JPS6028479A - Contact curing-type adhesive - Google Patents
Contact curing-type adhesiveInfo
- Publication number
- JPS6028479A JPS6028479A JP13608883A JP13608883A JPS6028479A JP S6028479 A JPS6028479 A JP S6028479A JP 13608883 A JP13608883 A JP 13608883A JP 13608883 A JP13608883 A JP 13608883A JP S6028479 A JPS6028479 A JP S6028479A
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- JP
- Japan
- Prior art keywords
- component
- acid
- resin
- curing
- adhesive
- 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.)
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- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
【発明の詳細な説明】 本発明は接触硬化型接着剤に関するものである。[Detailed description of the invention] The present invention relates to contact curing adhesives.
尿素、メラミンあるいはペンゾクアナミンなどとホルム
アルデヒドとの付加組合反応により得られる酸性硬化型
アミノプラスト樹脂を主剤とし、無機酸または有機酸の
少なくとも１種を硬化剤として用い、被着相間で接触硬
化させる接触硬化型接着剤は、短時間圧締で接着作業が
完了するという利点があり、また、硬化物が三次元網目
状高分子を形成するだめに強固な接着が行ない得ること
から、例えば、木材加工分野では、フローリングブロッ
クの集成、幅木材の縦継ぎ、家具類のエッヂ取り付けな
どに、また包装材料分野においては、段ボールと発泡ス
チロールの接着などに広く利用されている。Contact curing, in which the base material is an acidic curing aminoplast resin obtained by addition combination reaction of urea, melamine, penzoquanamine, etc. and formaldehyde, and at least one type of inorganic or organic acid is used as a curing agent, and contact curing is performed between adhered layers. Mold adhesives have the advantage of being able to complete the bonding process in a short period of time, and the cured product forms a three-dimensional network polymer, resulting in strong bonding, so it is used in the wood processing field, for example. It is widely used for assembling flooring blocks, vertically joining skirting boards, attaching edges to furniture, etc., and in the field of packaging materials, for adhering cardboard and Styrofoam.
しかし、これらの接触硬化型接着剤は、耐温水接着性ま
たは接着耐久性が低いという欠点があり、その利点は認
められながらも使用面で制約を受けており、この欠点の
改善が強く望まれている。However, these contact-curing adhesives have the disadvantage of low hot water resistance or adhesive durability, and although these advantages are recognized, they are limited in terms of use, and improvement of these disadvantages is strongly desired. ing.
本発明者らは、従来から多用されている接触硬化型接着
剤について、その利点を損うことなく、耐温水接着性お
よび接着耐久性（耐老化性）を改善することを目的に種
々検討の結果、硬化剤として用いられている無機酸また
は有機酸に、７７２−置換フェノー／ｌ／類を併用する
ことにより目的が達成されることを見出し、本発明を完
成するに至った。The present inventors have conducted various studies with the aim of improving the hot water resistance and adhesive durability (aging resistance) of contact-curing adhesives, which have been widely used in the past, without sacrificing their advantages. As a result, they discovered that the object could be achieved by using 772-substituted phenol/l/ in combination with the inorganic or organic acid used as a curing agent, and completed the present invention.
すなわち、本発明は、酸性硬化型アミノプラスト樹脂を
含有してなる成分Ａ）、および無機酸まだは有機酸と〃
ノー置換フェノール類を含有してなる成分Ｂ）から成る
接触硬化型接着剤を提供する。That is, the present invention provides component A) containing an acidic curable aminoplast resin, and an inorganic acid or an organic acid.
A contact curing adhesive comprising component B) containing unsubstituted phenols is provided.
本発明の接触硬化型接着剤によれば、酸性硬化型アミノ
プラスト樹脂が無機酸捷たは有機酸の存在下に硬化して
三次元網目状高分子を形成すると共に、併用するｍ−置
換ツボ、ノール類が無機酸または有機酸の存在下に酸性
硬化型アミノプラスト樹脂のメチロール基および、該ア
ミノプラスト樹脂に遊離のホルムアルデヒドが含有され
ている場合にはその遊離ホルムアルデヒド
高分子を形成するために、従来の接触硬化型接着剤の利
点を損うことなく、耐温水接着性および接着耐久性が一
挙に改善されるのである。According to the contact curing adhesive of the present invention, the acidic curing aminoplast resin is cured in the presence of an inorganic acid or an organic acid to form a three-dimensional network polymer, and the m-substituted acupoint used in combination is , in order to form a methylol group of an acidic curing aminoplast resin and a free formaldehyde polymer when the aminoplast resin contains free formaldehyde in the presence of an inorganic acid or an organic acid. , hot water resistance and adhesive durability are improved all at once without sacrificing the advantages of conventional contact curing adhesives.
本発明の接触硬化型接着剤において成分Ａ）として用い
られる酸性硬化型アミノプラスト樹脂は公知のいずれの
ものでもよく、ユリア樹脂、メラミン樹脂、ベンゾグア
ナミン樹脂およびそれらの共縮合樹脂などが例示される
。これらのアミノプラスト樹脂の中、ユリア樹脂、ユリ
アーメラミン共縮合樹脂、ユリアーフェノール共縮合樹
脂、ユリアーフェノールーメラミン共縮合樹脂が工業的
有利に使用され、とりわけ、木材接着剤用として市販の
樹脂、例えばユリア樹脂としてのインスフ−ボンドＲ−
１０１、ユリアーメラミン共縮合樹脂としてのニスレジ
ンＳｒ−２（いずれも松栄化学社製）などが有利に使用
される。The acidic curing aminoplast resin used as component A) in the contact curing adhesive of the present invention may be any known one, and examples thereof include urea resin, melamine resin, benzoguanamine resin, and cocondensation resins thereof. Among these aminoplast resins, urea resin, urea melamine cocondensation resin, urea phenol cocondensation resin, and urea phenol-melamine cocondensation resin are industrially advantageously used. Insufbond R- as a resin, e.g. urea resin
101, varnish resin Sr-2 as a urea melamine cocondensation resin (both manufactured by Shoei Kagaku Co., Ltd.), etc. are advantageously used.
これらの木材接着剤用として市販の樹脂には、通常、遊
離のホルムアルデヒドが含有されている。本発明におけ
る成分Ａ）には遊離のホルムアルデヒド
かかるホルムアルデヒド
ン、パラフォルムアルデヒド、ヘキサメチノンテトラミ
ン、トリオキサン、α−ポリオキシメチレンなどが例示
される。こ、のような遊離ホルムアルデヒドの含有量は
特に制限されるものではないが、ホルムアルデヒド臭気
による作業環境の悪化を考慮して、塩化アンモニウム法
による測定値がアミノプラスト樹脂に対して約７重量％
以下の量である事が望ましい。Commercially available resins for these wood adhesives usually contain free formaldehyde. Examples of component A) in the present invention include free formaldehyde, formaldehydone, paraformaldehyde, hexamethinonetetramine, trioxane, and α-polyoxymethylene. The content of free formaldehyde is not particularly limited, but in consideration of the deterioration of the working environment due to formaldehyde odor, the content measured by the ammonium chloride method is approximately 7% by weight based on the aminoplast resin.
It is desirable that the amount is as follows.
本発明の成分Ａ）には更に老化防止作用を有スル、酢酸
ビニル樹脂エマルジョン、フルフリルアルコールなどを
必要に応じて添加することができる。Component A) of the present invention may further contain a substance having an anti-aging effect, vinyl acetate resin emulsion, furfuryl alcohol, etc., as required.
本発明の成分Ａ）は、不揮発分が約４０乃至８０重量％
の水性樹脂液として用いる。Component A) of the present invention has a nonvolatile content of about 40 to 80% by weight.
Used as an aqueous resin liquid.
本発明の接触硬化型接着剤において成分Ｂ）として用い
る無機酸および有機酸としては、塩酸、リン酸、硝酸、
酢酸、スルファミノ酸、パラトルエンスルフォン酸、ペ
ンセンスルホン酸などが例示され、これらの１種または
２種以上が水溶液として用いられる。Inorganic acids and organic acids used as component B) in the contact curing adhesive of the present invention include hydrochloric acid, phosphoric acid, nitric acid,
Examples include acetic acid, sulfamino acid, p-toluenesulfonic acid, pencenesulfonic acid, etc., and one or more of these are used as an aqueous solution.
本発明の成分Ｂ）として用いられる〃７ー置換フェノー
ル類トシては、レゾルシノール、７７ノーアミノフエノ
ール、ｍ−クレゾール、３、５−キシレノール、〃ｌー
メ１ーキシフェノールなどが例示され、これらの１種ま
たは２種以上が用いられる。Examples of the 7-substituted phenols used as component B) of the present invention include resorcinol, 77-no-aminophenol, m-cresol, 3,5-xylenol, and 1-1-xyphenol. A species or two or more species may be used.
これらの〃７ー７−置換フニノー／ｌの使用量は特に制
限されないが、上記した無機酸まだは有機酸に対して０
．５重量％以上で耐温水接着性の向上が顕著となり、１
５重量％より多くなると成分Ｂ）の着色あるいは分離な
どが生じ易く、長期保存性が低下する傾向があるので好
ましくない。通常、無機酸または有機酸の水溶液に対し
て２乃至１０重量％である。The amount of these 7-7-substituted Funinot/l used is not particularly limited, but it is 0% compared to the above-mentioned inorganic acid and organic acid.
．． At 5% by weight or more, the improvement in hot water resistant adhesion becomes remarkable, and 1
If it exceeds 5% by weight, component B) tends to be discolored or separated, and long-term storage stability tends to deteriorate, which is not preferable. Usually, it is 2 to 10% by weight based on the aqueous solution of inorganic or organic acid.
本発明の成分Ｂ）には更にポリビニルアルコ ー ル、
メ チ ルセ ル ロ ー ス 、ポ リ ア り リ
ル酸などの増粘剤、または必要により有機溶剤など、
または通常行なわれているような酢酸ビニル樹脂エマル
ジョンなどを添加することができる。Component B) of the present invention further includes polyvinyl alcohol,
Thickeners such as methylcellulose and polyarylic acid, or organic solvents as necessary,
Alternatively, a commonly used vinyl acetate resin emulsion or the like can be added.
本発明の成分Ｂ）は無機酸または有機酸の少なくとも１
種の水溶液に７２１−置換フェノール類の少なくとも１
種を添加し、必要により増粘剤、有機溶剤などを添加し
て調整されるが、予め増粘水溶液を調整し、次いで無機
酸まだは有機酸の少なくとも１種、および〃１−置換フ
ェノーＪＶ類の少なくとも１種を添加して調整すること
もできる。Component B) of the invention comprises at least one inorganic or organic acid.
At least one of the 721-substituted phenols is added to the aqueous solution of the seeds.
A thickening aqueous solution is prepared in advance, and then at least one kind of inorganic acid or organic acid and 1-substituted phenol JV are added. It can also be adjusted by adding at least one of the following.
このようにして調整される酸性水溶液は、従来の接触硬
化型接着剤の硬化剤成分と同様にｐＨ値を１以下に調整
する。ｐＨ値が１より高い場合は硬化が遅くなり、接触
硬化型接着剤の特性を損い、一方ｐＨ値が過度に低い場
合は被着材を汚染し硬化物の老化を早めるので、通常、
ｐＨＱ乃至０．５に調整される。The pH value of the acidic aqueous solution prepared in this manner is adjusted to 1 or less, similar to the curing agent component of conventional contact curing adhesives. A pH value higher than 1 will slow curing and impair the properties of the contact curing adhesive, while an excessively low pH value will contaminate the adherend and accelerate the aging of the cured product, so it is usually
The pH is adjusted to 0.5.
本発明において、成分Ａ）と成分Ｂ）との使用割合は、
通常の接触硬化型接着剤において行なわれている方法に
よって決定することができ、例えば、セットタイムを測
定して適宜決定することができる。In the present invention, the usage ratio of component A) and component B) is as follows:
It can be determined by the method used for ordinary contact curing adhesives, for example, it can be determined appropriately by measuring the set time.
本発明の接触硬化型接着剤は、従来使用されている方法
と同様に被着材間で成分Ａ）と成分Ｂ）とを接触せしめ
、例えば常温でｌ乃至１５分間圧締することにより接着
を完了することができる。The contact curing adhesive of the present invention can be bonded by bringing component A) and component B) into contact between adherends in the same manner as in conventional methods, and by pressing for 1 to 15 minutes at room temperature, for example. can be completed.
以下、本発明を実施例により詳細に説明する。Hereinafter, the present invention will be explained in detail with reference to Examples.
例中、部とあるのは重量部を表わす。In the examples, parts represent parts by weight.
尚、下記実施例においては、成分Ａ）として、［インス
ターボンドＲ−１，ＯＩ Ａ液」（接触硬化型ユリア樹
脂接着剤、検束化学社製、以下Ａ−１と略称する。）「
ニスレジン５Ｆ＝２」（ユリアーメラミン共縮合樹脂木
材接着剤、同上社製、以下Ａ−２と略称する。）および
Ａ−１に３７重量％ホルムアルデヒド溶液を配合して得
た樹脂液（以下Ａ−３と略称する。）を用いた。In the following examples, component A) is [Instarbond R-1, OI A liquid] (contact curing urea resin adhesive, manufactured by Kenshu Kagaku Co., Ltd., hereinafter abbreviated as A-1).
Varnish Resin 5F=2'' (urea melamine co-condensed resin wood adhesive, manufactured by the same company, hereinafter abbreviated as A-2) and resin liquid obtained by blending A-1 with a 37% formaldehyde solution (hereinafter A-1). -3 for short) was used.
これらの樹脂液の物性値を第１表に示す。Table 1 shows the physical properties of these resin liquids.
（各物性はＪＩＳ Ｋ−６ ８ ０ １ユリア樹脂木利
接着剤試験方法に準じて測定した。）実施例 １〜３お
よび比較例１〜２
Ａ−］、Ａ−２およびＡ−３を成分Ａ）とし、ＩＮ塩酸
１００部にレゾルンノー／Ｌ／６部を配合して得た酸性
液を成分Ｂ）として、夫々接触硬化型接着剤を得だ。(Each physical property was measured according to JIS K-6 801 urea resin wood adhesive test method.) Examples 1 to 3 and Comparative Examples 1 to 2 A-], A-2, and A-3 were Contact curing adhesives were obtained by using component A) and an acidic solution obtained by blending 100 parts of IN hydrochloric acid with 6 parts of Resol No/L/ as component B).
厚さｌＯｆｆＪ幅５５騎、長さ２ ０ ０ ｍｍ、含水
率８重量％の横材を被着材とし、各成分Ａ）を被着材の
片面に２ ０ ０ ｆ ／ ７７１の割合で塗付し、ま
た他の被着材の片面に成分Ｂ）を１６０９ ／ ｎ？の
割合で塗イ」シだ。夫々の塗付面を合せ、常温で７ Ｋ
ｇ ／ ｃａの圧力で１０分間圧締して接着した。The adherend is a horizontal material with a thickness lOffJ width of 55 mm, a length of 200 mm, and a moisture content of 8% by weight, and each component A) is applied to one side of the adherend at a rate of 200 f/771. In addition, component B) was added to one side of the other adherend at a rate of 1609/n? Paint it at the rate of . Combine each coated surface and heat at room temperature to 7K.
It was bonded by pressing at a pressure of g/ca for 10 minutes.
一方成分Ａ）としてＡ−１を用い、成分Ｂ）としてＩＮ
塩酸（比較例１）、及び市販のインスターボンドＲ−
１ ０ １ ＢＭ（ 変性ヒール樹脂含有塩酸酸性液、
ｌ） Ｈ Ｏ． ４以下、検束化学社製、比較例２）を
用い、夫々上記と同様の方法で接着した。On the other hand, A-1 is used as component A), and IN as component B).
Hydrochloric acid (Comparative Example 1), and commercially available Instarbond R-
1 0 1 BM (hydrochloric acid acidic solution containing modified heel resin,
l) H O. 4 and below, manufactured by Kensoku Kagaku Co., Ltd., Comparative Example 2) were used, and each was adhered in the same manner as above.
これらの試験片を２４時間養生後、ＪＩＳＫ−６８５２
５．３（接着剤の圧縮せん断接着強さ試験方法、耐温
水試験）に準じて接着力試験を行ない、第１Ｕ表に示す
結果を得た。After curing these test pieces for 24 hours, JISK-6852
An adhesive strength test was conducted according to 5.3 (compression shear adhesive strength test method for adhesives, hot water resistance test), and the results shown in Table 1U were obtained.
第１Ｉ表
実施例４〜８
Ａ−１を成分Ａ）とし、第■表に示す組成の酸性液を成
分Ｂ）として夫々接触硬化型接着剤を得た。Table 1I Examples 4 to 8 Contact curing adhesives were obtained by using A-1 as component A) and using the acidic liquid having the composition shown in Table 1 as component B).
実施例１〜３と同様の方法で接着を行ない第■表に示す
結果を得た。Adhesion was carried out in the same manner as in Examples 1 to 3, and the results shown in Table 1 were obtained.
第■表
実施例９〜１３
Ａ−１を成分Ａ）とし、第１Ｖ表に示す組成の酸性液を
成分Ｂ）として夫々接触硬化型接着剤を得た。Table 1 Examples 9 to 13 Contact curing adhesives were obtained using A-1 as component A) and using an acidic liquid having the composition shown in Table 1V as component B).
実施例１〜３と同様の方法で接着を行い第１Ｖ表に示す
結果を得だ。Adhesion was carried out in the same manner as in Examples 1 to 3, and the results shown in Table 1V were obtained.
第１Ｖ表
実施例１４および比較例３
Ａ、 −１を成分Ａ）とし、ＩＮ−塩酸１００部にＶゾ
ルシノール６
液を成分Ｂ）として接触硬化型接着剤を得た。Table 1V Example 14 and Comparative Example 3 A, -1 was used as component A), and V-Sorcinol 6 solution was added as component B) in 100 parts of IN-hydrochloric acid to obtain a contact curing adhesive.
一方、比較例としてＡ−１およびＩＮ−塩酸から成る接
触硬化型接着剤を得だ。On the other hand, as a comparative example, a contact curing adhesive consisting of A-1 and IN-hydrochloric acid was obtained.
被着材として厚さ３０πｍ、幅７５馴、長さ２’ ５
０ ｍｌｌｌ、含水率８〜９重量％のニレ材を用い、夫
々の接着剤で４１ライの積層材を実施例１〜３の方法と
同様に作製した。Adherent material: thickness 30πm, width 75m, length 2'5
A laminate of 41 lye was prepared using each adhesive using elm wood having a water content of 0 ml and a moisture content of 8 to 9% by weight in the same manner as in Examples 1 to 3.
作製した試料の耐老化性試験として、寒熱繰返し試験（
６０’Ｃ／２時間→ー２０’Ｃ／２時間−６０°Ｃ／２
時間を１サイクルとした。）を行い、璋着層の剥離率を
めた。その粘果は第７表に示すとおりである。As an aging resistance test of the prepared sample, a cold/heat cyclic test (
60'C/2 hours → -20'C/2 hours -60°C/2
The time was defined as one cycle. ) to determine the peeling rate of the pruning layer. The viscous is as shown in Table 7.
第 ｖ 表Table v
Claims (1)
、および無機酸または有機酸と〃１−置換フエノール類
を含有してなる成分Ｂ）から成る接触硬化型接着剤。Component A) containing acidic curable aminoplast resin
, and component B) containing an inorganic or organic acid and a 1-substituted phenol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13608883A JPS6028479A (en) | 1983-07-26 | 1983-07-26 | Contact curing-type adhesive |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13608883A JPS6028479A (en) | 1983-07-26 | 1983-07-26 | Contact curing-type adhesive |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6028479A true JPS6028479A (en) | 1985-02-13 |
| JPH0471113B2 JPH0471113B2 (en) | 1992-11-12 |
Family
ID=15166971
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13608883A Granted JPS6028479A (en) | 1983-07-26 | 1983-07-26 | Contact curing-type adhesive |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6028479A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7235613B2 (en) | 2001-10-18 | 2007-06-26 | Akzo Nobel N.V. | Method of gluing wood based materials |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4948734A (en) * | 1972-09-11 | 1974-05-11 | ||
| JPS50109932A (en) * | 1974-02-07 | 1975-08-29 | ||
| JPS53117032A (en) * | 1977-03-23 | 1978-10-13 | Nagoya Yukagaku Kogyo Kk | Adhesive composition |
| JPS5520512A (en) * | 1978-07-28 | 1980-02-14 | Mitsubishi Heavy Ind Ltd | Binary/bcd conversion circuit of real variable |
| JPS5611977A (en) * | 1979-07-12 | 1981-02-05 | Sumitomo Bakelite Co Ltd | Aqueous adhesive suitable for wood |
-
1983
- 1983-07-26 JP JP13608883A patent/JPS6028479A/en active Granted
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4948734A (en) * | 1972-09-11 | 1974-05-11 | ||
| JPS50109932A (en) * | 1974-02-07 | 1975-08-29 | ||
| JPS53117032A (en) * | 1977-03-23 | 1978-10-13 | Nagoya Yukagaku Kogyo Kk | Adhesive composition |
| JPS5520512A (en) * | 1978-07-28 | 1980-02-14 | Mitsubishi Heavy Ind Ltd | Binary/bcd conversion circuit of real variable |
| JPS5611977A (en) * | 1979-07-12 | 1981-02-05 | Sumitomo Bakelite Co Ltd | Aqueous adhesive suitable for wood |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7235613B2 (en) | 2001-10-18 | 2007-06-26 | Akzo Nobel N.V. | Method of gluing wood based materials |
| US7452442B2 (en) | 2001-10-18 | 2008-11-18 | Akzo Nobel N.V. | Gluing wood based materials with melaminic amino resin and resorcinol or tannin resin |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0471113B2 (en) | 1992-11-12 |
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