of the formaldehyde-urea aqueous solution produced in this way at 25°C? JAJlIt color transparent, specific gravity 1
．． 1-1.2 calligraphy, dryness 5-10 centiboise (measured with a B-type rotational viscometer), pH approximately 6.5-7, active ingredient formaldehyde content of 150-55% by weight, free formaldehyde. The content is as high as 20-40%.
遊離のホルムアルデヒド含有吊が余りに高い場合は上述
のようにパラホルムアルデヒドが生成し易くなり、余り
に少なすぎるとアくノ樹脂原料として不適当になる。粘
度は予備綜合の割合を間接的に示すものであり、余りに
大きなもの４ホルムアルデヒド−尿素綜合物の濃度が大
でアミン樹脂原料どして不適当であり、小さすぎるもの
は遊離ホルムアルデヒド含有量が多いのと同じ結果を生
じる。If the free formaldehyde content is too high, paraformaldehyde tends to be generated as described above, and if it is too low, it becomes unsuitable as a raw material for acrylic resin. The viscosity indirectly indicates the pre-synthesis ratio; if it is too large, the concentration of the formaldehyde-urea complex is too high and it is unsuitable as an amine resin raw material, and if it is too small, the free formaldehyde content is high. produces the same result as .
また、この水溶液は、２０℃以下の常温で１カ月以上貯
蔵しても′Ｔ１離のホルムアルデヒド含有敏がほとんど
変化しないものである。Further, even if this aqueous solution is stored at room temperature below 20°C for more than one month, the formaldehyde content of 'T1' remains almost unchanged.
本発明のホルムアルデとドー尿素水溶液はアミノ樹脂の
製造に適したＩＸ淵度のホルムアルデヒド水溶液を常温
で貯蔵することを可能にしたものである。換言すれば５
０〜５５重量％、メタノール含有最が３重量％以下であ
るホルマリンに、尿素をホルムアルデヒド対尿素のモル
比が６〜１６対１になス七うζ活加１，子の混合流妨の
ロ口を８へ９の節囲に調整し、温度６５〜７５℃で１５
〜６０分間撹拌して予備縮合せしめ、この溶液に数平均
分子社が約１５００〜５０００、ホルマール化度が約６
５〜７５モル％である５〜３（ＩＩ）ｌ１ｆｆｌのポリ
ビニルホルマールを添加することにより高濃度ホルマリ
ン水溶液を常温で貯蔵可能に安定化せしめる方法とも云
うことができる。The formalde and dourea aqueous solution of the present invention makes it possible to store a formaldehyde aqueous solution of IX depth suitable for the production of amino resin at room temperature. In other words, 5
Add urea to formalin containing 0 to 55% by weight and 3% by weight or less of methanol at a molar ratio of formaldehyde to urea of 6 to 16 to 1. Adjust the opening to 8 to 9 joints, and heat at 65-75℃ for 15 minutes.
Stir for ~60 minutes to precondense, and the solution has a number average molecular weight of about 1500-5000 and a degree of formalization of about 6.
It can also be said to be a method of stabilizing a highly concentrated formalin aqueous solution so that it can be stored at room temperature by adding 5 to 3(II) l1ffl of polyvinyl formal, which is 5 to 75 mol%.
（充明の効果）
本発明のホルムアルデヒド−尿累水溶液をアミン樹脂製
造に供するとき、下記のような効果が奏される。(Effects of fullness) When the formaldehyde-urine aqueous solution of the present invention is used for producing an amine resin, the following effects are exhibited.
■ ３１％ホルマリン並みの温度で貯蔵でき、高濃度ホ
ルマリンのような高温で維持づ゛る必変がない。■ It can be stored at the same temperature as 31% formalin, and does not have to be maintained at high temperatures like high-concentration formalin.
■ ホルムアルデヒド有効成分のうら、１１１！ホルム
アルデヒド或分が約２０〜４０重量％と高いので、任意
に尿素とメラミン成分を設定して、アミノ樹脱ルｖ１；
告寸ス７シバＴキ７）
■ アくノ樹脂製造の原料として、３７％ホルマリンを
使用した場合のように脱水濃縮する必要がなく、廃水設
備が不要であり、また、固体のバラホルムアルデヒドの
ような取扱上の不便さもない。■ Behind the formaldehyde active ingredient, 111! Since the formaldehyde content is high at about 20 to 40% by weight, urea and melamine components are arbitrarily set and amino resin v1;
■ As a raw material for producing Akuno resin, there is no need for dehydration and concentration unlike when using 37% formalin, and no wastewater facilities are required. There is no such inconvenience in handling.
■ 低粘度の水溶液であり、容易にポンプ輸送ができ、
かつ１ケ月以上にわたって遊離ホルムアルデヒド成分の
変化がないので、品質の安定したアミノ樹脂を製造でき
る。■ It is a low viscosity aqueous solution and can be easily transported by pump.
Moreover, since there is no change in the free formaldehyde component for more than one month, it is possible to produce an amino resin with stable quality.
以上のような効果を本発明のホルムアルデヒド−尿素水
溶液が発現する理由は、高濃度ホルマリン中のホルムア
ルデヒド或分が、予備縮合反応によるメチロール尿素の
生成に消費され低濃度となり、かつホルマリン安定剤の
作用により低級ポリオキシメチレングリコールとしてメ
チロール尿素と水溶液中で安定な平衡状態で共存してい
るためと推察される。The reason why the formaldehyde-urea aqueous solution of the present invention exhibits the above-mentioned effects is that some of the formaldehyde in high-concentration formalin is consumed in the production of methylol urea through the precondensation reaction, resulting in a low concentration, and the effect of the formalin stabilizer It is presumed that this is because it coexists with methylol urea in a stable equilibrium state in an aqueous solution as a lower polyoxymethylene glycol.
このような特徴を有するホルムアルデヒド−尿素水溶液
は、従来全く提案されたことがなく新規なものである。A formaldehyde-urea aqueous solution having such characteristics has never been proposed before and is therefore novel.
かくて、本発明によるホルムアルデヒド−尿素水溶液を
アミノ樹脂製造の原料として工業的規模で使用するとき
、生産性、経済性において著しい利益をもたらすものと
いえる。Thus, when the formaldehyde-urea aqueous solution according to the present invention is used on an industrial scale as a raw material for producing amino resins, it can be said that it brings significant benefits in terms of productivity and economy.
（実施例等）
以下に実施例、比較例、参考例を挙げて本発明をさらに
説明する。なお、％は特に示されない限り重岳％である
。(Examples, etc.) The present invention will be further described below with reference to Examples, Comparative Examples, and Reference Examples. Note that percentages are Shigetake percentages unless otherwise specified.
参考例１
つぎに本発明に使用したホルマリン安定剤であるポリビ
ニルホルマールの製法を示す。Reference Example 1 Next, a method for producing polyvinyl formal, which is a formalin stabilizer used in the present invention, will be described.
反応容器に酢酸ビニル８００ｇ、イソプロビルアルコー
ル８００ｇを加え、撹拌下界温し、７０℃に達した時に
アゾピスイソブチロニトリル３、Ｏｇを加え、７２℃の
３１流下で約１時間反応させたのち、７０℃でさらに３
時間反応させた。800 g of vinyl acetate and 800 g of isopropyl alcohol were added to a reaction vessel, the temperature was brought to ambient temperature under stirring, and when the temperature reached 70°C, 30g of azopisisobutyronitrile was added, and the mixture was reacted for about 1 hour under a flow of 31°C at 72°C. , further 3 at 70℃
Allowed time to react.
アゾビスイソプチロニトリルを添加してから４時間後に
、ホルマール化剤として３７％ホルマリン３００ ９、
３５％塩Ｉ！！２０ｇ、水２００ ９を加え、７０℃で
１９時間反応させたところ、２０℃のメタノール：水容
積比＝６０：４Ｇの混合溶液中で白濁を生じたので、こ
の時点で直ちに室温に冷郎した。得られた粗ポリビニル
ホルマール溶液を熱水溶液中に投入し加熱処理して精製
した。4 hours after adding azobisisobutyronitrile, 37% formalin 3009 as a formalizing agent,
35% salt I! ! When 20g of water and 200g of water were added and the reaction was carried out at 70°C for 19 hours, a white cloudy appearance occurred in the mixed solution of methanol:water volume ratio = 60:4G at 20°C, so at this point it was immediately cooled to room temperature. . The obtained crude polyvinyl formal solution was poured into a hot aqueous solution and purified by heat treatment.
このポリビニルホルマールをメタノール：水一８０ ：
２０の混合液に溶解し、ポリビニルホルマール固形分
５〜１０％のホルマリン安定剤水溶液を得た。This polyvinyl formal was mixed with methanol:water and 80%:
20 to obtain an aqueous formalin stabilizer solution having a polyvinyl formal solid content of 5 to 10%.
このポリビニルホルマールのＧＰＣ法による平均分子吊
は、数平均１６４７、重ｍ平均４４２Ｂ、Ｚ平均１０５
４１であった。ポリビニルホルマールのＪＩＳＫ −
６７２９に準拠した化学分析値は、酢酸ビニル成分１６
，１モル％、ビニルアルコール成分１１．４モル％、ビ
ニルホルマール成分７１．９モル％であった。The average molecular weight of this polyvinyl formal by GPC method is number average 1647, weight m average 442B, Z average 105
It was 41. JISK of polyvinyl formal
The chemical analysis value based on 6729 is vinyl acetate component 16
, 1 mol %, vinyl alcohol component 11.4 mol %, and vinyl formal component 71.9 mol %.
実施例１
（Ｆ／ｕ＝ホルムアルデヒド／尿索のモル比）反応器に
温度５１℃の５１．６％高濃度ホルマリン《メタノー｛
レ含右量１．５％＞ ２０００ｇを仕込み、撹拌下、ポ
リビニルホルマール固形分２．５％のホルマリン安定剤
溶液０．４９を添加し、３０％水酸化ナトリウムでｐＨ
８．６に調整した後、尿素３４４ｇを添加し、液温６５
℃まで界温した。この温度で６０分予備縮合した後、室
温まで冷却した。Example 1 (F/u = formaldehyde/urechord molar ratio) A reactor was charged with 51.6% high concentration formalin (methanol) at a temperature of 51°C.
A formalin stabilizer solution with a polyvinyl formal solid content of 2.5% was added under stirring, and the pH was adjusted to pH with 30% sodium hydroxide.
After adjusting to 8.6, 344g of urea was added and the liquid temperature was 65.
The ambient temperature was ℃. After precondensing at this temperature for 60 minutes, it was cooled to room temperature.
このようにして得たホルムアルデヒド−尿素水溶液は、
外観無色透明、２５℃での粘度１０センチボイズ、比重
１．２０５ （浮秤法）、Ｅｌｌ−１７．１（ガラス電
極）であった。The formaldehyde-urea aqueous solution obtained in this way is
It had a colorless and transparent appearance, a viscosity of 10 centiboise at 25°C, a specific gravity of 1.205 (floating balance method), and Ell-17.1 (glass electrode).
そして、液体クロマトグラフィーでの尿素成分の分析の
結果、ホルムアルデヒド−尿素水溶液の溶出ピークは、
メチ１］一ル尿素のピークと一致した。As a result of analysis of the urea component by liquid chromatography, the elution peak of the formaldehyde-urea aqueous solution was
The peak coincided with that of methyl urea.
貯蔵試験方法とその結果
このようにして得た、ホルムアルデヒド−尿素水溶液を
５００ｍｌのガラス容器に移し、温度−５℃の恒温室に
３１日間保存し、その外観、粘度と塩化アンモニウム法
（ＪＩＳ Ｋ−６８０１準拠）による、Ｔ１ｌＩＩホ
ルムアルデヒド含有吊を分析した。Storage test method and results The formaldehyde-urea aqueous solution thus obtained was transferred to a 500 ml glass container and stored in a constant temperature room at -5°C for 31 days, and its appearance, viscosity, and ammonium chloride method (JIS K- T1lII formaldehyde-containing suspension was analyzed according to 6801).
貯蔵による安定性試験の結果は、−５℃で３１日間貯蔵
しても、外観は無色透明であり、粘度の変化はなクｆ２
離ホルムアルデヒド含有量はわずかに低下しただけであ
った。The results of the storage stability test showed that the appearance was colorless and transparent, and there was no change in viscosity even after storage at -5°C for 31 days.
The free formaldehyde content was only slightly reduced.
この結果を第１表に示した。The results are shown in Table 1.
実施例２〜１２
実施例１と同様な操作でＦ／Ｕのモル比，ポリビニルホ
ルマール出、予備縮合条件を第１表のように変えて製造
した。ただし、５１．６％と５４，５％の高Ｉ Ｉｆｆ
ホルマリンを使用し、ポリビニルホルマール固形分２．
５〜１０％のホルマリン安定剤を使用した。Examples 2 to 12 Products were produced in the same manner as in Example 1, except that the F/U molar ratio, polyvinyl formal production, and precondensation conditions were changed as shown in Table 1. However, the high Iff of 51.6% and 54.5%
Using formalin, polyvinyl formal solid content 2.
5-10% formalin stabilizer was used.
貯蔵 験 法と結果 実施例１と同様の貯蔵試験を行った。Storage experience method and results A storage test similar to Example 1 was conducted.
この結果を第１表に一括して示した。The results are summarized in Table 1.
第１表の実施例１〜１２の結果から明らかなように、本
発明のホルムアルデヒド−尿素水溶液は、モル比Ｆ／Ｕ
が６から１６と高くなるにつれて、ホルマリン安定剤の
添加出も高くなり、貯蔵できる温度も−５℃から１５℃
と高くなった。しかし、いずれも貯′Ｎｉ温度２０℃以
下で、３１日間の貯蔵においても白濁等を生ぜず粘度の
変化なく遊離ホルムアルデヒド含有量は、貯蔵前と貯蔵
後でほとんど変化せず極めて安定していることが判明し
た。As is clear from the results of Examples 1 to 12 in Table 1, the formaldehyde-urea aqueous solution of the present invention has a molar ratio of F/U
As the temperature increases from 6 to 16, the amount of formalin stabilizer added increases, and the storage temperature also increases from -5℃ to 15℃.
It became high. However, in both cases, the storage temperature was 20°C or lower, and even after storage for 31 days, there was no clouding, no change in viscosity, and the free formaldehyde content remained extremely stable, with almost no change between before and after storage. There was found.
比較例１
尿素との予備縮合を行なわない高濃度５１．６％のホル
マリン水溶液にポリビニルホルマールを３０ａｐｓｅ
ｍ加した。貯蔵編度２０℃では５時間でパラホルムアル
デヒドの析出により白濁を生じた。Comparative Example 1 Polyvinyl formal was added at 30 apse to a highly concentrated 51.6% formalin aqueous solution without precondensation with urea.
Added m. At a storage temperature of 20° C., cloudiness occurred due to precipitation of paraformaldehyde in 5 hours.
比較例２
安定剤であるポリビニルホルマールを使用しない以外は
実施例１と同様の条件でホルムアルデヒド−尿素水溶液
を製造した。２０℃の貯蔵温度で２１日で白濁を生じた
。Comparative Example 2 A formaldehyde-urea aqueous solution was produced under the same conditions as in Example 1 except that polyvinyl formal as a stabilizer was not used. Cloudiness occurred in 21 days at a storage temperature of 20°C.
比較例３
Ｆ／Ｕを５／１とした以外は実施例１と同様の条件で行
った。貯蔵性は優れているが、Ｍｗｉホルムアルデヒド
量が１２．７％と少なく、アミノ樹脂製造には不適当で
あった。Comparative Example 3 The same conditions as in Example 1 were conducted except that F/U was 5/1. Although the storage property was excellent, the amount of Mwi formaldehyde was as low as 12.7%, making it unsuitable for producing amino resins.
比較例４
Ｆ／ｔＪを１７７１としポリビニルホルマール量を３０
ｐｐ＋ｍとした以外は実施例１０と同様の条件で行った
。Comparative Example 4 F/tJ was 1771 and the amount of polyvinyl formal was 30
The same conditions as in Example 10 were used except that pp+m was used.
遊離ホルムアルデヒド量が４０．２％となり２０℃の貯
ｊｌ温度で１２日で白濁を生じた。The amount of free formaldehyde was 40.2%, and cloudiness occurred in 12 days at a storage temperature of 20°C.
比較例５〜６
実施例１０で予備縮合条件を変えてホルムアルデヒド−
尿素水溶液を製造した。Comparative Examples 5 to 6 Formaldehyde was prepared by changing the precondensation conditions in Example 10.
A urea aqueous solution was produced.
比較例５は予備縮合温度が低く、ｌ）Ｈが低い場合であ
り、遊離ホルムアルデヒドが４１．４％と大となり２０
℃の貯Ｍ温度で６日で白濁した。比較例６は予備綜合温
度が高く、反応時間が長い場合であり、樹脂状の綜合物
が生成し、２０℃の貯Ｒ温度で３日で白濁した。Comparative Example 5 is a case where the precondensation temperature is low and l) H is low, and the free formaldehyde is as high as 41.4%, and 20
It became cloudy in 6 days at the storage temperature of °C. Comparative Example 6 was a case where the pre-synthesis temperature was high and the reaction time was long, and a resin-like composite was produced and became cloudy in 3 days at the storage R temperature of 20°C.
これらの結果を第２表に一括して示した。These results are collectively shown in Table 2.
参考例２
凰ｌ』４し先艶見
実施例９のホルムアルデヒド−尿累水溶液を使用して、
ホルムアルデヒドと尿素の有効成分と水の含有量を算出
して、一次モル比Ｆ／Ｕ＝２．０、二次モル比Ｆ／ｔＪ
＝ １．３のパーティクルボード用尿素樹脂接着剤を
製造した。Reference Example 2 Using the formaldehyde-urine aqueous solution of Example 9,
Calculate the active ingredients of formaldehyde and urea and the content of water, and the primary molar ratio F/U = 2.0 and the secondary molar ratio F/tJ.
A urea resin adhesive for particle board of = 1.3 was produced.
反応器にホルムアルデヒド−尿素水溶液１０００９（Ｆ
／ｕ−１０）を仕込み、撹拌下３０％水酸化ナトリウム
でｐＨ８．６に調整した後、一次尿素３９５ｇを加えて
、８５℃に昇湿した。同温度で３０分間保持しｐＨ ６
．８に降トした時点で、２０％蟻酸を添加してｐＨ ４
．８に調整し、２５分間反応させたところ、２０℃の水
和点に到達した。その後、１０％炭酸ナトリウムでｐＨ
７．２に中和し、二次尿素２６３ｇを加えて、１０分
間保持し室温まで冷ＩＩ Ｌ，た。このようにして製造
した樹脂は、２５℃で粘度１．６ボイズ、比重１．２７
６、ｌ）｝ｌ ７．４、不揮発分６４．２％であった。Formaldehyde-urea aqueous solution 10009 (F
/u-10) was charged and the pH was adjusted to 8.6 with 30% sodium hydroxide while stirring, then 395 g of primary urea was added and the temperature was raised to 85°C. Hold at the same temperature for 30 minutes until pH 6.
．． When the pH drops to 8, add 20% formic acid to adjust the pH to 4.
．． When the temperature was adjusted to 8 and reacted for 25 minutes, the hydration point of 20°C was reached. Then, pH was adjusted with 10% sodium carbonate.
7.2, 263 g of secondary urea was added, and the mixture was kept for 10 minutes and cooled to room temperature. The resin produced in this way has a viscosity of 1.6 voids and a specific gravity of 1.27 at 25°C.
6, l)}l 7.4, non-volatile content 64.2%.
この樹脂の反応経過と樹脂物性は、高濃度ホルマリンを
使用した場合と同じであった。The reaction progress and physical properties of this resin were the same as when high concentration formalin was used.
参考例３
メラミンー尿素樹脂の製゛
実施例３のホルムアルデヒド−尿索水溶液を使用して、
メラミン：尿索：ホルムアルデヒドのモル比＝ １：０
．５：２．８の合板用接着剤を製造した。Reference Example 3 Production of melamine-urea resin Using the formaldehyde-urea aqueous solution of Example 3,
Molar ratio of melamine: urinary cord: formaldehyde = 1:0
．． A 5:2.8 plywood adhesive was produced.
反応器にホルムアルデヒド−尿素水溶液１０００’Ｊ（
Ｆ／ＬＪ＝１０）、水４１０ｇ、メタノール１５６９を
仕込み、撹拌下尿素７８ｇ、メラミン７１８ｇを加えて
、９０℃に昇温した。昇温の途中で３０％水酸化ナトリ
ウムを添加してｆ）Ｈ１１．８に調整した。９０℃で１
時間１０分反応した時点でｐＨ９．０に降下した。Add 1000'J of formaldehyde-urea aqueous solution to the reactor (
F/LJ=10), 410 g of water, and 1,569 g of methanol were charged, and while stirring, 78 g of urea and 718 g of melamine were added, and the temperature was raised to 90°C. During the temperature rise, 30% sodium hydroxide was added to adjust f) H to 11.8. 1 at 90℃
After reacting for 10 minutes, the pH dropped to 9.0.
そのまま、さらに５分反応させたところ、ｐ１１７．４
に降下し３５℃で２５０％の水和度に到達したので、１
０％炭酸ナトリウムで ｐＨ８．６に調整し室温まで冷
却した。このようにしてＷＥＪ造した樹脂は、２５℃で
粘度１．２ボイス、比重１．２２０， ｐＨ８、６、
不揮発分５６．４％であった。この樹脂の反応経過と樹
脂物性は、３７％ホルマリンを使用した場合と同じであ
った。When the reaction was continued for another 5 minutes, p117.4
The degree of hydration reached 250% at 35°C, so 1
The pH was adjusted to 8.6 with 0% sodium carbonate and cooled to room temperature. The resin produced by WEJ in this way has a viscosity of 1.2 voices at 25°C, a specific gravity of 1.220, and a pH of 8.6.
The nonvolatile content was 56.4%. The reaction progress and physical properties of this resin were the same as when 37% formalin was used.
Claims (1)
ノール含有量が３重量％以下であるホルマリンに、尿素
をホルムアルデヒド対尿素のモル比が６〜１６対１にな
るように添加しその混合溶液のｐＨを８〜９の範囲に調
整し、温度６５〜７５℃で１５〜６０分間撹拌して予備
縮合することにより得られた水溶液と数平均分子量が１
５００〜５０００、ホルマール化度が６５〜７５モル％
であるポリビニルホルマール５〜３０ｐｐｍとからなる
粘度５〜１０センチポイズ（２５℃）、遊離ホルムアル
デヒドが２０〜４０重量％のホルムアルデヒド−尿素水
溶液。(1) Urea is added to formalin with a formaldehyde concentration of 50-55% by weight and a methanol content of 3% by weight or less so that the molar ratio of formaldehyde to urea is 6-16:1, and the pH of the mixed solution is is adjusted to a range of 8 to 9, and precondensed by stirring at a temperature of 65 to 75°C for 15 to 60 minutes, and the number average molecular weight is 1.
500-5000, formalization degree 65-75 mol%
A formaldehyde-urea aqueous solution having a viscosity of 5 to 10 centipoise (25° C.) and 20 to 40% by weight of free formaldehyde, consisting of 5 to 30 ppm of polyvinyl formal.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1303817A JP2695256B2 (en) | 1989-11-22 | 1989-11-22 | Formaldehyde-urea aqueous solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1303817A JP2695256B2 (en) | 1989-11-22 | 1989-11-22 | Formaldehyde-urea aqueous solution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03163124A true JPH03163124A (en) | 1991-07-15 |
| JP2695256B2 JP2695256B2 (en) | 1997-12-24 |
Family
ID=17925663
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1303817A Expired - Fee Related JP2695256B2 (en) | 1989-11-22 | 1989-11-22 | Formaldehyde-urea aqueous solution |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2695256B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006524648A (en) * | 2003-04-28 | 2006-11-02 | ビーエーエスエフ アクチェンゲゼルシャフト | Starting compounds for polyurethane production |
| WO2014069620A1 (en) | 2012-11-02 | 2014-05-08 | 花王株式会社 | Method for producing and storing liquid composition comprising tetrahydro-4h-1,3,5-oxadiazine-4-one |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4320476Y1 (en) * | 1965-02-08 | 1968-08-28 | ||
| JPS63303944A (en) * | 1987-06-05 | 1988-12-12 | Mitsubishi Gas Chem Co Inc | Stabilizer for aqueous solution of formaldehyde |
-
1989
- 1989-11-22 JP JP1303817A patent/JP2695256B2/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4320476Y1 (en) * | 1965-02-08 | 1968-08-28 | ||
| JPS63303944A (en) * | 1987-06-05 | 1988-12-12 | Mitsubishi Gas Chem Co Inc | Stabilizer for aqueous solution of formaldehyde |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006524648A (en) * | 2003-04-28 | 2006-11-02 | ビーエーエスエフ アクチェンゲゼルシャフト | Starting compounds for polyurethane production |
| WO2014069620A1 (en) | 2012-11-02 | 2014-05-08 | 花王株式会社 | Method for producing and storing liquid composition comprising tetrahydro-4h-1,3,5-oxadiazine-4-one |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2695256B2 (en) | 1997-12-24 |
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