JPH03714A - Preparation of self-emulsifying polyisocyanate - Google Patents
Preparation of self-emulsifying polyisocyanateInfo
- Publication number
- JPH03714A JPH03714A JP13459989A JP13459989A JPH03714A JP H03714 A JPH03714 A JP H03714A JP 13459989 A JP13459989 A JP 13459989A JP 13459989 A JP13459989 A JP 13459989A JP H03714 A JPH03714 A JP H03714A
- Authority
- JP
- Japan
- Prior art keywords
- polyisocyanate
- weight
- self
- emulsifying
- parts
- 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
- 229920001228 polyisocyanate Polymers 0.000 title claims abstract description 51
- 239000005056 polyisocyanate Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 15
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 15
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims abstract description 7
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 7
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 238000004519 manufacturing process Methods 0.000 claims description 27
- 150000002440 hydroxy compounds Chemical class 0.000 claims description 13
- -1 polymethylene Polymers 0.000 claims description 8
- 229920006389 polyphenyl polymer Polymers 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 3
- 238000003860 storage Methods 0.000 abstract description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 abstract description 5
- 239000000047 product Substances 0.000 abstract description 3
- 239000007795 chemical reaction product Substances 0.000 abstract description 2
- 239000000839 emulsion Substances 0.000 description 13
- 239000006185 dispersion Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 9
- 239000012948 isocyanate Substances 0.000 description 7
- 150000002513 isocyanates Chemical class 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000007774 longterm Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000002023 wood Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005187 foaming Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 230000001804 emulsifying effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 241001106041 Lycium Species 0.000 description 1
- 229920002396 Polyurea Polymers 0.000 description 1
- IRYBKFGKUNZRSI-UHFFFAOYSA-N Pyrene-1,2-oxide Chemical group C1=C2C3OC3C=C(C=C3)C2=C2C3=CC=CC2=C1 IRYBKFGKUNZRSI-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 230000010062 adhesion mechanism Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 230000001684 chronic effect Effects 0.000 description 1
- 239000012792 core layer Substances 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011122 softwood Substances 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（ａ）発明の目的
（産業上の利用分野）
本発明は、長期関貯麓安定であ夛、水と混合してポリイ
ンシアネート水性分散体くし九場合に、安定表札化状態
を保つことのできる自己乳化性ポリイソシアネート、％
にノ辛−ティクルーード用の自己乳化性ポリイソシアネ
ートの製造法に関する。DETAILED DESCRIPTION OF THE INVENTION (a) Object of the invention (industrial application field) The present invention provides a stable nameplate, which is stable for long-term storage, and when mixed with water to form a polyincyanate aqueous dispersion. Self-emulsifying polyisocyanate that can maintain its emulsified state, %
This invention relates to a method for producing a self-emulsifying polyisocyanate for spicy crude.
（従来技術）
近年、木質系ｉ４−ティクルーードの製造において、従
来からＯＲ素樹脂、メランンー尿素樹脂、フェノール樹
脂などのホルムアルデヒド系接着剤に代えてイソシアネ
ート化合物、特にポリメチレンポリフェニルポリイソシ
アネートの使用が多くなってきている。この理由として
、かかるポリイソシアネートはパーティクル一−ドの結
合剤として用いた場合に、耐久性のある接着力を発揮し
、さらにホルムアルデヒド系樹脂接着剤のような放散ホ
ルムアルデヒドの発生がない長所があげられる。このよ
うなポリイソシアネートの接着機構は、イソシアネート
基が水分で十分に湿潤された木材チ、！中のセルロース
の水酸基とウレタン結合を生成し九シ、水分と反応して
尿素結合を生成して硬化することによるのである。かか
るポリイソシアネートは水に不溶である丸め、あらかじ
め自己乳化性ポリイソシアネートとし、次に水を加えて
水性エマルノ、ンにした溶液を、木材チップに均一に散
布し、加熱圧締することＫよシゴード製品を製造してい
る。(Prior art) In recent years, isocyanate compounds, especially polymethylene polyphenyl polyisocyanate, are often used in place of formaldehyde adhesives such as OR resin, melane-urea resin, and phenol resin in the production of wood-based i4-ticle. It has become to. The reason for this is that such polyisocyanates exhibit durable adhesive strength when used as a particle bonding agent, and also have the advantage that they do not emit formaldehyde emissions unlike formaldehyde-based resin adhesives. . The adhesion mechanism of such polyisocyanate is that the isocyanate group is sufficiently moistened with moisture on wood. This is due to the formation of urethane bonds with the hydroxyl groups of the cellulose inside, which in turn reacts with moisture to form urea bonds and harden. Such a polyisocyanate is insoluble in water.The polyisocyanate is made into a self-emulsifying polyisocyanate in advance, and then water is added to form an aqueous emulsion.The resulting solution is uniformly spread over the wood chips and then heated and pressed. manufactures products.
このような自己乳化性ポリイソシアネートを製造する方
法として、ポリイソシアネートと４リメチレンオキサイ
ドとポリｆａピレンオキサイドのプロ、クコ４リマーを
単独、あるいはポリエチレングリコールを併用して反応
させることが提案されている（特公昭６１−４３３９６
号）、シかし、このような自己乳化ｆｉｙｊ？リイソシ
アネートは、製造後直に水と混合し水性エマルソ、ンに
すれば、放置時間が１〜２時間の範囲内では安定なエマ
ルノ、ンを形成することができるが、２５〜３５℃で長
時間貯蔵すると短期間でも次第にその自己乳化性能が失
われ、炭酸ガス発生による発泡を伴うポリ尿素体沈降物
が生起し、ついにはｒル化するので、安定に使用すると
と゛ができない欠点があった。As a method for producing such self-emulsifying polyisocyanates, it has been proposed to react polyisocyanate, 4-limethylene oxide, polyfa pyrene oxide pro, Lycium 4-limer alone or in combination with polyethylene glycol. (Tokuko Sho 61-43396
No.), is this kind of self-emulsification fiyj? If liisocyanate is mixed with water immediately after production to form an aqueous emulsion, it can form a stable emulsion within a range of 1 to 2 hours, but it cannot be heated for a long time at 25 to 35°C. When stored for a long time, even for a short period of time, its self-emulsifying ability is gradually lost, and a polyurea substance precipitate with foaming due to the generation of carbon dioxide gas is generated, which eventually turns into a molten resin, which has the disadvantage that it cannot be used stably. .
（発明の課題）
本発明は、長期間の貯蔵安定性に優れた自己乳化性ポリ
イソシアネート、特にノナ−ティクル＆ −ド用に適す
る自己乳化性ポリイソシアネートを製造する方法を提供
しようとするものである。(Problems to be solved by the invention) The present invention aims to provide a method for producing a self-emulsifying polyisocyanate having excellent long-term storage stability, particularly a self-emulsifying polyisocyanate suitable for nonarticulate and adhesive applications. be.
価）発明の構成
ＣｎＲＯ解決手段）
本発明者らは、前記の課題を解決するために種種研究を
重ねた結果、特定の／ ＋フィンシアネートをあらかじ
め特定のポリエチレングリコールと加温下で部分ウレタ
ン化反応させ、冷却したのち、特定の／リエチレンオキ
サイドとボリア”Ｅ！♂レンォキサイドのプロ、クコ−
４リマー盤七ドはキシ化合物と混合する方法によりてそ
の目的を達成することができ九ものである。Structure of the Invention CnRO Solution) As a result of repeated research in order to solve the above problems, the present inventors have developed a method of partially urethanizing a specific / + fincyanate with a specific polyethylene glycol under heating in advance. After reacting and cooling, certain / lyethylene oxide and Boria “E!
The purpose of the 4-remer disk can be achieved by mixing it with an oxy compound.
すなわち、本発明の自己乳化性ポリイソシアネートの製
法は、
（ＪＬ）３５〜６５重量−のジフェニルメタンジイソシ
アネートを含み、残部が１０個よシも大きいインシアネ
ート基を有するオリがマー性のポリメチレンポリフェニ
ルポリイソシアネートからなるポリイソシアネート１０
０重量部に。That is, the method for producing the self-emulsifying polyisocyanate of the present invention comprises (JL) 35 to 65 weight of diphenylmethane diisocyanate, and the remainder is an oligomer polymethylene polyphenyl having more than 10 incyanate groups. Polyisocyanate 10 consisting of polyisocyanate
0 parts by weight.
（１＋） 平均分子ｆｉ４００〜８００のポリエチレ
ングリコール１〜５重量部を添加し、４０〜６０℃の温
度で１〜４時間反応させ冷却したのち、（、）式
で表わされる平均構造を有し、平均分子量が１２００〜
１４００、プロピレンオキサイド残基が２０〜５０重量
−であるヒドロキシ化合物を、前記ポリイソシアネー）
（ａ）１００重量部尚シｌ〜５重量部添加し混合するこ
とを特徴とする方法である。(1+) After adding 1 to 5 parts by weight of polyethylene glycol with an average molecular fi of 400 to 800 and reacting at a temperature of 40 to 60°C for 1 to 4 hours and cooling, it has an average structure represented by the formula (,), Average molecular weight is 1200~
1400, a hydroxy compound having 20 to 50 weight propylene oxide residues (the polyisocyanate)
(a) This method is characterized in that 100 parts by weight and 1 to 5 parts by weight are added and mixed.
以下、その製法等について詳述する。The manufacturing method etc. will be explained in detail below.
本発明の製法において用いるポリイソシアネート（ａ）
は、３５〜６５重量−〇ジフェニルメタンジイソシアネ
ートを含み、残部が１０個よシ大きいイノシアネート基
を有するオリゴマー性のポリメチレンポリフェニルポリ
イソシアネートからなるポリイソシアネートであシ、イ
ソシアネート基含有量が約３１重量−程度のものである
。Polyisocyanate (a) used in the production method of the present invention
is a polyisocyanate consisting of oligomeric polymethylene polyphenyl polyisocyanate containing 35 to 65 weight - 〇 diphenylmethane diisocyanate, the remainder having more than 10 inocyanate groups, and the isocyanate group content is about 31 weight - It is of a degree.
このポリイソシアネート（ａ）と反応させるポリエチレ
ングリコール（ｂ）は、平均分子量４００〜８００のも
のである。その反応割合は、４リイソシアネ−）（ａ）
１００重量部に対してポリエチレングリコール（ｂ）が
１〜５重量部、好ましくは２〜３重量部である。その反
応は、窒素雰囲気下、４０〜６０℃の温度で１〜４時間
反応させて部分ウレタン化反応させる。との際のポリエ
チレングリコール（ｂ）の反応割合が１重量部よシ少な
くなると、部分ウレタン化反応が不充分となるし、５重
量部よ＃）４１多くなると部分ウレタン化反応が過度に
進行し、粘度が高くなルすぎるので、いずれの場合も安
定な水性エマルジョンを与える自己乳化性ポリイソシア
ネートが得られない。またその反応温度を４０〜６０℃
とし、反応時間を１〜４時間とするのは、部分ウレタン
化反応を好ましく進行させるためである。The polyethylene glycol (b) to be reacted with this polyisocyanate (a) has an average molecular weight of 400 to 800. The reaction rate is 4-lisocyanate)(a)
The amount of polyethylene glycol (b) is 1 to 5 parts by weight, preferably 2 to 3 parts by weight, per 100 parts by weight. The reaction is carried out under a nitrogen atmosphere at a temperature of 40 to 60° C. for 1 to 4 hours to form a partial urethane. When the reaction proportion of polyethylene glycol (b) is less than 1 part by weight, the partial urethanization reaction becomes insufficient, and when it increases by 5 parts by weight, the partial urethanization reaction proceeds excessively. In both cases, self-emulsifying polyisocyanates which give stable aqueous emulsions cannot be obtained because the viscosity is too high. In addition, the reaction temperature was set at 40 to 60℃.
The reason why the reaction time is 1 to 4 hours is to allow the partial urethanization reaction to proceed preferably.
以上のようにして反応させた反応生成物を、好ましくは
２５〜３５℃に冷却してから、前記式で表わされる平均
構造を有し、平均分子量が１２００〜１４００、プロピ
レンオキサイド残基が２０〜５０重量％であるヒドロキ
シ化合物を添加して均一に混合する。このヒドロキシ化
合物は前記式で示されたように、エチレンオキナイド残
基が３〜２５モルで、その両末端に２〜１５モルのプロ
ピレンオキサイドを有するものであるが、エチレンオキ
サイド残基が約１４〜２２モル、プロピレンオキサイド
残基が約２〜１０モルのものが特に好ましい。The reaction product reacted as described above is preferably cooled to 25 to 35°C, and then is heated to have an average structure represented by the above formula, an average molecular weight of 1200 to 1400, and a propylene oxide residue of 20 to 35°C. Add 50% by weight of hydroxy compound and mix uniformly. As shown in the above formula, this hydroxy compound has 3 to 25 moles of ethylene oxide residues and 2 to 15 moles of propylene oxide at both ends, but about 14 moles of ethylene oxide residues. ~22 moles, with about 2 to 10 moles of propylene oxide residues being particularly preferred.
ヒドロキシ化合物の添加量は、ポリイソシアネ−）（ａ
）１００：Ｉｌ量部に対して１〜５重量部、好ましくは
２〜３重量部であシ、その添加混合する温度は２５〜３
５℃が好ましく、添加は攪拌下に添加し、３０分〜１時
間攪拌を続けて均一に混合するようＫする。ヒドロキシ
化合物の添加量が１重量部未満になると生成するポリイ
ソシアネートの乳化性能が不充分となるし、５重量部よ
シも多くなると生成するエマル２．７粒子が微細となる
ので、いずれの場合も生成する自己乳化性ポリイソシア
ネートエマルノ、ンの安定性が悪くなる。まえ、ヒトは
キシ化合物（、）を添加し混合する温度が、たとえば４
０〜６０℃になると部分ウレタン化反応が急速に進行す
るために、５００〜８００・、ｐ、ｓの生成物が得られ
、安定性に劣るエマルゾ、ンを与える自己乳化性ポリイ
ソシアネートとなるので、好ましくないし、を九七の添
加・混合温度が２５℃未満、特に２０℃以下になると、
部分ウレタン化されたＩリメチレンポリフェニルーリイ
ソシアネートの粘度が高くなシ、攪拌が回磁になる。The amount of the hydroxy compound added is polyisocyanate)(a
) 100:1 to 5 parts by weight, preferably 2 to 3 parts by weight based on the amount of Il, and the temperature at which it is added and mixed is 25 to 3 parts by weight.
The temperature is preferably 5° C., and the mixture is added under stirring, and the stirring is continued for 30 minutes to 1 hour to ensure uniform mixing. If the amount of the hydroxy compound added is less than 1 part by weight, the emulsifying performance of the polyisocyanate produced will be insufficient, and if it exceeds 5 parts by weight, the emul particles produced will become fine. The stability of the self-emulsifying polyisocyanate emulsion produced also deteriorates. For humans, the temperature at which the xyl compound (,) is added and mixed is, for example, 4
At 0 to 60°C, the partial urethanization reaction proceeds rapidly, resulting in a product of 500 to 800 p, s, resulting in a self-emulsifying polyisocyanate that gives emulsion with poor stability. , it is not preferable, and if the addition/mixing temperature of 97 is below 25°C, especially below 20°C,
Since the viscosity of the partially urethanized I-rimethylene polyphenylisocyanate is not high, stirring is performed by rotating the magnet.
また、ポリイソシアネート（ａ）をポリエチレングリコ
ール価）で部分ウレタン化する際に同時にヒドロキシ化
合物（ｅ）を添加すると、生成する自己乳化性ポリイソ
シアネートが長期貯蔵安定性に劣るものとなるので、好
ましくない。Furthermore, if the hydroxy compound (e) is added at the same time when polyisocyanate (a) is partially urethanized with polyethylene glycol value, the self-emulsifying polyisocyanate produced will have poor long-term storage stability, which is undesirable. .
本発明の製法で得られる自己乳化性ポリイソシアネート
は、粘度２００〜３００センチポイズ／２５℃、イソシ
アネート基含有ｆｉ２７〜３０−であシ、所定量の水を
加えて高速下、機械的攪拌することによシ、安定な水性
エマルジョンが得られ、インシアネート濃度３０〜５０
重量−の水性分散体として、・譬−ティクル♂−ドの製
造に有利に使用することができる。The self-emulsifying polyisocyanate obtained by the production method of the present invention has a viscosity of 200 to 300 centipoise/25°C, an isocyanate group-containing fi of 27 to 30, and is mechanically stirred at high speed after adding a predetermined amount of water. Well, a stable aqueous emulsion can be obtained with an incyanate concentration of 30-50.
As a heavy aqueous dispersion, it can be advantageously used for the production of Tickle oxides.
（発明の効果）
性
本発明の製法によりて得られる自己乳化ｌリインシアネ
ートは、次のような効果が得られる。(Effects of the Invention) The self-emulsifying l-inocyanate obtained by the production method of the present invention has the following effects.
■ 自己乳化性ポリインシアネートは、４ケ月以上にわ
たる長期の貯蔵においても、イソシアネート基含量の低
下がなく、水との混合によシ製造直後と同等な水性エマ
ルノ、ンが得られる。(2) Self-emulsifying polyinsyanate does not lose its isocyanate group content even after long-term storage for more than 4 months, and when mixed with water, an aqueous emulsion equivalent to that immediately after production can be obtained.
■ 自己乳化性ポリイソシアネートは、水に対する分散
性が曳好で６＃）、高速インライン電キサ−による機械
的攪拌で２〜３時間にわ九って安定な放置時間を有する
水性エマル−）、ンが得られる。■ Self-emulsifying polyisocyanate is an aqueous emul that has good dispersibility in water (6#) and has a stable standing time of 2 to 3 hours with mechanical stirring using a high-speed in-line electric mixer). can be obtained.
■ がリイソシアネート水性分散体を木材チ。■ Add the aqueous lysocyanate dispersion to the wood.
ｆｔ１ｃ散布し九際Ｋ、水分のチップ中への浸透を促進
し、チｙ ７” ’ＩＲ面に４リイソシアネートを分離
させることから、イソシアネート基が活性を失うことな
く、グルートチ、ｆを放置できる時間が長い。Spreading ft1c promotes the penetration of moisture into the chip and separates the 4-lyisocyanate on the IR surface, allowing the isocyanate groups to be left alone without losing their activity. It's a long time.
このように、本発明の自己乳化性ポリイソシアネートが
、棗好な貯蔵安定性とポリイソシアネート水性分散体の
安定性とを発揮する理由は、ポリイソシアネート、特に
ジフェニルメタンジイソシアネートが、低分子量のポリ
エチレングリコールによ）部分ウレタン化され、さらに
末端Ｋｆロビレンオキサイド蓬を有するブロックコポリ
マーであるヒドロキシ化合物が部分ウレタン化している
ことによシ、親水性と疎水性の適度なパ２ンスを保持し
ている丸めと推察される。As described above, the reason why the self-emulsifying polyisocyanate of the present invention exhibits excellent storage stability and stability of an aqueous polyisocyanate dispersion is that polyisocyanate, particularly diphenylmethane diisocyanate, has a low molecular weight polyethylene glycol. 2) The hydroxy compound, which is a block copolymer that is partially urethanized and further has Kf-robylene oxide at the end, is partially urethanized, so it maintains an appropriate balance of hydrophilicity and hydrophobicity. It is presumed that.
すなわち従来技術では、本発明とは逆にポリイソシアネ
ートにヒドロキシ化合物を反応させるか、又はＩリイソ
シアネートとヒドロキシ化合物とポリエチレングリコー
ルを一緒に反応させていたが、本発明のごとく先にポリ
エチレングリコールを反応させた後、ヒドロキシ化合物
を反応させることなしに単に混合することによって、か
かる優れた自己乳化性？リイソシアネートを製造法でき
るのは全く意外なことといえる。That is, in the prior art, contrary to the present invention, polyisocyanate was reacted with a hydroxy compound, or I-lysocyanate, a hydroxy compound, and polyethylene glycol were reacted together, but as in the present invention, polyethylene glycol was reacted first. Such excellent self-emulsifying properties can be obtained by simply mixing without reacting the hydroxyl compound after making it? It can be said that it is completely surprising that liisocyanate can be produced by a method.
（実施例等）
以下、実施例及び比較例をあげてさらに説明する。なお
、これらの例において記載の儂は重量％、部は重量部で
ある。(Examples etc.) Hereinafter, further explanation will be given with reference to Examples and Comparative Examples. In addition, in these examples, "I" means % by weight, and "part" means parts by weight.
実施例１
■自己乳化性ポリイソシアネートの製造：１００１反応
缶に４リイソシアネート（イソシアネート当量１３７
、 ＮＣＯ含量３Ｌ５％、ジフェニルメタンジイソシア
ネート含量約５ｏｓ、粘度１８０ ｃｐ／ ２５℃）９
６．２１５に９、ぼりエチレングリコール（平均分子量
６１６、水酸基価１８２）１、７５ ｋＦを仕込み、窒
素シール後、攪拌下で５０℃まで昇温し、同温度で２時
間反応させた後、３５℃に冷却した。この反応液にヒド
ロキシ化合物（平均分子量１２００、水酸基価７２、エ
チレンオキサイド残基１７モル、グ筒ピレンオキサイド
残基８モルのプロ、り：１−リマー＞ ｚｏ’ｑを添加
し、２９℃まで冷却しながら３０分保持した。Example 1 ■Production of self-emulsifying polyisocyanate: 4-liisocyanate (isocyanate equivalent: 137
, NCO content 3L5%, diphenylmethane diisocyanate content approx. 5os, viscosity 180 cp/25℃)9
6.215 was charged with 1.75 kF of ethylene glycol (average molecular weight 616, hydroxyl value 182), and after being sealed with nitrogen, the temperature was raised to 50°C with stirring, and after reacting at the same temperature for 2 hours, 35 Cooled to ℃. A hydroxy compound (average molecular weight 1200, hydroxyl value 72, 17 moles of ethylene oxide residue, 8 moles of pyrene oxide residue) was added to this reaction solution, and the mixture was cooled to 29°C. It was held for 30 minutes while
得られた自己乳化性ポリイソシアネートは、粘度２２０
センチポイズ／２５℃、ＮＣＯ含量２＆６％であった。The obtained self-emulsifying polyisocyanate has a viscosity of 220
Centipoise/25°C, NCO content 2 & 6%.
■イソシアネート水性分散体の装造；
定量ポンプ、インバーター付きのホモ電キサ−（特殊機
化工業社製、タイ７’ｌｌ屋）Ｋ水６００ｋＩ／ｈｒと
前記のようＫして製造した１己乳化性ポリイソシアネー
）４００ｋＦ／ｈｒを連続的に導入して、回転数２００
Ｏｒｐｍで乳化し、ポリイソシアネート濃度４０１の
水性分散体を製造した。■ Preparation of the isocyanate aqueous dispersion; Homoelectric xer with metering pump and inverter (manufactured by Tokushu Kika Kogyo Co., Ltd., Thailand 7'll store) K water at 600 kI/hr and K-emulsion produced as above. Continuously introduce 400kF/hr
An aqueous dispersion having a polyisocyanate concentration of 401 was produced by emulsifying with Orpm.
■Ｉポリイソシアネート水性分散体安定性試験：前記■
の製造法によりて′得られた／＋フイソシアネート分散
体中に含まれるインシアネート含有量の、３０分後から
３時間後の経時変化を化学分析によシ追跡し九〇
３０分後では、製造直後のイソシアネート含量の９５％
、２時間後では８８ｔＩＩ、３時間後では７９％であり
た。そして、製造後３時間経過してもエマルジョンの分
離沈降がなく、著しい発泡も認められなかりた。■I polyisocyanate aqueous dispersion stability test: above ■
Chemical analysis was used to track changes in the incyanate content contained in the /+physocyanate dispersion obtained by the production method after 30 minutes and 3 hours, and after 9030 minutes, 95% of isocyanate content immediately after production
, 88tII after 2 hours and 79% after 3 hours. Even after 3 hours had passed after production, there was no separation and sedimentation of the emulsion, and no significant foaming was observed.
■ノーティクルボードの製造試験：
このポリイソシアネート水性分散体を用いて下記の製造
条件で・ｆ−ティクル？−ドの製造試験を行なった結果
は表１に示すとおシでありた。■Manufacturing test of noticle board: Using this polyisocyanate aqueous dispersion, under the following manufacturing conditions: f-ticle? Table 1 shows the results of a manufacturing test of the -de.
（製造条件）
チップ 針葉樹、２ワン系混合−−Ｐ厚
さ １２■
密度 ０．７１０ｇ７ｍ”
テ、７′′含水率 表層、芯層とも５慢熱圧喰件
１７０℃、４分、２８蝙ｔ２表１の各Δ−テ
ィクル＆−Ｐ製造試験の結果は、ＪＩＳ Ａ３９０８に
定められているＰタイｆＡ−ティクル？−ドの性能を十
分に満足しておシ、工業的実施において十分なものであ
りた。(Manufacturing conditions) Chips Softwood, 2-one type mixture - P thickness 12 ■ Density 0.710 g 7 m'' Te, 7'' Moisture content Both surface layer and core layer 5 chronic heat pressurization 170℃, 4 minutes, 28 minutes t2 The results of each Δ-ticle & -P manufacturing test in Table 1 fully satisfy the performance of P type fA-ticle?-de specified in JIS A3908, and are sufficient for industrial implementation. There was.
水性分散体にした場合のエマルジョンは、３０分で発泡
しグル化した。When made into an aqueous dispersion, the emulsion foamed and gelled in 30 minutes.
比較例２
上記の製造法で得られ九自己乳化ポリイソシアネートを
３０℃の温度で４ケ月貯蔵した。貯蔵後の粘度は、２４
６センチポイｔ７２５℃、イソシアネート含量２９．３
％であシ、この物を用いてパーティクルポードの製造試
験を行なり九結果は、ゲート物性において貯鷺前のもの
を用い九結果と同等であった。Comparative Example 2 Nine self-emulsifying polyisocyanates obtained by the above production method were stored at a temperature of 30° C. for 4 months. The viscosity after storage is 24
6 centipoints 725°C, isocyanate content 29.3
%, a particle pod production test was carried out using this material, and the results were equivalent to those obtained before using the material before storage in terms of gate physical properties.
比較例１
ポリエチレングリコールを全く添加・反応させずに、そ
のほかは実施例１と同様にして自己乳化ｌリイソシアネ
ートを製造した。Comparative Example 1 A self-emulsifying l-lysocyanate was produced in the same manner as in Example 1 except that polyethylene glycol was not added or reacted at all.
得られた自己乳化性がリイソシアネートは、水を加えて
エマルジョン化し九とζろ、製造直後は良好なエマルジ
、ン状態を１〜２時間保持することができたが、３０℃
、１０日間の貯蔵した後、−トを調造した。The obtained self-emulsifying isocyanate was emulsified by adding water and filtered. Immediately after production, it was possible to maintain a good emulsion state for 1 to 2 hours, but at 30°C.
After storage for 10 days, a -t was prepared.
得られた自己乳化性ポリイソシアネートに、水を加えて
エマルジョン化したとζろ、３０分後のイソシアネート
含量は約８Ｃ１で、１時間後では約１５０％であうた。Water was added to the obtained self-emulsifying polyisocyanate to form an emulsion. After 30 minutes, the isocyanate content was about 8C1, and after 1 hour it was about 150%.
このため、水性分散体製造後、直ちにが−ド裂造に使用
する必要があり九。For this reason, it is necessary to use the aqueous dispersion immediately after production.
比較例３
？リエチレンダリ；−ルの添加と同時にとドキ得られｆ
Ｆ−４リイソシアネ一ト水性分散体は、１時間後発泡を
伴いグル化した。Comparative example 3? At the same time as the addition of ethylene chloride, it is possible to obtain
The F-4 aqueous diisocyanate dispersion was glued with foaming after 1 hour.
特許出顔入 日本化成株式会社Patented face Nippon Kasei Co., Ltd.
Claims (2)
ソシアネートを含み、残部が２０個よりも大きいイソシ
アネート基を有するオリゴマー性のポリメチレンポリフ
ェニルポリイソシアネートからなるポリイソシアネート
１００重量部に、 （ｂ）平均分子量４００〜８００のポリエチレングリコ
ール１〜５重量部を添加し、４０〜６０℃の温度で１〜
４時間反応させ、冷却したのち、（ｃ）式 ▲数式、化学式、表等があります▼ で表わされる平均構造を有し、平均分子量が１２００〜
１４００、プロピレンオキサイド残基が２０〜５０重量
％であるヒドロキシ化合物を、前記ポリイソシアネート
（ａ）１００重量部当り１〜５重量部添加し混合するこ
とを特徴とする自己乳化性ポリイソシアネートの製法。(1) (a) 100 parts by weight of a polyisocyanate consisting of an oligomeric polymethylene polyphenyl polyisocyanate containing 35 to 65% by weight of diphenylmethane diisocyanate, the remainder having more than 20 isocyanate groups, (b) average Add 1 to 5 parts by weight of polyethylene glycol with a molecular weight of 400 to 800, and add 1 to 5 parts by weight of polyethylene glycol with a molecular weight of 400 to 800, and
After reacting for 4 hours and cooling, it has an average structure represented by formula (c) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ and an average molecular weight of 1200 ~
1400, a method for producing a self-emulsifying polyisocyanate, which comprises adding and mixing 1 to 5 parts by weight of a hydroxy compound containing 20 to 50% by weight of propylene oxide residues per 100 parts by weight of the polyisocyanate (a).
２５〜３５℃である第１請求項記載の自己乳化性ポリイ
ソシアネートの製法。(2) The method for producing a self-emulsifying polyisocyanate according to claim 1, wherein the temperature at which the hydroxy compound (c) is added and mixed is 25 to 35°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13459989A JPH0735429B2 (en) | 1989-05-30 | 1989-05-30 | Manufacturing method of self-emulsifying polyisocyanate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13459989A JPH0735429B2 (en) | 1989-05-30 | 1989-05-30 | Manufacturing method of self-emulsifying polyisocyanate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03714A true JPH03714A (en) | 1991-01-07 |
| JPH0735429B2 JPH0735429B2 (en) | 1995-04-19 |
Family
ID=15132165
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13459989A Expired - Fee Related JPH0735429B2 (en) | 1989-05-30 | 1989-05-30 | Manufacturing method of self-emulsifying polyisocyanate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0735429B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03297456A (en) * | 1990-04-18 | 1991-12-27 | Fuji Photo Optical Co Ltd | Ultrasonic inspection device |
| JP2013166868A (en) * | 2012-02-16 | 2013-08-29 | Sekisui Plastics Co Ltd | Pad for electrode |
-
1989
- 1989-05-30 JP JP13459989A patent/JPH0735429B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03297456A (en) * | 1990-04-18 | 1991-12-27 | Fuji Photo Optical Co Ltd | Ultrasonic inspection device |
| JP2013166868A (en) * | 2012-02-16 | 2013-08-29 | Sekisui Plastics Co Ltd | Pad for electrode |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0735429B2 (en) | 1995-04-19 |
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