JPS6232164A - Adhesive composition - Google Patents
Adhesive compositionInfo
- Publication number
- JPS6232164A JPS6232164A JP60170909A JP17090985A JPS6232164A JP S6232164 A JPS6232164 A JP S6232164A JP 60170909 A JP60170909 A JP 60170909A JP 17090985 A JP17090985 A JP 17090985A JP S6232164 A JPS6232164 A JP S6232164A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- melamine
- component
- phenol
- 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
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- Polyurethanes Or Polyureas (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は接着剤組成物に係り、特に合板の製造に用いる
に好適な、イソシアネート化合物を含むフェノール変性
アミノ樹脂系接着剤組成物に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to an adhesive composition, and particularly to a phenol-modified amino resin adhesive composition containing an isocyanate compound and suitable for use in the production of plywood.
［従来の技術］
合板等の製造に用いられる木材用接着剤として、尿素−
ホルムアルデヒド樹脂（尿素樹脂）。[Prior art] Urea is used as a wood adhesive used in the manufacture of plywood, etc.
Formaldehyde resin (urea resin).
メラミン−尿素−ホルムアルデヒド樹脂（メラミン−尿
素樹脂）、メラミン−ホルムアルデヒド樹脂（メラミン
樹脂）、メラミンーフェノールーホルムアルデヒド樹脂
（メラミン−フェノール樹脂）、メラミン−フェノール
−尿素−ホルムアルデヒド樹脂（メラミン−フェノール
−尿素樹脂）等のアミノ系樹脂後着剤が知られている。Melamine-urea-formaldehyde resin (melamine-urea resin), melamine-formaldehyde resin (melamine resin), melamine-phenol-formaldehyde resin (melamine-phenol resin), melamine-phenol-urea-formaldehyde resin (melamine-phenol-urea resin) ) and other amino resin post-adhesive agents are known.
合板製造に際しては、これらのアミノ系樹脂後着剤は、
塩化アンモニウム等の酸性物質を硬化剤として加え、更
に小麦粉等の充填剤及び水を添加して配合糊液として使
用されている。そして、合板は、この配合糊液を木材単
板に塗布した後積層して加熱圧締することにより製造さ
れている。When manufacturing plywood, these amino resin post-adhesives are
An acidic substance such as ammonium chloride is added as a hardening agent, and a filler such as wheat flour and water are further added to form a mixed sizing solution. Plywood is manufactured by applying this mixed size solution to wood veneers, then laminating them and pressing them under heat.
しかしながら、従来のアミノ系樹脂接着剤ではその接着
力が十分ではなく、製造される合板の耐久性に問題があ
った。また、より高い接着強度を得るためには、被着材
である単板の含水率を１０％以下の低い水準に保つ必要
があるが、単板の乾燥コストが膨大となったり、また過
乾燥により、製造される合板に欠陥を生じるなどの問題
もあった。However, conventional amino-based resin adhesives do not have sufficient adhesive strength and have problems with the durability of the manufactured plywood. In addition, in order to obtain higher adhesive strength, it is necessary to maintain the moisture content of the veneer, which is the adherend material, at a low level of 10% or less, but this increases the cost of drying the veneer, and it also This caused problems such as defects in the manufactured plywood.
従来、高含水率の被着材単板によっても、耐久性に優れ
た合板を製造し得る接着剤として、アミノ系樹脂にイソ
シアネート化合物を架橋硬化剤として使用し、充填剤及
び水を添加配合して接着剤配合糊液としたものが知られ
ている０例えば、メラミン−フェノール樹脂等のホルマ
リン系縮合樹脂に水性ラテックス、イソシアネート化合
物及びノニオン系界面活性剤を配合した接着剤組成物が
提案されている（特開昭６Ｏ−５５０７０）。Conventionally, as an adhesive that can produce plywood with excellent durability even with high moisture content adherend veneers, an isocyanate compound is used as a crosslinking hardening agent in an amino resin, and a filler and water are added and blended. For example, adhesive compositions have been proposed in which formalin-based condensed resins such as melamine-phenol resins are blended with aqueous latex, isocyanate compounds, and nonionic surfactants. (Japanese Unexamined Patent Publication No. 6O-55070).
［発明が解決しようとする問題点］
特開昭６０−５５０７０に記載されているイソシアネー
ト化合物を架橋剤とする接着剤組成物においては、ホル
マリン系縮合樹脂中の末端のメチロール基、アミ７基、
水酸基、更には樹脂中の水 ・と、イソシアネート化合
物の末端のイソシアネート基とが容易に反応を生起する
。[Problems to be Solved by the Invention] In the adhesive composition using an isocyanate compound as a crosslinking agent described in JP-A No. 60-55070, terminal methylol groups, amide 7 groups,
The hydroxyl group, furthermore, the water in the resin easily reacts with the terminal isocyanate group of the isocyanate compound.
この反応は、ウレタン結合又は尿素結合を生じさせるも
のであり、ウレタン結合による高分子化に起因する樹脂
組成物の配合糊液の粘度上昇（増 ・粘）や、炭酸ガ
ス発生をともなう尿素結合による接着剤組成物の発泡、
ゲル化等の様々な不都合が起きる。その結果、接着剤組
成物の配合糊液の安定性が損なわれ、可使時間が極めて
短いものとなる。This reaction generates urethane bonds or urea bonds, and increases the viscosity (increasing and viscosity) of the paste solution of the resin composition due to polymerization due to urethane bonds, and urea bonds that generate carbon dioxide gas. Foaming of adhesive compositions,
Various inconveniences such as gelation occur. As a result, the stability of the paste solution of the adhesive composition is impaired, resulting in an extremely short pot life.
従って、特開昭６０−５５０７０においては、このよう
な問題を改善し、単板への塗布作業性の悪化や接着力の
低下を防止するために、イソシアネート基と他の官能基
との反応を遅くさせることを目的として、水性ラテック
ス、界面活性剤等の添加剤の使用が必須とされていた。Therefore, in JP-A No. 60-55070, in order to improve such problems and prevent the deterioration of coating workability on veneers and the decrease in adhesive strength, the reaction between isocyanate groups and other functional groups was introduced. For the purpose of slowing down the process, the use of additives such as water-based latex and surfactants was considered essential.
しかしながら、特開昭６０−５５０７０においては、こ
れらの添加剤が多量に添加されるため、接着剤組成物が
水−エマルジ□ン系の配合糊液となり、均一性に乏しく
、塗布作業に困難が伴なう等の欠点があった。However, in JP-A No. 60-55070, since these additives are added in large quantities, the adhesive composition becomes a water-emulgin type compounded paste liquid, which lacks uniformity and makes coating work difficult. There were drawbacks such as:
このようなことから、添加剤を使用しない、優れた接着
性能を有する接着剤組成物の出現が強く望まれていた。For these reasons, there has been a strong desire for an adhesive composition that does not use additives and has excellent adhesive performance.
［問題点を解決するための手段］
本発明は上記従来の問題点を解決し、接着性能、塗布性
能に極めて優れた接着剤組成物を提供するものであって
、
メラミン、フェノール及びホルムアルデヒドを必須成分
とする熱硬化性樹脂と、′イソシアネート化合物とを主
成分とする接着剤組成物で、あって、その組成が、メラ
ミン成分１００重量部に対し、フェノール成分１０〜３
０重量部、イソシアネート成分４〜２５重量部（ＮＣＯ
基換算値）であることを特徴とする接着剤組成物、
を要旨とするものである。[Means for Solving the Problems] The present invention solves the above-mentioned conventional problems and provides an adhesive composition with extremely excellent adhesion performance and coating performance, which essentially contains melamine, phenol, and formaldehyde. An adhesive composition whose main components are a thermosetting resin and an isocyanate compound, the composition of which is 10 to 3 parts by weight of a phenol component per 100 parts by weight of a melamine component.
0 parts by weight, 4 to 25 parts by weight of isocyanate component (NCO
An adhesive composition characterized in that:
本発明者らは、水性ラテックス等の添加剤を使用する必
要のない、優れた接着剤組成物を得るべく、まず、公知
のアミノ樹脂、即ち尿素樹脂、メラミン−尿素樹脂、メ
ラミン樹脂、メラミン−フェノール樹脂、及びフェノー
ル樹脂を種々のモル比、縮合度で製造し、これらの樹脂
に充填剤と水を加え混合攪拌し、更に各種のイソシアネ
ート化合物を添加混合して配合糊液を調整し、増粘と発
泡の状態を観察し、接着力試験を行なった。しかるに、
この結果、公知のアミノ樹脂及びフェノール樹脂では、
配合糊液は３０分〜１時間以内の短詩間で発泡するか又
は増粘してしまい、その塗布性能が著しく低下し、接着
力も極めて劣るものであることが判明した。In order to obtain an excellent adhesive composition that does not require the use of additives such as aqueous latex, the present inventors firstly used known amino resins, namely urea resins, melamine-urea resins, melamine resins, and melamine-urea resins. Phenol resins and phenolic resins are manufactured at various molar ratios and degrees of condensation, fillers and water are added to these resins, mixed and stirred, and various isocyanate compounds are added and mixed to adjust the blended paste liquid. The state of viscosity and foaming was observed, and an adhesion test was conducted. However,
As a result, with known amino resins and phenolic resins,
It was found that the blended paste solution foamed or thickened within a short period of 30 minutes to 1 hour, resulting in a marked decline in coating performance and extremely poor adhesive strength.
そこで、本発明者らは、フェノール樹脂のモル比と水混
和性を変えたうえでイソシアネート化合物を添加するこ
とを試みたところ、イソシアネート基の反応が遅くなる
配合範囲があり、更にアミン樹脂を加えてもこの所定の
範囲であればイソシアネート基の反応を抑制することが
でき、得られる配合糊液は、増粘することも発泡するこ
ともないこと、しかも、接着力試験を行なったところ、
木材単板に対する塗布性能は極めて良好であり、耐久性
の良い優れた接着性が発現されることを見い出し、本発
明を完成した。Therefore, the present inventors tried adding an isocyanate compound after changing the molar ratio and water miscibility of the phenol resin, but found that there was a blending range in which the reaction of the isocyanate group was slow, and that by adding an amine resin. However, within this predetermined range, the reaction of the isocyanate groups can be suppressed, and the resulting blended paste liquid does not thicken or foam. Moreover, when an adhesive strength test was conducted,
The present invention was completed based on the discovery that the coating performance on wood veneers is extremely good and that excellent adhesiveness with good durability is exhibited.
以下に本発明をより詳細に説明する。The present invention will be explained in more detail below.
本発明の接着剤組成物は、メラミン、フェノール及びホ
ルムアルデヒドを必須成分とする熱硬化性樹脂（以下「
第１成分」ということがある、）と、イソシアネート化
合物（以下「第２成分」ということがある。）とを主成
分とするものである。The adhesive composition of the present invention is a thermosetting resin (hereinafter referred to as "
The main components are an isocyanate compound (hereinafter sometimes referred to as a "second component").
本発明において、第１成分である、メラミン、フェノー
ル及びホルムアルデヒドを必須成分とする熱硬化性樹脂
は。In the present invention, the first component is a thermosetting resin containing melamine, phenol, and formaldehyde as essential components.
■ フェノールとホルムアルデヒドをアルカリ性条件下
で反応させ、さらにメラミン及びホルマリンを添加して
フェノール−メラミン共縮合樹脂を製造する。(2) Phenol and formaldehyde are reacted under alkaline conditions, and melamine and formalin are further added to produce a phenol-melamine cocondensation resin.
又は
■ アミノ樹脂にフェノール樹脂子＠縮合物を混合し、
常温又は加温下に反応させてフェノール変性アミノ樹脂
を製造する。Or ■ Mix phenolic resin condensate with amino resin,
A phenol-modified amino resin is produced by reacting at room temperature or under heating.
の方法により容易に製造し得る。これらの方法のうち、
■の方法において、アミン樹脂としてはメラミン樹脂、
メラミン−尿素樹脂等が挙げられ−る。また、フェノー
ル樹脂予備縮合物としては低アルカリレゾールが好まし
い。It can be easily manufactured by the following method. Of these methods,
In method (2), the amine resin is melamine resin,
Examples include melamine-urea resin. Further, as the phenolic resin precondensate, a low alkaline resol is preferable.
アミン樹脂、フェノール樹脂予備縮合物の好適な製造法
を下記■及び■に示す。Suitable methods for producing amine resins and phenol resin precondensates are shown in (1) and (2) below.
■ アミノ樹脂の製法
よムラ−辷２ＪＬ脂
メラミン１モルに対して、ホルムアルデヒド２．３〜２
．８モルを加え、更にポリビニルアルコール及びメタノ
ールを少量添加し、水酸化ナトリウムでｐ）１１１−１
２に調整する。このものを温度８５〜９０℃で縮合反応
させて、粘度１．５〜２．０ボイズ、不揮発分５０〜６
０％の樹脂を得る。■ Amino resin manufacturing method: 2.3 to 2 formaldehyde per mole of melamine.
．． Add 8 mol, further add a small amount of polyvinyl alcohol and methanol, and add p) 111-1 with sodium hydroxide.
Adjust to 2. This material is subjected to a condensation reaction at a temperature of 85 to 90°C, and has a viscosity of 1.5 to 2.0 voids and a nonvolatile content of 50 to 6.
Obtain 0% resin.
メラミン−
メラミン１モルに対して尿素０．６〜１．０モル及びホ
ルムアルデヒド３．０〜４．０モルを加え、更にポリビ
ニルアルコール及びメタノールを少量添加し、水酸化ナ
トリウムでＰＨ１１〜１２に調整する。このものを８８
〜９２℃で縮合反応させて、粘度１．５〜２．５ボイズ
、不揮発分５０〜６０％の樹脂を得る。Melamine - Add 0.6 to 1.0 moles of urea and 3.0 to 4.0 moles of formaldehyde to 1 mole of melamine, then add a small amount of polyvinyl alcohol and methanol, and adjust the pH to 11 to 12 with sodium hydroxide. . 88 this thing
A condensation reaction is carried out at ~92°C to obtain a resin having a viscosity of 1.5 to 2.5 voids and a nonvolatile content of 50 to 60%.
■ フェノール樹脂予備縮合物の製法
フェノール１モルに対してホルムアルデヒド１．５〜２
．５モル、水酸化ナトリウム０．０４〜０．１０モルを
加え、温度８０〜８５℃で３〜４昨間縮合して、粘度６
０〜８０センチボイズ、不揮発分４５〜５０％、水混和
性（ＪＩＳＫ ６８０２）１〜３倍の樹脂を得る。■ Production method of phenol resin precondensate 1.5 to 2 formaldehyde per mole of phenol
．． Add 5 moles of sodium hydroxide and 0.04 to 0.10 moles of sodium hydroxide, and condense at a temperature of 80 to 85°C for 3 to 4 hours to obtain a viscosity of 6.
A resin having a centivoise of 0 to 80, a nonvolatile content of 45 to 50%, and a water miscibility (JISK 6802) of 1 to 3 times is obtained.
なお、フェノール樹脂予備縮合物を製造する際、フェノ
ール１モルに対する水酸化ナトリウムのモル比が０．０
４より少ないと、得られる綜合物のアミノ樹脂との相溶
性が低く、また０、１０モルより多いと、得られる接着
剤組成物が増粘し易くなる。In addition, when producing the phenol resin precondensate, the molar ratio of sodium hydroxide to 1 mole of phenol is 0.0.
When the amount is less than 4, the resulting composite has low compatibility with the amino resin, and when it is more than 0.10 moles, the resulting adhesive composition tends to thicken.
また、フェノール樹脂予備縮合物の水混和性が１倍より
少ないとアミン樹脂との相溶性が悪くなり、３倍より大
きいと、得られる接着剤組成物の接着力が低下する。Moreover, if the water miscibility of the phenolic resin precondensate is less than 1 time, the compatibility with the amine resin will be poor, and if it is more than 3 times, the adhesive strength of the resulting adhesive composition will be reduced.
次にアミノ樹脂とフェノール樹脂予備縮合物とからフェ
ノール変性アミン樹脂を製造する方法について説明する
。Next, a method for producing a phenol-modified amine resin from an amino resin and a phenol resin precondensate will be described.
まず、原料であるアミン樹脂（メラミン樹脂又はメラミ
ン−尿素樹脂）とフェノール樹脂予備縮合物とを、メラ
ミン成分１００重量部に対してフェノール成分１０〜３
０重量部となるように記合し、これを温度３５〜７５℃
で１０〜３０分間攪拌下顎熱して反応させた後、室温に
冷却する。First, amine resin (melamine resin or melamine-urea resin) as a raw material and phenol resin precondensate are added in an amount of 10 to 3 parts by weight of phenol component per 100 parts by weight of melamine component.
0 parts by weight, and heat it at a temperature of 35 to 75°C.
After stirring and heating for 10 to 30 minutes, the reaction mixture is cooled to room temperature.
この際、加熱は温度６５℃程度で約１５分間行うのが好
ましい。At this time, heating is preferably performed at a temperature of about 65° C. for about 15 minutes.
このアミノ樹脂とフェノール樹脂予備縮合物との反応は
、メラミン樹脂又はメラミン−尿素樹脂の製造工程にお
いて、縮合反応後の冷却過程でフェノール樹脂予備縮合
物を添加することにより、連続的に行わせても良い。This reaction between the amino resin and the phenolic resin precondensate can be carried out continuously by adding the phenolic resin precondensate during the cooling process after the condensation reaction in the melamine resin or melamine-urea resin manufacturing process. Also good.
熱硬化性樹脂中のフェノール成分は、メラミン成分１０
０重量部に対して１０〜３０重量部であるが、フェノー
ル成分が１０重量部よりも少ないと増粘と発泡が生起し
、また３０重量部よりも多いと増粘してゲル状物になる
ため好ましくない。The phenol component in the thermosetting resin is melamine component 10
If the phenol component is less than 10 parts by weight, thickening and foaming will occur, and if it is more than 30 parts by weight, the phenol component will thicken and become a gel-like substance. Therefore, it is undesirable.
本発明においては、このようにして製造されるフェノー
ル変性アミノ樹脂を熱硬化性樹脂として用いるが、熱硬
化性樹脂としてはこれに限られず、その他の方法で製造
されたものでも良い。In the present invention, the phenol-modified amino resin produced in this manner is used as the thermosetting resin, but the thermosetting resin is not limited to this, and may be produced by other methods.
その他の熱硬化性樹脂の製法としては、メラミン、フェ
ノール、ホルムアルデヒド（及び必要に応じ尿素）を同
時に混合して反応させる方法。Another method for producing thermosetting resins is to simultaneously mix and react melamine, phenol, and formaldehyde (and urea if necessary).
メラミン（又はフェノール）とホルムアルデヒド（及び
必要に応じ尿素）を反応させた後、フェノール（又はメ
ラミン）を反応させる方法が挙げられる。A method may be mentioned in which melamine (or phenol) is reacted with formaldehyde (and urea if necessary) and then reacted with phenol (or melamine).
本発明においては、このようにして得られる熱硬化性樹
脂はＪＩＳ Ｋ ６８０１に従って測定されたゲル
化時間が３０〜９０分／４０℃の樹脂であることが好ま
しい、ゲル化時間が３０分よりも短いと配合糊液の安定
性が悪くなり、また９０分よりも長いと接着性が低下す
る。また、ＪＩＳＫ ６８０１に従って測定されたｐ
Ｈが７〜１０、粘度が１〜３ボイズ、不揮発分が５０〜
′６０％であることが好ましい。In the present invention, the thermosetting resin thus obtained is preferably a resin with a gelation time of 30 to 90 minutes/40°C measured according to JIS K 6801, and a gelation time of less than 30 minutes. If it is too short, the stability of the blended paste solution will deteriorate, and if it is longer than 90 minutes, the adhesiveness will be reduced. In addition, p measured according to JISK 6801
H is 7-10, viscosity is 1-3 voids, non-volatile content is 50-
'60% is preferred.
なお１本発明においては、熱硬化性樹脂中に尿素成分を
含有させる場合の熱硬化性樹脂中の尿素成分の含有量は
、メラミン成分１００重量部に対し１００重量部以下と
するのが好ましい、尿素成 分がメラミン１００重量
部に対して１００重量部を超えると、得られる接着剤組
成物の接着力が低下する傾向がある。Note that in the present invention, when the urea component is contained in the thermosetting resin, the content of the urea component in the thermosetting resin is preferably 100 parts by weight or less per 100 parts by weight of the melamine component. If the urea component exceeds 100 parts by weight per 100 parts by weight of melamine, the adhesive strength of the resulting adhesive composition tends to decrease.
熱硬化性樹脂に尿素成分を含有させるには、前述のよう
に、メラミン又はフェノールをホルムアルデヒドと反応
させるに際して尿素を付加させても良く、あるいは、次
のようにしても良い、即ち、例えばアミノ樹脂とフェノ
ール樹脂とから製造されたフェノール変性アミノ樹脂に
、更に加熱することなしに室温下で尿素樹脂を添加する
方法である。この場合に使用される尿素樹脂の好適な製
造法を下記に示す。In order to make the thermosetting resin contain a urea component, as mentioned above, urea may be added when reacting melamine or phenol with formaldehyde, or it may be done as follows. In this method, a urea resin is added to a phenol-modified amino resin produced from a phenol resin and a phenol resin at room temperature without further heating. A preferred method for producing the urea resin used in this case is shown below.
の な
ｊ［１モルに対してホルムアルデヒド１．８〜２．２モ
ルを加え、更にコーンスターチとポリビニルアルコール
とを少量添加する。このものを２５％アンモニア水溶液
を触媒として、ｐＨ７，０〜ａ、Ｏに調整して、温度８
２〜８７℃で約６０〜８０分量線合反応させる０次いで
、炭酸ナトリウムでＰＨ７，０〜８．０に再度調整し、
更に尿素０．１〜０．２モルを添加した後、１０分間縮
合反応させて、粘度１．５〜２．０ボイズ、不揮発分４
７〜５２％の樹脂を得る。Add 1.8 to 2.2 moles of formaldehyde per 1 mole, and further add a small amount of cornstarch and polyvinyl alcohol. This material was adjusted to pH 7.0 - a, O using a 25% ammonia aqueous solution as a catalyst, and the temperature was 8.
Linear reaction is carried out for about 60 to 80 minutes at 2 to 87°C.Then, the pH is adjusted to 7.0 to 8.0 again with sodium carbonate,
Further, after adding 0.1 to 0.2 mole of urea, a condensation reaction was performed for 10 minutes to obtain a viscosity of 1.5 to 2.0 voids and a nonvolatile content of 4.
7-52% resin is obtained.
本発明の接着剤組成物の第２成分であるイソシアネート
化合物としては１．ヘキサメチレンジイソシアネート（
ＨＭＤＩ）、４，４°−ジフェニルメタンジイソシアネ
ート（ＭＤＩ）、ポリメチレンポリフェニルポリイソシ
アネート（ポリメリックＭＤＩ）、その他、これらを水
、アルコール、アミン、アミド、カルボン酸等で変性し
たポリイソシアネート化合物等が挙げられる。これらの
中では、特にポリメチレンポリフェニルポリイソシアネ
ート系化合物であるポリメリックＭＤＩが好ましい。The isocyanate compound which is the second component of the adhesive composition of the present invention includes 1. Hexamethylene diisocyanate (
HMDI), 4,4°-diphenylmethane diisocyanate (MDI), polymethylene polyphenyl polyisocyanate (polymeric MDI), and other polyisocyanate compounds modified with water, alcohol, amine, amide, carboxylic acid, etc. . Among these, polymeric MDI, which is a polymethylene polyphenyl polyisocyanate compound, is particularly preferred.
本発明の接着剤組成物は第１成分の熱硬化性樹脂と第２
成分のイソシアネート化合物とを主成分とするものであ
るが、組成物中のイソシアネート成分はメラミン成分１
００重量部に対してＮＣＯ基換算で４〜２５重量部であ
る。The adhesive composition of the present invention comprises a thermosetting resin as a first component and a thermosetting resin as a second component.
The main component is an isocyanate compound, but the isocyanate component in the composition is a melamine component 1.
It is 4 to 25 parts by weight in terms of NCO group based on 00 parts by weight.
即ち、本発明の接着剤組成物の組成は、メラミン成分１
００重量部に対し、フェノール成分１０〜３Ｑｆｆｉ量
部、イソシアネート成分４〜２５重量部（ＮＣＯ基換算
値）であるが、メラミン成分、フェノール成分、イソシ
アネート成分の各成分が、この限定範囲よりも多量でも
、少量でも、得られる接着剤組成物の配合糊液の増粘や
発泡、更。That is, the composition of the adhesive composition of the present invention is as follows: melamine component 1
00 parts by weight, the phenol component is 10 to 3 Qffi parts, and the isocyanate component is 4 to 25 parts by weight (NCO group equivalent value), but each of the melamine component, phenol component, and isocyanate component is in an amount larger than this limited range. However, even in a small amount, the resulting adhesive composition can thicken, foam, and foam.
にはゲル化が生起し、塗布性の悪化と接着力の低下をま
ねくので好ましくない。This is undesirable because gelation occurs, leading to deterioration in coating properties and a decrease in adhesive strength.
本発明の接着剤組成物は、このような第１成分及び第２
成分の他に小麦粉、カオリンクレー等の通常用いられる
充填剤を含有していても良い。The adhesive composition of the present invention comprises such a first component and a second component.
In addition to the ingredients, it may contain commonly used fillers such as wheat flour and kaolin clay.
このような本発明の接着剤組成物の配合糊液の調合方法
としては、特に制限はなく、各成分の配合順序等も任意
であるが、例えば、フェノール変性アミノ樹脂にイソシ
アネート化合物として、ポリメチレンポリフェニルポリ
イソシアネートを所定の割合で添加し、同時に小麦粉、
カオリンクレー等の充填剤及び水を加えて混合攪拌して
配合糊液とするのが好ましい。There are no particular restrictions on the method for preparing the paste solution of the adhesive composition of the present invention, and the order of blending each component is arbitrary. Add polyphenyl polyisocyanate at a predetermined ratio, and at the same time add flour,
It is preferable to add a filler such as kaolin clay and water and mix and stir to form a blended paste solution.
本発明の接着剤組成物が水性ラテックス等の添加剤を添
加することもなく、イソシアネート化合物の化学的反応
を防止して、安定な配合糊液で高い接着力を発揮し得る
理由についての詳細は必ずしも明確ではないが、本発明
の接着剤組成物の各成分の限定された組成範囲において
は、化学的に極めて安定となり、末端メチロール基、ア
ミン基、フェノラート基、フェノール性水酸基、更には
水溶液である配合糊液中の水酸基等が水素結合により強
く再編成されるため、これらがイソシアネート基と急激
な化学的反応を生起しにくいためと考えられる。For details on the reason why the adhesive composition of the present invention can prevent chemical reactions of isocyanate compounds without adding additives such as water-based latex, and can exhibit high adhesive strength with a stable compounded glue solution, please see below. Although it is not necessarily clear, within a limited composition range of each component of the adhesive composition of the present invention, it is chemically extremely stable and has terminal methylol groups, amine groups, phenolate groups, phenolic hydroxyl groups, and even aqueous solutions. This is thought to be because hydroxyl groups and the like in a certain blended size liquid are strongly reorganized by hydrogen bonds, making it difficult for these groups to cause rapid chemical reactions with isocyanate groups.
［実施例］
以下に実施例及び比較例を挙げて本発明を更に具体的に
説明するが、本発明はそ９要旨を超えない限り以下の実
施例に限定されるものではない。[Examples] The present invention will be described in more detail below with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples as long as they do not exceed the gist of the invention.
なお、本例において、樹脂の粘度、比重、ｐＨ１不揮発
分、ゲル化時間等の物性は、ＪＩＳＫ ６８０１に準
拠して測定したものである。また、部は「重量部」、％
は「重量％」を示す。In this example, the physical properties of the resin, such as viscosity, specific gravity, pH 1 nonvolatile content, and gelation time, were measured in accordance with JISK 6801. Also, parts are "parts by weight", %
indicates "% by weight".
各側において使用したアミノ樹脂、フェノール樹脂予備
縮合物、尿素樹脂の製造法は次の（Ａ）〜（Ｄ）に示す
通りである。また、イソシアネート化合物としては、下
記■、■の市販ポリメチレンポリフェニルポリイソシア
ネートを用いた（なお、いずれも固形分がほぼ１００％
のものであった。）。The methods for producing the amino resin, phenol resin precondensate, and urea resin used on each side are as shown in the following (A) to (D). In addition, as the isocyanate compound, the following commercially available polymethylene polyphenyl polyisocyanates (1) and (2) were used (in both cases, the solid content was approximately 100%).
It belonged to ).
■ ＰＡＰＩ−ｔ３５ （化成アップジョン■製）ＮＧ
Ｏ含量二３１％
粘度：２．０ボイズ／２５℃
■ ＰＡＰＩ−２０（化成アップジョン■製）ＮＧＯ含
量：２９．８％
粘度：２１ポイズ／２５℃
反応器に３７％ホルマリン５８３．５部（７，２５モル
）及びメタノール５６．４部を仕込み、攪拌下、メラミ
ン３４６．４部（２，７５・モル）及びポリビニルアル
コール（ケン化度９７％１重合度１７００）５．２部を
加え、更に３０％水酸化ナトリウム水溶液８．１部を添
加してＰＨ１１，６に調整した。このものを約３０分間
を要して温度９０℃に昇温し、同温度で約３時量線合反
応を行った０次いで、１０％炭酸ナトリウム水溶液３部
を添加し、室温に冷却した。得られたメラミン樹脂は粘
度２．０ボイズ、ｐＨ８，６、不揮発分５７％であった
。■ PAPI-t35 (manufactured by Kasei Upjohn ■) NG
O content: 231% Viscosity: 2.0 poise/25℃ ■ PAPI-20 (manufactured by Kasei Upjohn ■) NGO content: 29.8% Viscosity: 21 poise/25℃ 583.5 parts of 37% formalin ( 7.25 mol) and 56.4 parts of methanol were added, and while stirring, 346.4 parts (2.75 mol) of melamine and 5.2 parts of polyvinyl alcohol (degree of saponification 97% 1 degree of polymerization 1700) were added. Furthermore, 8.1 parts of a 30% aqueous sodium hydroxide solution was added to adjust the pH to 11.6. This mixture was heated to 90°C over a period of about 30 minutes, and a linear combination reaction was carried out at the same temperature for about 3 hours.Next, 3 parts of a 10% aqueous sodium carbonate solution was added, and the mixture was cooled to room temperature. The obtained melamine resin had a viscosity of 2.0 voids, a pH of 8.6, and a nonvolatile content of 57%.
反応器に３７％ホルマリン６１１．４（７，５４モル）
、メラミン２５０部（１，９８モル）、尿１９５ｆｆｌ
！ （１、５８モル）、ポリビニルアルコール（ケン化
度９７％１重合度１．７００）１０部及びメタノール１
９．１部を仕込み、更に３０％水酸化ナトリウム水溶液
９．５部を加えて、約３０分間を要して９０℃まで昇温
した。このものを同温度で約２時開綿合反応を行った後
、１０％炭酸ナトリウム水溶液５部を添加し、室温まで
冷却した。得られたメラミン−尿素樹脂は、粘度１．７
７ボイズ、ｐＨ８，６，不揮発分５６％であった。37% formalin 611.4 (7.54 mol) in the reactor
, 250 parts (1,98 mol) of melamine, 195 ffl of urine
! (1.58 mol), 10 parts of polyvinyl alcohol (degree of saponification 97% 1 degree of polymerization 1.700) and 1 part of methanol
9.1 parts of the mixture was charged, and 9.5 parts of a 30% aqueous sodium hydroxide solution was added thereto, and the temperature was raised to 90°C over about 30 minutes. This product was subjected to a cotton-combining reaction at the same temperature for about 2 hours, then 5 parts of a 10% aqueous sodium carbonate solution was added, and the mixture was cooled to room temperature. The obtained melamine-urea resin has a viscosity of 1.7
7 voids, pH 8.6, and non-volatile content 56%.
（Ｃ）： フェノール １ ・ ホルムア反応
器に３７％ホルマリン５９３．５部（７，３２モル）、
フェノール３４６．９部（３，６９モル）及びメタノー
ル３０．１部を仕込み、攪拌下、３０％水酸化ナトリウ
ム水溶液２９．５部（０，２２モル）を加えてｐＨ９，
２に調整した。このものを約３０分間を要して８０℃ま
で昇温し、同温度で約４時量線合反応を行った後、室温
に冷却した。得られたフェノール樹脂予備縮合物は、粘
度７５センチボイズ、ＰＨ８，４、不揮発分４９％、水
混和性（Ｊ Ｉ Ｓ Ｋ ６８０２）２倍であった
。(C): Phenol 1 593.5 parts (7.32 mol) of 37% formalin in a formrea reactor,
346.9 parts (3.69 mol) of phenol and 30.1 parts of methanol were charged, and while stirring, 29.5 parts (0.22 mol) of a 30% aqueous sodium hydroxide solution was added to adjust the pH to 9.
Adjusted to 2. The temperature of this product was raised to 80° C. over about 30 minutes, and the line combination reaction was carried out at the same temperature for about 4 hours, and then cooled to room temperature. The obtained phenolic resin precondensate had a viscosity of 75 centiboise, a pH of 8.4, a non-volatile content of 49%, and a water miscibility (JIS K 6802) twice as high.
反応器に３７％ホルマリン６７４．９部（８，３２モル
）及び２５％アンモニア水１６．８部を仕込み、ＰＨ７
，２に調節して、攪拌下、尿素２５９．５部（４，３３
モル）、ポリビニルアルコール（ケン化度９９％、重合
度１７００）６．０部及びコーンスターチ１．３部を添
加した。このものを約３０分間を要して８５℃まで昇温
し、同温度で７０分間開綿反応を行った０次いで、１０
％炭酸ナトリウム水溶液４．９部を添加し、ｐＨ７，４
に調整して、尿素２７．５部（０，４６モル）を加え同
温度で１０分間反応を行った後、室温まで冷却した。得
られた尿素樹脂は、粘度１．８ボイズ、ＰＨ７，２、不
揮発分４９％であった。674.9 parts (8.32 moles) of 37% formalin and 16.8 parts of 25% aqueous ammonia were charged into a reactor, and the pH was adjusted to 7.
, 259.5 parts of urea (4,33 parts) under stirring.
mol), 6.0 parts of polyvinyl alcohol (degree of saponification 99%, degree of polymerization 1700), and 1.3 parts of cornstarch were added. This material was heated to 85°C over about 30 minutes, and a cotton opening reaction was performed at the same temperature for 70 minutes.
% sodium carbonate aqueous solution was added, and the pH was adjusted to 7.4.
After adjusting the temperature to 27.5 parts (0.46 mol) of urea and reacting at the same temperature for 10 minutes, the mixture was cooled to room temperature. The obtained urea resin had a viscosity of 1.8 voids, a pH of 7.2, and a nonvolatile content of 49%.
実施例１
■、 フェノール変性アミン樹脂の製造前記（Ａ）で得
られたメラミン樹脂８５０部と（Ｃ）で得られたフェノ
ール樹脂予備縮合物１５０部を反応器に仕込み、攪拌混
合しながら昇温し、６０℃で１５分間加加熱台した後、
室温まで冷却した。得られたフェノール変性アミン樹脂
は粘度１．７１ボイズ、比重１．２０６、ｐＨ８，４、
不揮発分５６％、ゲル化時間４５分／℃であり、温度３
０℃で貯蔵した場合、粘度が２倍に上昇するまで安定に
貯蔵し得る日数は４０日であった。Example 1 (2) Production of phenol-modified amine resin 850 parts of the melamine resin obtained in (A) above and 150 parts of the phenol resin precondensate obtained in (C) were charged into a reactor, and the temperature was raised while stirring and mixing. After heating at 60℃ for 15 minutes,
Cooled to room temperature. The obtained phenol-modified amine resin had a viscosity of 1.71 voids, a specific gravity of 1.206, a pH of 8.4,
The non-volatile content was 56%, the gelation time was 45 minutes/°C, and the temperature was 3.
When stored at 0° C., the number of days it could be stably stored until the viscosity doubled was 40 days.
■、 配合糊液の調合
糊液調合容器に、上記■で得られたフェノール変性アミ
ノ樹脂１００部をとり、充填剤として小麦粉１５部、カ
オリンクレー１０部ヲ添加して。(2) Preparation of blended size solution 100 parts of the phenol-modified amino resin obtained in step (2) above was placed in a size solution mixing container, and 15 parts of wheat flour and 10 parts of kaolin clay were added as fillers.
十分に攪拌混合した後、水１０部を添加した。このもの
に攪拌下、イソシアネート化合物としてＰＡＰＩ−１３
５を１０部添加し、十分に攪拌混合して接着剤組成物の
配合糊液を調合した。After thorough stirring and mixing, 10 parts of water was added. PAPI-13 was added to this as an isocyanate compound while stirring.
10 parts of No. 5 were added thereto and thoroughly stirred and mixed to prepare a blended paste solution of an adhesive composition.
得られた接着剤組成物中のメラミン、フェノール、尿素
、イソシアネートの各成分の割合を第１表に示す。Table 1 shows the proportions of each component of melamine, phenol, urea, and isocyanate in the obtained adhesive composition.
■、 接着剤組成物の性能試験
増粘性
配合糊液を温度３０℃にて放置し、１時間後、２時間後
、３時間後の粘度を測定し、配合直後の粘度（実施例１
においては２３ポイズ／３０℃）で徐した値を配合糊液
の増粘倍率として表した。■ Performance test of adhesive composition The thickening compounded paste liquid was left at a temperature of 30°C, and the viscosity was measured after 1 hour, 2 hours, and 3 hours, and the viscosity immediately after compounding (Example 1
In this case, the value obtained by increasing the viscosity at a rate of 23 poise/30° C.) was expressed as the thickening ratio of the blended paste solution.
結果を第１表に示す。The results are shown in Table 1.
塗布性能
配合糊液を温度３０℃に１時間、２時間又は３時間放置
した後、３ブライ合板製造時の芯板単板に塗布し、その
塗布性を調べ、経過時間に伴う配合糊液の塗布性能の変
化を評価した。結果を第１表に示す。Coating performance After leaving the compounded size solution at a temperature of 30°C for 1, 2, or 3 hours, it was applied to a core board veneer used in the manufacture of 3-brie plywood, and its applicability was investigated. Changes in coating performance were evaluated. The results are shown in Table 1.
接着力
配合糊液を３０℃に放置し、放置１時間後、２時間後、
３時間後の配合糊液を芯板単板に塗布して、各々、３プ
ライ合板を製造した、なお、合板の製造条件は下記の通
りである。The adhesive strength compounded paste solution was left at 30°C, and after 1 hour and 2 hours,
After 3 hours, the mixed paste solution was applied to the core veneer to produce 3-ply plywood. The production conditions for the plywood were as follows.
単板構成 １．８＋１．．８＋１．８ｍｍ（ラワ
ン材、５．４ｍｍ合板）
単板の含水率 １５〜２０％
配合糊液塗布量 ３０ ｇ ／ ９００ ｃは堆積時間
１０〜１５分間
冷 圧 １０ｋｇ／ｃｒｎ’、２０分熱
圧 １ ２．０℃、 １０ｋｇ／ｃｍ″、
２分間
このようにして製造した合板を、ＪＡＳＩ類の接着力試
験方法に準じて、接着力試験を行った。Single board configuration 1.8+1. ．． 8+1.8mm (lauan wood, 5.4mm plywood) Moisture content of veneer 15-20% Amount of mixed paste applied 30 g / 900 c is deposition time 10-15 minutes cold Pressure 10 kg/crn', 20 minutes heat
Pressure 1 2.0℃, 10kg/cm'',
The plywood thus produced for 2 minutes was subjected to an adhesion test according to the JASI adhesion test method.
この結果を第１表に示す。The results are shown in Table 1.
実施例２〜８及び比較例１〜６
■、 フェノール変性アミノ樹脂の製造前記（Ａ）〜（
Ｃ）で製造したメラミン樹脂又はメラミン−尿素樹脂と
フェノール樹脂予備縮合物とを、第１表に示す配合割合
で反応器に仕込み、実施例１と同様にしてフェノール変
性アミン樹脂を製造した。得られたフェノール変性アミ
ン樹脂のゲル化時間は第１表に示す通りであった。Examples 2 to 8 and Comparative Examples 1 to 6 (1) Production of phenol-modified amino resin (A) to (
The melamine resin or melamine-urea resin produced in step C) and the phenol resin precondensate were charged into a reactor in the proportions shown in Table 1, and a phenol-modified amine resin was produced in the same manner as in Example 1. The gelation time of the obtained phenol-modified amine resin was as shown in Table 1.
ＩＩ 、 配合糊液の調合
実施例１と同様にして配合糊液を調合した。なお、実施
例３．５〜８．比較例４．６では、上記工のフェノール
変性アミノ樹脂に更に前記（Ｄ）で製造した尿素樹脂を
室温で配合して、糊液を調合した。配合糊液はいずれも
粘度２０〜２５ボイズ／３０℃となるように調整した。II. Preparation of a blended size solution A blended size solution was prepared in the same manner as in Example 1. In addition, Examples 3.5 to 8. In Comparative Example 4.6, the urea resin produced in step (D) above was further blended with the phenol-modified amino resin prepared above at room temperature to prepare a size solution. All of the blended size solutions were adjusted to have a viscosity of 20 to 25 voids/30°C.
接着剤組成物中のメラミン、フェノール、尿素、イソシ
アネートの各成分の割合を第１表に示す。Table 1 shows the proportions of each component of melamine, phenol, urea, and isocyanate in the adhesive composition.
ｍ、 接着剤組成物の性濠試験
実施例１と同様にして、増粘性、塗布性能及び接着力を
調べた。結果を第１表に示す。m. Properties of Adhesive Composition Test In the same manner as in Example 1, the thickening properties, coating performance, and adhesive strength were investigated. The results are shown in Table 1.
第１表より、本発明の接着剤組成物は、極めて安定で可
使時間が長く、またその接着力が極めて優れていること
が明らかである。From Table 1, it is clear that the adhesive composition of the present invention is extremely stable, has a long pot life, and has extremely excellent adhesive strength.
［発明の効果］ 以ト詳述した通り１本発明の接着剤組成物は。[Effect of the invention] As detailed above, the adhesive composition of the present invention is as follows.
メラミン、フェノール及びホルムアルデヒドを必須成分
とする熱硬化性樹脂と、イソシアネート化合物とを主成
分とし、その組成が、メラミン成分１００１１部に対し
、フェノール成分１０〜３０重量部、イソシアネート成
分４〜２５重量部（ＮＣＯ基換算値）であるものであっ
て、（０配合糊液の安定性が高く、経時による増粘が極
めて少ないため、可使時間が長い。The main components are a thermosetting resin containing melamine, phenol, and formaldehyde as essential components, and an isocyanate compound, and the composition is 10 to 11 parts by weight of the melamine component, 10 to 30 parts by weight of the phenol component, and 4 to 25 parts by weight of the isocyanate component. (NCO group equivalent value), and the pot life is long because the stability of the 0-blended paste liquid is high and there is very little thickening over time.
（■ 塗布性が良好で、合板製造の単板等に極めて均一
に塗布することができ、作業性に優れる。(■ It has good applicability and can be applied extremely uniformly to veneers used in plywood manufacturing, providing excellent workability.
■ 接着力が極めて大きく、標準的な熱圧条件下にて、
含水率１５〜２０％の単板でも、ＪＡＳＩ類接着力試験
に合格する高い接着力を発揮し得る。■ Extremely strong adhesive strength, under standard heat and pressure conditions.
Even a veneer with a moisture content of 15 to 20% can exhibit high adhesive strength that passes the JASI type adhesive strength test.
■ 従来用いられていた水性ラテックス等の添加剤を全
く使用しないので、経済的であり、また均一な配合糊液
を調整することが可能である。(2) Since no additives such as water-based latex used in the past are used, it is economical and it is possible to prepare a uniformly mixed paste solution.
■ 接着剤組成物の配合糊液調合手順が簡単で、現行の
配合槽で配合でき、合板製造の配管ライン、スプレッダ
−もそのまま使用することができる。(2) Composition of Adhesive Composition The procedure for preparing the adhesive composition is simple and can be carried out in existing compounding tanks, and the piping lines and spreaders used in plywood production can also be used as they are.
等の効果を有する。It has the following effects.
Claims (5)
須成分とする熱硬化性樹脂と、イソシアネート化合物と
を主成分とする接着剤組成物であって、その組成が、メ
ラミン成分１００重量部に対し、フェノール成分１０〜
３０重量部、イソシアネート成分４〜２５重量部（ＮＣ
Ｏ基換算値）であることを特徴とする接着剤組成物。(1) An adhesive composition mainly consisting of a thermosetting resin containing melamine, phenol, and formaldehyde as essential components and an isocyanate compound, the composition of which is 100 parts by weight of the melamine component and 10 parts by weight of the phenol component. ~
30 parts by weight, 4 to 25 parts by weight of isocyanate component (NC
An adhesive composition characterized in that:
の樹脂であることを特徴とする特許請求の範囲第１項に
記載の接着剤組成物。(2) Thermosetting resin gels for 30-90 minutes/40°C
The adhesive composition according to claim 1, wherein the adhesive composition is a resin.
縮合物とを反応させて得られたフェノール変性アミノ樹
脂であることを特徴とする特許請求の範囲第１項又は第
２項に記載の接着剤組成物。(3) The adhesive according to claim 1 or 2, wherein the thermosetting resin is a phenol-modified amino resin obtained by reacting an amino resin and a phenolic resin precondensate. agent composition.
量部に対し１００重量部以下の尿素成分を含有している
ことを特徴とする特許請求の範囲第１項ないし第３項の
いずれか１項に記載の接着剤組成物。(4) Any one of claims 1 to 3, wherein the thermosetting resin contains 100 parts by weight or less of a urea component per 100 parts by weight of a melamine component in the resin. The adhesive composition according to item 1.
ルポリイソシアネート系化合物であることを特徴とする
特許請求の範囲第１項ないし第４項のいずれか１項に記
載の接着剤組成物。(5) The adhesive composition according to any one of claims 1 to 4, wherein the isocyanate compound is a polymethylene polyphenyl polyisocyanate compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60170909A JPH0680157B2 (en) | 1985-08-02 | 1985-08-02 | Adhesive composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60170909A JPH0680157B2 (en) | 1985-08-02 | 1985-08-02 | Adhesive composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6232164A true JPS6232164A (en) | 1987-02-12 |
| JPH0680157B2 JPH0680157B2 (en) | 1994-10-12 |
Family
ID=15913585
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60170909A Expired - Fee Related JPH0680157B2 (en) | 1985-08-02 | 1985-08-02 | Adhesive composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0680157B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6296578A (en) * | 1985-10-24 | 1987-05-06 | Mitsui Toatsu Chem Inc | Adhesive |
| JPS62119285A (en) * | 1985-11-19 | 1987-05-30 | Mitsui Toatsu Chem Inc | Adhesive composition |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5845476A (en) * | 1981-09-11 | 1983-03-16 | 株式会社東芝 | Quick cooling device for refrigerator |
| JPS58185669A (en) * | 1982-04-22 | 1983-10-29 | Eidai Co Ltd | Preparation of adhesive |
| JPS5933374A (en) * | 1982-08-18 | 1984-02-23 | Mitsui Toatsu Chem Inc | Adhesive |
| JPS59197478A (en) * | 1983-04-25 | 1984-11-09 | Mitsui Toatsu Chem Inc | Adhesive |
-
1985
- 1985-08-02 JP JP60170909A patent/JPH0680157B2/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5845476A (en) * | 1981-09-11 | 1983-03-16 | 株式会社東芝 | Quick cooling device for refrigerator |
| JPS58185669A (en) * | 1982-04-22 | 1983-10-29 | Eidai Co Ltd | Preparation of adhesive |
| JPS5933374A (en) * | 1982-08-18 | 1984-02-23 | Mitsui Toatsu Chem Inc | Adhesive |
| JPS59197478A (en) * | 1983-04-25 | 1984-11-09 | Mitsui Toatsu Chem Inc | Adhesive |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6296578A (en) * | 1985-10-24 | 1987-05-06 | Mitsui Toatsu Chem Inc | Adhesive |
| JPS62119285A (en) * | 1985-11-19 | 1987-05-30 | Mitsui Toatsu Chem Inc | Adhesive composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0680157B2 (en) | 1994-10-12 |
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