JP2590647B2 - Manufacturing method of binder for glass fiber non-woven fabric - Google Patents
Manufacturing method of binder for glass fiber non-woven fabricInfo
- Publication number
- JP2590647B2 JP2590647B2 JP3269797A JP26979791A JP2590647B2 JP 2590647 B2 JP2590647 B2 JP 2590647B2 JP 3269797 A JP3269797 A JP 3269797A JP 26979791 A JP26979791 A JP 26979791A JP 2590647 B2 JP2590647 B2 JP 2590647B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- aliphatic amine
- parts
- binder
- epoxy resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Landscapes
- Adhesives Or Adhesive Processes (AREA)
- Nonwoven Fabrics (AREA)
- Epoxy Resins (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、積層板の基材として用
いるガラス繊維不織布のためのバインダの製造法に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a binder for a glass fiber nonwoven fabric used as a substrate of a laminate.
【０００２】[0002]
【従来の技術】従来、積層板用ガラス繊維不織布のバイ
ンダは、次のようにして製造されている。すなわち、ま
ず、窒素原子に結合した活性水素を少なくとも１個以上
有する脂肪族アミンを、２個以上のエポキシ基を有する
エポキシ樹脂に、等モル量（アミン当量／エポキシ当
量）付加反応させる。この反応は、４０〜５０ｗｔ％の
有機溶剤の存在下で行なう。そして、前記生成物に、さ
らに酸を付加して水溶性あるいは水分散性のアミン・エ
ポキシド酸性塩とするものである。2. Description of the Related Art Conventionally, a binder of a glass fiber nonwoven fabric for a laminate has been manufactured as follows. That is, first, an aliphatic amine having at least one active hydrogen bonded to a nitrogen atom is added to an epoxy resin having two or more epoxy groups in an equimolar amount (amine equivalent / epoxy equivalent). This reaction is performed in the presence of 40 to 50% by weight of an organic solvent. Then, an acid is further added to the product to form a water-soluble or water-dispersible amine / epoxide acid salt.
【０００３】[0003]
【発明が解決しようとする課題】上記バインダは、エポ
キシ樹脂の硬化剤である脂肪族アミンを一度にエポキシ
基と等モル量付加反応させてしまうため、付加反応の制
御がしにくい。エポキシ樹脂と脂肪族アミンとの反応は
発熱反応であり、大量の有機溶剤を添加して付加反応を
制御しやすくしている。従って、上記バインダは有機溶
剤の量が多く、ガラス繊維不織布に付着させて乾燥炉内
で硬化させる際、爆発および火災に対する安全面や衛生
面での十分な配慮が必要であり、設備に対する負担が大
きい。本発明が解決しようとする課題は、少ない溶剤で
エポキシ樹脂と脂肪族アミンの付加反応を行なわせ、ガ
ラス繊維不織布用のバインダを製造することである。The above-mentioned binder causes an addition reaction of an aliphatic amine, which is a curing agent for an epoxy resin, with an epoxy group at a time in an equimolar amount, so that it is difficult to control the addition reaction. The reaction between the epoxy resin and the aliphatic amine is an exothermic reaction, and a large amount of an organic solvent is added to make it easier to control the addition reaction. Therefore, the above-mentioned binder has a large amount of organic solvent, and when it is attached to a glass fiber nonwoven fabric and cured in a drying oven, sufficient consideration must be given to safety and hygiene against explosions and fires, and the burden on equipment is increased. large. The problem to be solved by the present invention is to produce a binder for a glass fiber nonwoven fabric by performing an addition reaction between an epoxy resin and an aliphatic amine with a small amount of a solvent.
【０００４】[0004]
【課題を解決するための手段】上記課題を解決するた
め、本発明に係る方法は、窒素原子に結合した活性水素
を少なくとも１個以上有する脂肪族アミンを、２個以上
のエポキシ基を有するエポキシ樹脂に、アミン当量／エ
ポキシ当量が０.１〜０.５の範囲で付加反応させる。そ
して、前記反応生成物に、酸によって中和した脂肪族ア
ミンを添加することを特徴とする。To solve the above-mentioned problems, a method according to the present invention is directed to a method for preparing an aliphatic amine having at least one active hydrogen bonded to a nitrogen atom by using an epoxy compound having at least two epoxy groups. The resin is subjected to an addition reaction in an amine equivalent / epoxy equivalent range of 0.1 to 0.5. Then, an aliphatic amine neutralized with an acid is added to the reaction product.
【０００５】[0005]
【作用】エポキシ樹脂と脂肪族アミンの付加反応は発熱
反応であるが、脂肪族アミンを上記の当量比の範囲で添
加することにより発熱を少なくし、有機溶剤の量を減少
させることができる。そして、不足分を補うために、付
加反応終了後に添加する脂肪族アミンを酸によって中和
しておくことにより、貯蔵中の付加反応を抑制できる。
最初に付加反応させる脂肪族アミンの量は、アミン当量
／エポキシ当量が０.１未満では付加反応が十分進行せ
ず、０.５を越えると反応進行に伴う粘度上昇のため
に、有機溶剤使用量を増加しなければならなくなる。The addition reaction between the epoxy resin and the aliphatic amine is an exothermic reaction. By adding the aliphatic amine in the above equivalence ratio, heat generation can be reduced and the amount of the organic solvent can be reduced. Then, to compensate for the shortage, the addition reaction during storage can be suppressed by neutralizing the aliphatic amine added after the addition reaction with an acid.
When the amount of the aliphatic amine to be firstly subjected to the addition reaction is less than 0.1, the addition reaction does not proceed sufficiently. If the amount exceeds 0.5, the viscosity increases with the progress of the reaction. The amount has to be increased.
【０００６】[0006]
【実施例】本発明で使用するエポキシ樹脂は、エポキシ
当量が１７０〜１０００程度のビスフェノールＡ型ある
いはＦ型エポキシ樹脂やクレゾールあるいはフェノール
ノボラック型エポキシ樹脂、三官能のものを含む多官能
エポキシ樹脂等であり、特に限定するものではない。硬
化剤である脂肪族アミンとしては、ジエチレントリアミ
ンやトリエチレンテトラミン等直鎖脂肪族の水溶性アミ
ンであればよい。付加反応を行なわせる溶媒として使用
する有機溶剤は、エポキシ樹脂と反応性のあるメタノー
ル等のアルコール類を除けば特に不都合はない。また、
脂肪族アミンを中和する酸は、不織布製造工程の乾燥工
程で人体に有毒とならないギ酸や酢酸等の有機酸が好ま
しいが、特に限定はしない。以下の例で、エポキシ樹脂
はＥｐ８２８（油化シェル製，エポキシ当量１８９）を
用い、直鎖脂肪族アミンはトリエチレンテトラミン（ア
ミン当量２７.３４）を用いた。有機溶剤はアセトンを
用い、脂肪族アミンを中和する酸は酢酸を用いた。The epoxy resin used in the present invention is a bisphenol A type or F type epoxy resin having an epoxy equivalent of about 170 to 1,000, cresol or phenol novolak type epoxy resin, a polyfunctional epoxy resin including trifunctional epoxy resin and the like. There is no particular limitation. The aliphatic amine serving as a curing agent may be any linear aliphatic water-soluble amine such as diethylenetriamine and triethylenetetramine. The organic solvent used as the solvent for performing the addition reaction is not particularly inconvenient except for alcohols such as methanol which are reactive with the epoxy resin. Also,
The acid that neutralizes the aliphatic amine is preferably an organic acid such as formic acid or acetic acid that does not become toxic to the human body in the drying step of the nonwoven fabric manufacturing step, but is not particularly limited. In the following examples, Ep828 (manufactured by Yuka Shell, epoxy equivalent: 189) was used as the epoxy resin, and triethylenetetramine (amine equivalent: 27.34) was used as the linear aliphatic amine. Acetone was used as the organic solvent, and acetic acid was used as the acid for neutralizing the aliphatic amine.
【０００７】（実施例１）エポキシ樹脂３７８重量部、
脂肪族アミン４.５４重量部を、有機溶剤４７重量部中
で８時間反応させた。脂肪族アミン４０.８６重量部と
酸４８重量部を混合したものを、前記反応生成物に添加
してガラス繊維不織布用のバインダを得た。最初に混合
した脂肪族アミンとエポキシ樹脂の当量比は０.１であ
る。また、有機溶剤の割合は１０ｗｔ％である。(Example 1) 378 parts by weight of an epoxy resin,
4.54 parts by weight of an aliphatic amine was reacted in 47 parts by weight of an organic solvent for 8 hours. A mixture of 40.86 parts by weight of an aliphatic amine and 48 parts by weight of an acid was added to the reaction product to obtain a binder for a glass fiber nonwoven fabric. The equivalent ratio of the aliphatic amine to the epoxy resin initially mixed is 0.1. The ratio of the organic solvent is 10% by weight.
【０００８】（実施例２）エポキシ樹脂３７８重量部、
脂肪族アミン９.０８重量部を、有機溶剤４７重量部中
で８時間反応させた。脂肪族アミン３６.３２重量部と
酸４８重量部を混合したものを、前記反応生成物に添加
してガラス繊維不織布用のバインダを得た。最初に混合
した脂肪族アミンとエポキシ樹脂の当量比は０.３であ
る。また、有機溶剤の割合は１０ｗｔ％である。(Example 2) 378 parts by weight of an epoxy resin,
9.08 parts by weight of an aliphatic amine was reacted in 47 parts by weight of an organic solvent for 8 hours. A mixture of 36.32 parts by weight of an aliphatic amine and 48 parts by weight of an acid was added to the reaction product to obtain a binder for a glass fiber nonwoven fabric. The equivalent ratio of the aliphatic amine to the epoxy resin mixed first is 0.3. The ratio of the organic solvent is 10% by weight.
【０００９】（実施例３）エポキシ樹脂３７８重量部、
脂肪族アミン２２.７重量部を、有機溶剤４７重量部中
で８時間反応させた。脂肪族アミン２２.７重量部と酸
４８重量部を混合したものを、前記反応生成物に添加し
てガラス繊維不織布用のバインダを得た。最初に混合し
た脂肪族アミンとエポキシ樹脂の当量比は０.５であ
る。また、有機溶剤の割合は１０ｗｔ％である。(Example 3) 378 parts by weight of an epoxy resin,
22.7 parts by weight of an aliphatic amine were reacted in 47 parts by weight of an organic solvent for 8 hours. A mixture of 22.7 parts by weight of an aliphatic amine and 48 parts by weight of an acid was added to the reaction product to obtain a binder for a glass fiber nonwoven fabric. The equivalent ratio of the aliphatic amine to the epoxy resin mixed first is 0.5. The ratio of the organic solvent is 10% by weight.
【００１０】（比較例１）エポキシ樹脂３７８重量部、
脂肪族アミン３.６３重量部を、有機溶剤４７重量部中
で８時間反応させた。脂肪族アミン４１.７７重量部と
酸４８重量部を混合したものを、前記反応生成物に添加
してガラス繊維不織布用のバインダを得た。最初に混合
した脂肪族アミンとエポキシ樹脂の当量比は０.０８で
ある。また、有機溶剤の割合は１０ｗｔ％である。Comparative Example 1 378 parts by weight of an epoxy resin,
3.63 parts by weight of an aliphatic amine was reacted in 47 parts by weight of an organic solvent for 8 hours. A mixture of 41.77 parts by weight of an aliphatic amine and 48 parts by weight of an acid was added to the reaction product to obtain a binder for a glass fiber nonwoven fabric. The equivalent ratio of the aliphatic amine to the epoxy resin mixed first is 0.08. The ratio of the organic solvent is 10% by weight.
【００１１】（比較例２）エポキシ樹脂３７８重量部、
脂肪族アミン２７.２４重量部を、有機溶剤４７重量部
中で８時間反応させた。脂肪族アミン１８.１６重量部
と酸４８重量部を混合したものを、前記反応生成物に添
加してガラス繊維不織布用のバインダを得た。最初に混
合した脂肪族アミンとエポキシ樹脂の当量比は０.６で
ある。また、有機溶剤の割合は１０ｗｔ％である。Comparative Example 2 378 parts by weight of an epoxy resin
27.24 parts by weight of an aliphatic amine were reacted in 47 parts by weight of an organic solvent for 8 hours. A mixture of 18.16 parts by weight of an aliphatic amine and 48 parts by weight of an acid was added to the reaction product to obtain a binder for a glass fiber nonwoven fabric. The equivalent ratio of the aliphatic amine to the epoxy resin mixed first is 0.6. The ratio of the organic solvent is 10% by weight.
【００１２】（従来例１）エポキシ樹脂３７８重量部、
脂肪族アミン４５.４重量部を、有機溶剤４７重量部中
で８時間反応させた。酸４８重量部を前記反応生成物に
添加してガラス繊維不織布用のバインダを得た。有機溶
剤の割合は１０ｗｔ％である。(Conventional Example 1) 378 parts by weight of epoxy resin,
45.4 parts by weight of an aliphatic amine was reacted in 47 parts by weight of an organic solvent for 8 hours. 48 parts by weight of an acid were added to the reaction product to obtain a binder for a glass fiber nonwoven fabric. The ratio of the organic solvent is 10% by weight.
【００１３】（従来例２）エポキシ樹脂３７８重量部、
脂肪族アミン４５.４重量部を、有機溶剤２８２重量部
中で８時間反応させた。酸４８重量部を前記反応生成物
に添加してガラス繊維不織布用のバインダを得た。有機
溶剤の割合は４０ｗｔ％である。(Conventional Example 2) 378 parts by weight of an epoxy resin,
45.4 parts by weight of an aliphatic amine were reacted in 282 parts by weight of an organic solvent for 8 hours. 48 parts by weight of an acid were added to the reaction product to obtain a binder for a glass fiber nonwoven fabric. The ratio of the organic solvent is 40% by weight.
【００１４】図１に、実施例１〜３、比較例１〜２、従
来例１〜２における反応経過時間と反応液の粘度の関係
を示す。実施例１〜３は、図からも明らかなように粘度
が高くならず、バインダとして実用に適するものであっ
た。従来例１では、有機溶剤量を少なくしているものの
粘度が高くなりすぎている。従来例２では、粘度に問題
はないが有機溶剤量が多すぎる。比較例１では、有機溶
剤量を少なくして粘度も低いが、付加する脂肪族アミン
が所定量に達していないためバインダとして使用できな
い。比較例２では、付加する脂肪族アミンが所定量を越
えているために粘度が高い。FIG. 1 shows the relationship between the reaction elapsed time and the viscosity of the reaction solution in Examples 1 to 3, Comparative Examples 1 and 2, and Conventional Examples 1 and 2. In Examples 1 to 3, the viscosity did not increase, as is clear from the figure, and was suitable for practical use as a binder. In Conventional Example 1, although the amount of the organic solvent is reduced, the viscosity is too high. In Conventional Example 2, there is no problem in viscosity, but the amount of organic solvent is too large. In Comparative Example 1, although the amount of the organic solvent was reduced and the viscosity was low, the aliphatic amine to be added could not be used as a binder because the amount of the aliphatic amine to be added did not reach a predetermined amount. In Comparative Example 2, the viscosity was high because the aliphatic amine to be added exceeded a predetermined amount.
【００１５】[0015]
【発明の効果】上述したように本発明に係る方法によれ
ば、使用する有機溶剤の量を従来方法より減らしても、
急激な付加反応が起こらず安定した状態でバインダを生
産することができる。As described above, according to the method of the present invention, even if the amount of the organic solvent used is reduced compared to the conventional method,
The binder can be produced in a stable state without a rapid addition reaction.
【図１】実施例、比較例、従来例における反応経過時間
と反応液の粘度との関係を示す曲線図である。FIG. 1 is a curve diagram showing a relationship between a reaction elapsed time and a viscosity of a reaction solution in Examples, Comparative Examples, and Conventional Examples.
Claims (1)
１個以上有する脂肪族アミンを、２個以上のエポキシ基
を有するエポキシ樹脂に、アミン当量／エポキシ当量が
０.１〜０.５の範囲で付加反応させた後、酸で中和した
脂肪族アミンを添加することを特徴とするガラス繊維不
織布用バインダの製造法。1. An aliphatic amine having at least one active hydrogen bonded to a nitrogen atom is added to an epoxy resin having two or more epoxy groups, wherein the amine equivalent / epoxy equivalent is in the range of 0.1 to 0.5. A method for producing a binder for a glass fiber nonwoven fabric, wherein an aliphatic amine neutralized with an acid is added after the addition reaction is performed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3269797A JP2590647B2 (en) | 1991-10-18 | 1991-10-18 | Manufacturing method of binder for glass fiber non-woven fabric |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3269797A JP2590647B2 (en) | 1991-10-18 | 1991-10-18 | Manufacturing method of binder for glass fiber non-woven fabric |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05106151A JPH05106151A (en) | 1993-04-27 |
| JP2590647B2 true JP2590647B2 (en) | 1997-03-12 |
Family
ID=17477301
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3269797A Expired - Lifetime JP2590647B2 (en) | 1991-10-18 | 1991-10-18 | Manufacturing method of binder for glass fiber non-woven fabric |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2590647B2 (en) |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5239474B2 (en) * | 1973-09-07 | 1977-10-05 |
-
1991
- 1991-10-18 JP JP3269797A patent/JP2590647B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH05106151A (en) | 1993-04-27 |
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