JP5036382B2 - Adhesive composition - Google Patents
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- JP5036382B2 JP5036382B2 JP2007108878A JP2007108878A JP5036382B2 JP 5036382 B2 JP5036382 B2 JP 5036382B2 JP 2007108878 A JP2007108878 A JP 2007108878A JP 2007108878 A JP2007108878 A JP 2007108878A JP 5036382 B2 JP5036382 B2 JP 5036382B2
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Abstract
Description
本発明はホルムアルデヒド含有樹脂を使用することなく、化粧紙への浸透性や耐水性、表面硬度に優れ、堆積時間が長い場合であっても接着可能で、特にポリエステル化粧板の製造工程における木質基材と化粧紙との接着に有用な接着剤組成物に関する。 The present invention is excellent in permeability to decorative paper, water resistance and surface hardness without using formaldehyde-containing resin, and can be bonded even when the deposition time is long. The present invention relates to an adhesive composition useful for bonding a material and decorative paper.
ポリエステル化粧板は合板等の木質基材に化粧紙を接着し、さらに耐久性を持たせるためにポリエステル樹脂塗装を行うことにより製造される化粧板であり、家具の表面材や壁面用化粧材等に使用されている。ポリエステル化粧板に要求される物理的特性としては、耐水性に優れること、化粧紙層ではく離せず高い強度を有すること、表面硬度が高いこと等が挙げられるが、これらは木質基材と化粧紙を貼り合わせる際に用いられる接着剤の性能に依存する部分が大きい。 A polyester decorative board is a decorative board manufactured by bonding decorative paper to a woody base material such as plywood and applying polyester resin to make it more durable. Is used. The physical properties required for the polyester decorative board include excellent water resistance, high strength that does not peel off the decorative paper layer, and high surface hardness. A large part depends on the performance of the adhesive used when bonding the paper.
尿素やメラミンとホルムアルデヒドを縮重合したアミノ系樹脂は、化粧紙への浸透性、耐水性、硬化物の硬度に優れるため化粧紙の接着に好適であるが、熱硬化性樹脂であるため単独で用いると接着層が脆くなり、化粧紙の風合いが損なわれるという欠点があった。そこで弾性を有する熱可塑性樹脂、例えば酢酸ビニル系樹脂エマルジョンやゴム系ラテックスとアミノ系樹脂をブレンドした接着剤が用いられてきた。 Amino-based resins obtained by condensation polymerization of urea, melamine and formaldehyde are suitable for adhesion to decorative paper because of their excellent permeability to decorative paper, water resistance, and hardness of cured products. When used, the adhesive layer becomes brittle and the texture of the decorative paper is impaired. Therefore, an elastic thermoplastic resin such as a vinyl acetate resin emulsion or an adhesive obtained by blending a rubber latex and an amino resin has been used.
しかしながら、いわゆるシックハウス症候群の問題により、ホルムアルデヒドを一定量以上放散する建材は使用面積が制限される等、建材やこれに使用される接着剤はホルムアルデヒドを使用しないタイプのものが求められるようになった。このような要求に対して、特許文献１にはビニル樹脂系エマルジョンおよび合成ゴム系ラテックスから選択される少なくとも一種の乳濁液と、アミド基を有する水溶性樹脂からなるポリエステル化粧板用接着剤組成物が開示されており、アミノ系樹脂を使用しない場合の問題の一つである紙間剥離が起こらないようにしたものである。
しかし、化粧紙の接着にアミノ系樹脂を使用しない場合の問題は紙間はく離のみではなく、耐水性や表面硬度が低下する点も挙げられる。また、アミノ系樹脂は熱戻り性が良いという特徴があるため、木質基材に接着剤を塗布して化粧紙を貼り合わせてから加熱圧締を行うまでの堆積時間が長くなった場合であっても、接着性能が低下しにくいという利点も失われることとなる。このように、アミノ系樹脂が有していた特徴を全て兼ね備えた非ホルムアルデヒド系接着剤は見出されていない。 However, the problem in the case of not using an amino resin for adhesion of decorative paper is not only the separation between papers, but also the point that water resistance and surface hardness are lowered. In addition, the amino resin has a feature of good heat return, and therefore, the deposition time from applying the adhesive to the wooden base material and attaching the decorative paper to the heat pressing becomes longer. However, the advantage that the adhesive performance is hardly lowered is also lost. As described above, no non-formaldehyde adhesive has been found that has all the characteristics of amino resins.
本発明はアミノ系樹脂のようなホルムアルデヒド含有樹脂を使用することなく、化粧紙への浸透性や耐水性、表面硬度に優れ、堆積時間が長い場合であっても接着性能の低下が少ないという、従来のホルムアルデヒド含有樹脂と同等以上の特徴を有する接着剤組成物を提供するものである。 The present invention is excellent in permeability to decorative paper, water resistance and surface hardness without using formaldehyde-containing resins such as amino resins, and there is little decrease in adhesion performance even when the deposition time is long. The present invention provides an adhesive composition having characteristics equivalent to or better than those of conventional formaldehyde-containing resins.
本発明者らが鋭意検討を重ねた結果、アセトアセチル基を含有する酢酸ビニル系樹脂エマルジョン（ａ）、アクリルアミド樹脂（ｂ）、イソシアネート化合物（ｃ）、および植物粉を含有する接着剤組成物により前記課題が解決されることを見出した。また、アセトアセチル基を含有する酢酸ビニル系樹脂エマルジョン（ａ）が、アセトアセチル基含有ポリビニルアルコールを保護コロイドとし、酢酸ビニル及びアセトアセチル基含有単量体を共重合して得られたものであることが好ましく、また、植物粉を含有することが好ましいことを併せて見出した。 As a result of extensive studies by the present inventors, an adhesive composition containing a vinyl acetate resin emulsion (a) containing an acetoacetyl group, an acrylamide resin (b), an isocyanate compound (c) , and a plant powder It has been found that the above problems can be solved. The vinyl acetate resin emulsion (a) containing an acetoacetyl group is obtained by copolymerizing vinyl acetate and an acetoacetyl group-containing monomer using acetoacetyl group-containing polyvinyl alcohol as a protective colloid. It was also found that it is preferable to contain plant powder.
ところで、イソシアネート化合物のような架橋剤を添加した場合、化学反応硬化の進行によって堆積時間が長い場合は接着性能が大幅に低下すると予想されるが、意外にも本発明の接着剤組成物は逆に接着性能が低下しにくくなった。特に、小麦粉等の植物粉を加えた場合、接着性能の低下を顕著に抑制できるため、何らかの相互作用があるものと推察される。 By the way, when a cross-linking agent such as an isocyanate compound is added, it is expected that the adhesion performance will be significantly lowered when the deposition time is long due to the progress of chemical reaction curing, but the adhesive composition of the present invention is surprisingly reversed. In addition, the adhesive performance is less likely to deteriorate. In particular, when plant flour such as wheat flour is added, it is presumed that there is some interaction because a decrease in adhesion performance can be remarkably suppressed.
本発明の接着剤組成物及び接着方法は高度な耐水性、表面硬度を有し、また、堆積時間が長い場合であっても接着性能の低下が少ないという特徴を有するため、ポリエステル化粧板の製造工程において、ライントラブル等により加熱圧締前の仕掛り品が滞留した場合であっても十分な接着力を得ることができる。また、ホルムアルデヒドの放散源となるアミノ系樹脂を使用していないため、住宅等に使用される建材の製造にも問題なく使用できる。 Since the adhesive composition and bonding method of the present invention have high water resistance and surface hardness, and are characterized by little deterioration in bonding performance even when the deposition time is long, the polyester decorative board is produced. In the process, a sufficient adhesive force can be obtained even when the work-in-process product before heating and pressing stays due to line trouble or the like. Moreover, since the amino resin used as a formaldehyde emission source is not used, it can be used for the production of building materials used in houses and the like.
以下、本発明について詳細に説明する。
本発明で使用されるアセトアセチル基を含有する酢酸ビニル系樹脂エマルジョン（ａ）は、例えば、ケン化度７５〜９９．５％、平均重合度３００〜４０００であるポリビニルアルコールのような水溶性高分子を保護コロイドとするか、あるいは界面活性剤等の乳化剤を併用して、酢酸ビニル単独または酢酸ビニルと共重合可能な単量体を乳化重合することにより合成される。アセトアセチル基を含有するという点については、例えばアセトアセチル基含有ポリビニルアルコール水溶液を酢酸ビニル系樹脂エマルジョンに添加する方法でも良いが、酢酸ビニル系樹脂エマルジョン自体がアセトアセチル基を有していた方が耐水性に優れる。したがって、アセトアセチル基含有ポリビニルアルコールを保護コロイドとするか、アセトアセトキシエチルメタクリレートのようなアセトアセチル基含有単量体を共重合することが好ましく、両者とも行うことがさらに好ましい。
Hereinafter, the present invention will be described in detail.
The vinyl acetate resin emulsion (a) containing an acetoacetyl group used in the present invention is, for example, highly water-soluble such as polyvinyl alcohol having a saponification degree of 75 to 99.5% and an average polymerization degree of 300 to 4000. The polymer is synthesized by emulsion polymerization of vinyl acetate alone or a monomer copolymerizable with vinyl acetate using a protective colloid as a molecule or an emulsifier such as a surfactant. Regarding the point of containing an acetoacetyl group, for example, a method of adding an aqueous solution of polyvinyl alcohol containing an acetoacetyl group to a vinyl acetate resin emulsion may be used, but the vinyl acetate resin emulsion itself has an acetoacetyl group. Excellent water resistance. Therefore, it is preferable to use acetoacetyl group-containing polyvinyl alcohol as a protective colloid or copolymerize an acetoacetyl group-containing monomer such as acetoacetoxyethyl methacrylate, and it is more preferable to carry out both.
アクリルアミド樹脂（ｂ）を使用することにより、化粧紙のようなセルロース系基材への接着剤の浸透性を向上させることができ、応力がかかった際に容易に化粧紙層ではく離することを防止し、接着力を向上させることができる。アクリルアミド樹脂としてはポリアクリルアミドの他、変性ポリアクリルアミドを用いても良い。アクリルアミド樹脂は、一般に紙力増強剤等として各社から市販されており、これらの市販品を用いることができる。前記（ａ）の固形分１００重量部に対する（ｂ）の配合量は固形分で１０〜５０重量部とすることが好ましい。 By using the acrylamide resin (b), it is possible to improve the permeability of the adhesive to the cellulosic base material such as decorative paper, and to easily peel off the decorative paper layer when stress is applied. It is possible to prevent and improve the adhesive force. In addition to polyacrylamide, modified polyacrylamide may be used as the acrylamide resin. Acrylamide resins are generally commercially available from various companies as paper strength enhancers and the like, and these commercially available products can be used. The blending amount of (b) with respect to 100 parts by weight of the solid content of (a) is preferably 10 to 50 parts by weight in terms of solid content.
イソシアネート化合物（ｃ）を前記（ａ）及び（ｂ）と共に接着剤組成物に含有させることにより、耐水性の向上の他、表面硬度を向上させることができる。イソシアネート化合物としては、ＭＤＩ（ジフェニルメタンジイソシアネート）やＨＤＩ（ヘキサメチレンジイソシアネート）等の公知のものや、これらの誘導体を用いることができる。中でも好ましいのＭＤＩであり、より好ましいのはポリメリックＭＤＩや、２，４´−ＭＤＩ、４，４´−ＭＤＩの混合物（クルードＭＤＩと称される）である。前記（ａ）の固形分１００重量部に対する（ｃ）の配合量は２〜５０重量部とすることが好ましい。この範囲であれば、表面硬度が向上し、作業性に影響を及ぼすほどの増粘がない。 By including the isocyanate compound (c) in the adhesive composition together with the above (a) and (b), the surface hardness can be improved in addition to the improvement in water resistance. As an isocyanate compound, well-known things, such as MDI (diphenylmethane diisocyanate) and HDI (hexamethylene diisocyanate), and these derivatives can be used. Among them, preferred is MDI, and more preferred is polymeric MDI or a mixture of 2,4′-MDI and 4,4′-MDI (referred to as crude MDI). The blending amount of (c) with respect to 100 parts by weight of the solid content of (a) is preferably 2 to 50 parts by weight. If it is this range, surface hardness will improve and there will be no thickening which affects workability | operativity.
本発明の接着剤組成物には、前記三成分に加えて植物粉を添加することが好ましい。植物粉の添加によって、接着剤組成物の粘度を高めたり、接着剤組成物が化粧紙層の表面側へ染み出すことを防止する効果が得られるのは公知だが、本発明の接着剤組成物に用いた場合、堆積時間が長い場合であっても接着性能の低下が抑制されるという特異的な効果をもたらす。植物粉としては、小麦粉、木粉、椰子粉、クルミ粉、米粉等が挙げられる。前記（ａ）の固形分１００重量部に対する植物粉の配合量が５０重量部を超えると接着剤の粘度が上がり過ぎて作業性が低下するため、５０重量部以下とすることが好ましい。 In addition to the three components, it is preferable to add vegetable powder to the adhesive composition of the present invention. Although it is known that the addition of plant powder can increase the viscosity of the adhesive composition or prevent the adhesive composition from exuding to the surface side of the decorative paper layer, the adhesive composition of the present invention is known. When used for the above, it brings about a specific effect that even if the deposition time is long, a decrease in adhesion performance is suppressed. Examples of plant flour include wheat flour, wood flour, coconut flour, walnut flour, and rice flour. When the blending amount of the plant powder with respect to 100 parts by weight of the solid content (a) exceeds 50 parts by weight, the viscosity of the adhesive is excessively increased and workability is deteriorated.
本発明の接着剤組成物は前記各成分の他、公知の添加剤を用いることができる。例えば、増粘剤、充填材、ｐＨ調整剤、粘着付与樹脂、界面活性剤、防腐剤、消泡剤、防錆剤等が挙げられる。 In the adhesive composition of the present invention, known additives can be used in addition to the above components. For example, a thickener, a filler, a pH adjuster, a tackifier resin, a surfactant, an antiseptic, an antifoaming agent, an antirust agent, and the like can be given.
以下、実施例に基づいて本発明をより具体的に説明するが、本発明は実施例に制限されるものではない。なお、特にことわりのない限り、部は重量部を示し、％は重量％を示す。 EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example, this invention is not restrict | limited to an Example. Unless otherwise specified, “part” means “part by weight” and “%” means “% by weight”.
アセトアセチル基を含有する酢酸ビニル系樹脂エマルジョンの合成
アセトアセチル化ポリビニルアルコールであるゴーセファイマーＺ−２００（日本合成化学工業株式会社製、商品名）１０部、未変性ポリビニルアルコールであるＨ−１７（電気化学工業株式会社製、商品名）１４部、及びＢ−０５（電気化学工業株式会社製、商品名）６部を水２２０部に分散し、８０℃にて１時間撹拌して溶解した。その後、洒石酸の１０％水溶液５部と、過酸化水素の１％水溶液１０部を加えた後、酢酸ビニルモノマー１８０部、アセトアセトキシエチルメタクリレート２０部、過酸化水素の１％水溶液４０部を、３時間で滴下して乳化重合を行い、さらに８０℃で１時間熟成後、フェニルグリコール−Ｈ（日本乳化剤株式会社製、商品名）９部、重亜硫酸ソーダ（重合禁止剤）の１０％水溶液１部を添加して冷却した。平均粒子径２μｍの重質炭酸カルシウム７０部を水７０部に混合分散させたペースト合計１４０部を加え、アセトアセチル基を含有する酢酸ビニル系樹脂エマルジョンａ１（固形分４５％）を得た。
Synthesis of vinyl acetate-based resin emulsion containing acetoacetyl group 10 parts of Gosefimer Z-200 (trade name, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) which is an acetoacetylated polyvinyl alcohol, H-17 which is unmodified polyvinyl alcohol (Electrochemical Industry Co., Ltd., trade name) 14 parts and B-05 (Electrochemical Industry Co., Ltd., trade name) 6 parts were dispersed in 220 parts of water and dissolved by stirring at 80 ° C. for 1 hour. . Then, after adding 5 parts of 10% aqueous solution of arsenic acid and 10 parts of 1% aqueous solution of hydrogen peroxide, 180 parts of vinyl acetate monomer, 20 parts of acetoacetoxyethyl methacrylate and 40 parts of 1% aqueous solution of hydrogen peroxide were added. After 3 hours of dropwise addition, emulsion polymerization was performed, and after aging at 80 ° C. for 1 hour, 9 parts of phenyl glycol-H (trade name, manufactured by Nippon Emulsifier Co., Ltd.), 10% aqueous solution of sodium bisulfite (polymerization inhibitor) One part was added and cooled. A total of 140 parts of paste in which 70 parts of heavy calcium carbonate having an average particle diameter of 2 μm was mixed and dispersed in 70 parts of water was added to obtain a vinyl acetate resin emulsion a1 (solid content 45%) containing acetoacetyl groups.
参考例１
アセトアセチル基を含有する酢酸ビニル系樹脂エマルジョンａ１を１００部、アクリルアミド樹脂であるポリストロン１１７（固形分１５％、荒川化学工業株式会社製、商品名）１００部、クルードＭＤＩであるＡＵＨ−１（アイカ工業株式会社製、商品名）２０部を混合し、参考例１の接着剤組成物を得た。
Reference example 1
100 parts of vinyl acetate resin emulsion a1 containing an acetoacetyl group, 100 parts of Polystron 117 (solid content 15%, manufactured by Arakawa Chemical Industries, Ltd., trade name) which is an acrylamide resin, AUH-1 which is Crude MDI ( 20 parts of Aika Kogyo Co., Ltd., trade name) were mixed to obtain an adhesive composition of Reference Example 1 .
実施例２、３、比較例１〜４
表１記載の配合に基づいて各材料を混合し、実施例、比較例の各接着剤組成物を得た。なお、参考例１で使用した以外の配合材料として、アセトアセチル基を含有しない酢酸ビニル系樹脂エマルジョンであるＡ−３２１Ｋ（固形分４０％、アイカ工業株式会社製、商品名）、小麦粉（日清製粉株式会社製、商品名：銀杏）、尿素−メラミン系樹脂であるＵＭＸ−１５Ｊ（固形分５４％、アイカ工業株式会社製、商品名）を用いた。
Examples 2 and 3 and Comparative Examples 1 to 4
Each material was mixed based on the mixing | blending of Table 1, and each adhesive composition of an Example and a comparative example was obtained. In addition, as compounding materials other than those used in Reference Example 1 , A-321K which is a vinyl acetate resin emulsion not containing an acetoacetyl group (solid content: 40%, manufactured by Aika Kogyo Co., Ltd., trade name), flour (Nisshin) UMX-15J (solid content of 54%, manufactured by Aika Kogyo Co., Ltd., trade name) which is a urea-melamine resin was used.
実施例、比較例の各接着剤組成物について、以下の試験方法に基づいて性能評価を行い、表１、表２にまとめた。 About each adhesive composition of an Example and a comparative example, performance evaluation was performed based on the following test methods, and it summarized in Table 1 and Table 2. FIG.
試験体の作成条件
ＪＡＳ２類合板（厚み２．５ｍｍ、Ｆ☆☆☆☆）に各接着剤組成物を６０ｇ／ｍ2塗布し、チタン紙（坪量６５ｇ／ｍ2）を貼り合わせた。所定の堆積時間放置後（１０分または６０分）、１００℃、０．５ＭＰａで４０秒間圧締した。１日養生後にポリエステル樹脂を塗装し、さらに３日間養生することにより、ポリエステル化粧合板を作成した。
２類浸漬はく離
ＪＡＳ特殊化粧合板の試験方法に準拠して行い、はく離の有無を確認した。
碁盤目テープはく離
２ｍｍ幅の升目が１０×１０個できるように試験体の表面に切り込みを入れ、升目にセロハンテープを貼り付けて勢い良く剥がし、界面はく離又は紙間はく離となった升目の数を確認した。
表面硬度
ＪＩＳ Ｋ５６００−５−４に準拠し、引っかき硬度を測定した。
ホルムアルデヒド放散量試験
ＪＡＳ特殊化粧合板の試験方法に準拠して行った。
Preparation conditions of test body Each adhesive composition was applied to JAS2 plywood (thickness 2.5 mm, F ☆☆☆☆) at 60 g / m 2 , and titanium paper (basis weight 65 g / m 2 ) was bonded. After standing for a predetermined deposition time (10 minutes or 60 minutes), pressing was performed at 100 ° C. and 0.5 MPa for 40 seconds. After curing for 1 day, a polyester resin was coated and further cured for 3 days to prepare a polyester decorative plywood.
It was performed in accordance with the test method for type 2 immersion peel JAS special decorative plywood, and the presence or absence of peel was confirmed.
Cut the surface of the specimen so that 10 × 10 squares with a 2 mm width of the cross-cut tape peel can be made, and apply cellophane tape to the grid and peel off vigorously. confirmed.
Surface hardness Scratch hardness was measured according to JIS K5600-5-4.
Formaldehyde emission test The test was performed according to the test method for JAS special decorative plywood.
実施例２、３の接着剤組成物は、堆積時間が長い場合であっても良好な性能を示した。一方、比較例の接着剤組成物は、いずれかの項目が不適であった。
The adhesive compositions of Examples 2 and 3 showed good performance even when the deposition time was long. On the other hand, any item of the adhesive composition of the comparative example was unsuitable.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007108878A JP5036382B2 (en) | 2007-04-18 | 2007-04-18 | Adhesive composition |
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| Application Number | Priority Date | Filing Date | Title |
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| JP2007108878A JP5036382B2 (en) | 2007-04-18 | 2007-04-18 | Adhesive composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2008266398A JP2008266398A (en) | 2008-11-06 |
| JP5036382B2 true JP5036382B2 (en) | 2012-09-26 |
Family
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| JP2007108878A Active JP5036382B2 (en) | 2007-04-18 | 2007-04-18 | Adhesive composition |
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| JP5349110B2 (en) * | 2009-03-27 | 2013-11-20 | アイカ工業株式会社 | Adhesive composition and method for producing veneer decorative material |
| JP2015034197A (en) * | 2013-08-07 | 2015-02-19 | 日本合成化学工業株式会社 | Dispersant for emulsion polymerization and vinyl acetate-based resin emulsion using the same, and adhesive agent |
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| JPS5690870A (en) * | 1979-12-24 | 1981-07-23 | Sumitomo Bakelite Co Ltd | Odorless adhesive for plywood |
| JPH06172740A (en) * | 1992-12-09 | 1994-06-21 | Aica Kogyo Co Ltd | Quick-curing water-base adhesive |
| JPH07268300A (en) * | 1994-04-01 | 1995-10-17 | Aica Kogyo Co Ltd | Adhesive |
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