JP6425999B2 - Aqueous adhesive composition for wrapping and wood building material using the same - Google Patents
Aqueous adhesive composition for wrapping and wood building material using the same Download PDFInfo
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Description
本発明は、ラッピング用水性接着剤組成物及びそれを用いた木質建材に関する。更に詳しくは、本発明は、特に、幅木、廻縁、窓枠等の建材として幅広く用いられているラッピング部材の接着に有用なラッピング用水性接着剤組成物及びそれを用いた木質建材に関する。 The present invention relates to an aqueous adhesive composition for lapping and a wood building material using the same. More particularly, the present invention relates to a water-based adhesive adhesive composition for wrapping useful for adhering a wrapping member widely used as a building material such as a baseboard, an edge of a window, etc., and a wood building material using the same.
ラッピング部材の接着には、ジクロロメタン等の有機溶剤を用いた溶剤型接着剤が用いられており、労動安全衛生法で特定化学物質障害予防規則(特化則)に順じた発癌性を踏まえた措置が義務付けられている。このようなラッピング用接着剤を水性化することができれば、特化則に順ずる全ての対応が不要になり、作業環境測定及び有機溶剤検診等の維持管理コストが低減されるとともに、労働者の健康障害のリスクを大幅に低減させることができる。また、建材に残存する発癌性の揮発性有機化合物(VOC)を除去することも可能となるなど、優位点は多々あるが、技術的には難しい接着技術で、有用なラッピング用水性接着剤は未だないのが実情である。 A solvent type adhesive using an organic solvent such as dichloromethane is used for adhesion of the wrapping member, and based on the carcinogenicity according to the specified chemical substance injury prevention rule (specialized rule) by the Labor Safety and Health Law. Measures are required. If such a wrapping adhesive can be made water-based, all the correspondence according to the specialization rule becomes unnecessary, and maintenance costs such as work environment measurement and organic solvent examination are reduced, and it is also possible for workers The risk of health problems can be significantly reduced. In addition, although there are many advantages such as removal of carcinogenic volatile organic compounds (VOCs) remaining in building materials, it is a technically difficult bonding technology, and useful lapping adhesive is The fact is that there is not yet.
更に、溶剤型ラッピング用接着剤に代替可能な接着剤として、設備投資は伴うものの、ポリウレタン系ホットメルト接着剤が挙げられ、実績もある。この接着剤は、反応性ホットメルト接着剤とも呼ばれ、一般的なホットメルト接着剤と同様に加熱溶融した状態で塗布し、被着材の圧着により冷却固化した後、水分と架橋反応することにより、従来のホットメルト接着剤より高い耐熱性、接着強度及び耐久性が発現されるホットメルト接着剤である。しかし、ホットメルト接着剤では、溶剤系ラッピングマシンを改造するための設備投資費用が発生する。また、反応性ホットメルト接着剤は、溶剤型接着剤に比べて接着に必要な塗布量は少量でよいものの、接着剤の単価が高いため、ランニングコストが増加する傾向にある。 Furthermore, as an adhesive that can be substituted for the solvent type lapping adhesive, although there is investment in equipment, a polyurethane-based hot melt adhesive can be mentioned and has been proven. This adhesive is also called a reactive hot melt adhesive, and is applied in the heat-melted state in the same manner as a general hot melt adhesive, cooled and solidified by pressure bonding of the adherend, and then cross-linking with water. It is a hot melt adhesive in which heat resistance, adhesive strength and durability higher than conventional hot melt adhesives are exhibited. However, with hot melt adhesives, there is a capital outlay to retrofit a solvent based lapping machine. In addition, although the reactive hot-melt adhesive may require a smaller amount of application for adhesion than a solvent-based adhesive, the running cost tends to increase because the unit price of the adhesive is high.
一方、ラッピング用水性接着剤の最大の優位性は、現有設備での切替使用が可能な点で、ホットメルト接着剤では必須となる接着剤の溶融設備及びアプリケーション(塗布)設備が不要である。また、水で容易に洗浄することができ、使用上及び使用管理上、取り扱いが容易である。しかし、現行の溶剤型接着剤と比べると接着可能な条件設定が難しいという問題がある。更に、現行の水性接着剤は、エマルジョン及びラテックスをベースとしており、水分の拡散、乾燥とともにエマルジョン粒子が接近して凝集し、接着力が発現される。そのため、接着剤の完全乾燥前に、被着面の双方に接着剤が転写されて濡れた状態になっていることが必須である。 On the other hand, the greatest advantage of the water-based adhesive for wrapping is that the existing equipment can be switched and used, and the equipment for melting the adhesive and application (application) necessary for hot melt adhesives are not required. Moreover, it can be easily washed with water, and is easy to handle in terms of use and management of use. However, there is a problem that it is difficult to set bonding conditions as compared with the existing solvent-based adhesives. Furthermore, the current aqueous adhesives are based on emulsions and latexes, and the emulsion particles approach and coagulate with the diffusion of water and drying to develop adhesion. Therefore, before the adhesive is completely dried, it is essential that the adhesive be transferred to both of the adherend surfaces to be in a wet state.
また、ラッピングラインでは、ドライラミネートするように、ある程度乾燥させておかなければ充分な初期接着性能が得られない。しかし、エマルジョン系接着剤及びラテックス系接着剤では、乾燥が進むと、過乾燥状態となり、極端に接着性が低下して接着不良を起こすことがある。更に、乾燥が不十分であると初期接着力が低下し、過乾燥になると接着不良になるといった点で難易度が高い条件設定が必要となる。また、エマルジョン及びラテックスは、長時間使用すると乾燥皮膜となって水洗性が低下する。更に、接着剤調製後、長時間経過すると、エマルジョン粒子等の凝集によってアプリケーション部分での不具合が生じて使用し難くなるという問題もある。 In addition, in the wrapping line, sufficient initial adhesion performance can not be obtained without drying to a certain extent so as to dry laminate. However, in the case of the emulsion-based adhesive and the latex-based adhesive, when the drying progresses, the adhesive becomes excessively dry, and the adhesion may be extremely reduced to cause adhesion failure. Furthermore, if the drying is insufficient, the initial adhesion is reduced, and if the drying becomes excessive, it is necessary to set conditions having a high degree of difficulty in that the adhesion becomes poor. In addition, when the emulsion and the latex are used for a long time, they become a dry film and the water washing property decreases. Furthermore, after preparation of the adhesive, if a long time elapses, there is a problem that the aggregation of the emulsion particles and the like causes problems in the application part and the use becomes difficult.
特許文献1〜7の接着剤は全て水性ではあるもののエマルジョンやラテックスからなり、例えば、引用文献1に記載の接着剤ではシリル化変性するため、極めて高価な接着剤となってしまい、初期接着も必ずしも十分ではない。また、特許文献1〜7の接着剤は、高分子材料を用いたエマルジョン型又はラテックス型の接着剤であるため、ラッピングのように溶媒をある程度揮発させて貼り合わせるような場合、凝集が進むとともに粘着性及び接着性が著しく低下することがある。また、ウエット状態とドライ状態の接着性が相違し過ぎ、接着に適した乾燥状態の許容幅が狭いため、実際に用いる場合、使用し難いという問題もある。更に、特許文献8に記載のエマルジョン型感圧接着剤の場合、接着剤を塗工するアプリケーター開閉時のシェアによって樹脂が凝集するため、現有設備の場合に塗工部分での不具合が生じることがある。 The adhesives of Patent Documents 1 to 7 are all aqueous but consist of an emulsion or latex, and for example, the adhesive described in Patent Document 1 becomes a very expensive adhesive because it is silylated and modified, and initial adhesion is also possible. It is not always enough. Moreover, since the adhesive of patent documents 1-7 is an emulsion type or latex type adhesive using a polymer material, when volatilizing a solvent and pasting together like wrapping, while aggregation advances, Tack and adhesion may be significantly reduced. Further, the adhesion between the wet state and the dry state is too different, and the allowable range of the dry state suitable for the adhesion is narrow, so that there is a problem that it is difficult to use in actual use. Furthermore, in the case of the emulsion-type pressure-sensitive adhesive described in Patent Document 8, since the resin is coagulated due to shear at the time of opening and closing of the applicator to which the adhesive is applied, in the case of existing equipment is there.
一方、不飽和カルボン酸を重合してなる水溶性の重合体であるオリゴマー又はポリマーを主成分とする非エマルジョン型の水性接着剤は、ラッピング部材の接着適性に優れ、環境負荷が少ない。また、粘着力が強く粘着保持時間も長く、実際に用いる場合に、使用し易い接着剤である。更に、上述の特性が損なわれない範囲で、不飽和カルボン酸エステルとの共重合、エマルジョン形接着剤等の混合、架橋剤の添加なども可能である。また、使用時には、媒体である水分を揮発させることで、ポリアクリル酸等のカルボキシル基含有ポリマー特有の高い粘着力を有するとともに、粘着保持時間の長い水性接着剤とすることができる。更に、安価で環境負荷が少なく、溶剤型接着剤用の現有設備で使用することができ、ホットメルト接着剤等では必須となる設備投資も不要になるなど、多くの優位点を備える。
本発明は、このような知見に基づいてなされたものである。
On the other hand, a non-emulsion type aqueous adhesive comprising an oligomer or a polymer, which is a water-soluble polymer formed by polymerizing an unsaturated carboxylic acid as a main component, is excellent in the adhesion aptitude of the wrapping member and has less environmental impact. In addition, the adhesive has a strong adhesive strength and a long adhesive holding time, and is an adhesive that is easy to use in actual use. Furthermore, copolymerization with an unsaturated carboxylic acid ester, mixing of an emulsion adhesive, etc., addition of a crosslinking agent, etc. are also possible as long as the above-mentioned properties are not impaired. Further, at the time of use, by volatilizing water as a medium, it is possible to obtain an aqueous adhesive having a high adhesive strength peculiar to a carboxyl group-containing polymer such as polyacrylic acid and having a long adhesion retention time. Furthermore, it has many advantages, such as low cost, low environmental impact, and can be used in existing equipment for solvent-based adhesives, eliminating the need for equipment investment which is essential for hot melt adhesives and the like.
The present invention has been made based on such findings.
本発明は以下のとおりである。
1.不飽和カルボン酸が水媒体中で重合されて得られる水溶性の重合体を主成分とするラッピング用水性接着剤組成物。
2.前記重合時にポリビニルアルコールを併存させる前記1.に記載のラッピング用水性接着剤組成物。
3.前記不飽和カルボン酸として、アクリル酸とメタクリル酸が併用され、前記アクリル酸を100質量部とした場合に、前記メタクリル酸が3〜50質量部である前記1.又は2.に記載のラッピング用水性接着剤組成物。
4.前記重合時に、不飽和カルボン酸エステルが併用されて共重合体とされ、前記不飽和カルボン酸を100質量部とした場合に、前記不飽和カルボン酸エステルが0.01〜30質量部である前記1.乃至3.のうちのいずれか1項に記載のラッピング用水性接着剤組成物。
5.アミノエチル化アクリル重合体、エチレン−酢酸ビニル樹脂系エマルジョン、アクリル樹脂系エマルジョン、合成ゴム系ラテックス及びウレタン樹脂ディスパージョンのうちの少なくとも1種が配合されている前記1.乃至4.のうちのいずれか1項に記載のラッピング用水性接着剤組成物。
6.粘着付与剤が配合されている前記1.乃至5.のうちのいずれか1項に記載のラッピング用水性接着剤組成物。
7.架橋剤が配合されている前記1.乃至6.のうちのいずれか1項に記載のラッピング用水性接着剤組成物。
8.前記架橋剤が、イソシアネート系化合物、カルボジイミド系化合物、オキサゾリン系化合物及びヒドラジン系化合物から選ばれる少なくとも1種の化合物である前記7.に記載のラッピング用水性接着剤組成物。
9.前記1.乃至8.のうちのいずれか1項に記載のラッピング用水性接着剤組成物を用いて製造されたことを特徴とする木質建材。
The present invention is as follows.
1. An aqueous adhesive composition for wrapping comprising a water-soluble polymer obtained by polymerizing an unsaturated carboxylic acid in an aqueous medium as a main component.
2. In the above 1. The water-based adhesive composition for wrapping as described in 4.
3. Acrylic acid and methacrylic acid are used in combination as the unsaturated carboxylic acid, and when the amount of the acrylic acid is 100 parts by mass, the amount of the methacrylic acid is 3 to 50 parts by mass. Or 2. The water-based adhesive composition for wrapping as described in 4.
4. In the polymerization, an unsaturated carboxylic acid ester is used in combination to form a copolymer, and when the unsaturated carboxylic acid is 100 parts by mass, the unsaturated carboxylic acid ester is 0.01 to 30 parts by mass. 1. To 3. An aqueous adhesive composition for wrapping according to any one of the preceding claims.
5. 1. At least one of an aminoethylated acrylic polymer, an ethylene-vinyl acetate resin emulsion, an acrylic resin emulsion, a synthetic rubber latex, and a urethane resin dispersion is blended. To 4. An aqueous adhesive composition for wrapping according to any one of the preceding claims.
6. The above-mentioned 1. where the tackifier is blended. To 5. An aqueous adhesive composition for wrapping according to any one of the preceding claims.
7. The above 1. To 6. An aqueous adhesive composition for wrapping according to any one of the preceding claims.
8. 7. The method according to 7 above, wherein the crosslinking agent is at least one compound selected from an isocyanate compound, a carbodiimide compound, an oxazoline compound and a hydrazine compound. The water-based adhesive composition for wrapping as described in 4.
9. Said 1. To 8. A wood building material manufactured using the aqueous adhesive composition for wrapping according to any one of the above.
本発明のラッピング用水性接着剤組成物は、不飽和カルボン酸を重合してなる水溶性の重合体を主成分としており、粘着性が高く、且つ粘着保持時間が長いため、ラッピングマシン等での接着適性に優れる。また、非エマルジョン、非ラテックス型接着剤なので、緩やかに乾燥し、貼り合わせ前の凝集による物性の大幅な変化が極めて少ない。そのため、品質の安定した木質建材を製造することができるとともに、建材から発散する揮発性の有害化学物質を低減させることもできる。更に、水溶性の重合体であるため、水に不溶の重合体を用いたときと比べて耐水性がやや低下するかもしれないが、洗浄性に優れるという大きな長所がある。また、溶剤型接着剤のような有機溶剤を用いることによる健康面での対応等の管理コストが不要、又は少なくとも低減され、作業者の健康障害のリスクを大幅に低減させることもできる。更に、ホットメルト系接着剤のように加熱設備等の設備投資に多額の費用を必要とすることもない。 The aqueous adhesive composition for wrapping of the present invention is mainly composed of a water-soluble polymer formed by polymerizing unsaturated carboxylic acid and has high tackiness and long tack holding time, so that it can be used in a lapping machine or the like. Excellent adhesion suitability. In addition, since it is a non-emulsion, non-latex adhesive, it dries gently and there is very little significant change in physical properties due to aggregation before bonding. Therefore, it is possible to manufacture a wood building material with stable quality, and to reduce volatile harmful chemical substances emanating from the building material. Furthermore, since it is a water-soluble polymer, its water resistance may be slightly reduced as compared with the case of using a water-insoluble polymer, but it has a great advantage of being excellent in the cleaning property. In addition, management costs such as health care by using an organic solvent such as a solvent type adhesive are unnecessary or at least reduced, and the risk of health hazards for workers can be significantly reduced. Furthermore, unlike the hot melt adhesive, there is no need to spend a large amount of money on equipment investment such as heating equipment.
また、重合時にポリビニルアルコールを併存させる場合は、十分な接着強度が得られ、且つ接着剤組成物そのものの破壊強度も大きく、接着時の条件設定の許容幅も広い。
更に、不飽和カルボン酸として、アクリル酸とメタクリル酸が併用され、アクリル酸を100質量部とした場合に、メタクリル酸が3〜50質量部である場合は、接着強度をより高めることができ、接着時の条件設定の許容幅も併用しないときと同等とすることができる。
また、重合時に、不飽和カルボン酸エステルが併用されて共重合体とされ、不飽和カルボン酸を100質量部とした場合に、不飽和カルボン酸エステルが0.01〜30質量部である場合は、共重合体が水溶性となり、併用しないときと同等の接着強度を有する。
更に、アミノエチル化アクリル重合体、エチレン−酢酸ビニル樹脂系エマルジョン、アクリル樹脂系エマルジョン、合成ゴム系ラテックス及びウレタン樹脂ディスパージョンのうちの少なくとも1種が配合されている場合は、接着強度をより高めることができ、接着時の条件設定の許容幅も併用しないときと同等とすることができる。
また、粘着付与剤が配合されている場合は、接着時の条件設定の幅を微調整することができる。
更に、架橋剤が配合されており、特に架橋剤が、イソシアネート系化合物、カルボジイミド系化合物、オキサゾリン系化合物及びヒドラジン系化合物から選ばれる少なくとも1種の化合物である場合は、接着強度を更に大きく向上させることができるとともに、耐熱性を向上させることもできる。
In addition, when polyvinyl alcohol is allowed to coexist during polymerization, sufficient adhesive strength is obtained, the breaking strength of the adhesive composition itself is also large, and the allowable range of setting of conditions for bonding is also wide.
Furthermore, when acrylic acid and methacrylic acid are used in combination as the unsaturated carboxylic acid, and the amount of acrylic acid is 100 parts by mass, when the amount of methacrylic acid is 3 to 50 parts by mass, adhesion strength can be further enhanced. The allowable range of setting of conditions for bonding can be equal to that when not used in combination.
In addition, at the time of polymerization, unsaturated carboxylic acid ester is used in combination to form a copolymer, and when unsaturated carboxylic acid is 100 parts by mass, 0.01 to 30 parts by mass of unsaturated carboxylic acid ester is used. The copolymer is water soluble and has an adhesive strength equivalent to that when not used in combination.
Furthermore, when at least one of an aminoethylated acrylic polymer, an ethylene-vinyl acetate resin emulsion, an acrylic resin emulsion, a synthetic rubber latex and a urethane resin dispersion is blended, the adhesive strength is further enhanced. The allowable range of setting of conditions for bonding can be equal to that when not used in combination.
Moreover, when the tackifier is mix | blended, the range of the condition setting at the time of adhesion | attachment can be finely adjusted.
Furthermore, when a crosslinking agent is blended, and in particular, the crosslinking agent is at least one compound selected from an isocyanate compound, a carbodiimide compound, an oxazoline compound, and a hydrazine compound, the adhesion strength is further greatly improved. Heat resistance can also be improved.
本発明の木質建材は、ラッピング用水性接着剤組成物を用いて製造されているため、木質基材と意匠面となるポリオレフィンシート等とが十分な強度で接着されており、大気雰囲気で加熱したとき、及び温水に浸漬したときに剥離し難く、木質建材製造時の被着材への塗布時の作業性も優れている。 Since the wood building material of the present invention is manufactured using the aqueous adhesive composition for wrapping, the wood substrate and the polyolefin sheet or the like to be a design surface are bonded with sufficient strength and heated in the atmosphere. It is difficult to peel off when immersed in warm water and water, and the workability at the time of application to the adherend at the time of producing the wood building material is also excellent.
以下、本発明を詳しく説明する。
本発明のラッピング用水性接着剤組成物(以下、「水性接着剤組成物」と略記することもある。)は、不飽和カルボン酸が水媒体中で重合されて得られる水溶性の重合体を主成分とする。
このラッピング用水性接着剤組成物は、強い粘着性と長い粘着保持時間とを有し、水分の拡散(乾燥)による凝集機構による接着形態であるエマルジョン型等の接着剤と比べ、ラッピング用の接着剤としてより好適である。
Hereinafter, the present invention will be described in detail.
The aqueous adhesive composition for wrapping of the present invention (hereinafter sometimes abbreviated as "aqueous adhesive composition") is a water-soluble polymer obtained by polymerizing unsaturated carboxylic acid in an aqueous medium. Main component
This aqueous adhesive composition for wrapping has a strong tack and a long tack holding time, and has an adhesive for wrapping as compared with an adhesive such as an emulsion type which has an adhesive form by an aggregation mechanism by diffusion (drying) of water. It is more suitable as an agent.
また、水性接着剤組成物の製造方法は特に限定されないが、例えば、媒体である水に、撹拌しながら所定量のアクリル酸等の不飽和カルボン酸及び重合開始剤を添加し、加温して重合させ(初期の重合工程)、続いて、液温を保ったまま、所定量のアクリル酸等の不飽和カルボン酸及び重合開始剤を連続的に滴下して更に重合させ(後段の重合工程)、滴下終了後、熟成させる方法等が挙げられる。更に、重合工程では、重合安定性、重合度及び粘度制御などのため、亜硫酸水素ナトリウム、連鎖移動剤等を仕込み、分散させておくことが好ましい。 Also, the method for producing the aqueous adhesive composition is not particularly limited, but, for example, a predetermined amount of unsaturated carboxylic acid such as acrylic acid and a polymerization initiator are added to water as a medium while stirring, and then heated. It is polymerized (initial polymerization step), and then, while maintaining the liquid temperature, predetermined amounts of unsaturated carboxylic acid such as acrylic acid and the like and a polymerization initiator are continuously dropped and further polymerized (the latter polymerization step) The method of making it ripe | cure etc. is mentioned after completion | finish of dripping. Furthermore, in the polymerization step, it is preferable to charge and disperse sodium bisulfite, a chain transfer agent and the like in order to control the polymerization stability, polymerization degree and viscosity.
重合開始剤としては、過酸化水素、過硫酸アンモニウム、過硫酸カリウム等の過酸化物及び水溶性アゾ重合開始剤等を用いることができ、これらの重合開始剤は、重合反応が完結される系であれば特に限定されない。重合開始剤は、例えば、予め10〜20質量%程度の濃度の水溶液として調製され、使用される。重合開始剤の使用量は、初期の重合工程では、不飽和カルボン酸を100質量部とした場合に、0.1〜5.0質量部、特に0.5〜3.0質量部とすることができる。また、後段の重合工程では、0.5〜10.0質量部、特に1.0〜5.0質量部とすることができる。 As a polymerization initiator, peroxides such as hydrogen peroxide, ammonium persulfate, potassium persulfate, a water-soluble azo polymerization initiator, etc. can be used, and these polymerization initiators are systems in which the polymerization reaction is completed. There is no particular limitation as long as it is. The polymerization initiator is, for example, previously prepared and used as an aqueous solution having a concentration of about 10 to 20% by mass. In the initial polymerization step, the amount of the polymerization initiator used is 0.1 to 5.0 parts by mass, in particular 0.5 to 3.0 parts by mass, based on 100 parts by mass of the unsaturated carboxylic acid. Can. Moreover, in the polymerization step of the latter stage, it can be 0.5 to 10.0 parts by mass, in particular 1.0 to 5.0 parts by mass.
更に、媒体である水の温度は、初期の重合工程において不飽和カルボン酸等を添加する時点では室温(例えば、25〜35℃)であり、その後、加温して重合反応を促進させる。加温により設定される反応温度は特に限定されないが、媒体が水であること、及び反応を十分に促進させること、を勘案すると、50〜90℃、特に70〜85℃とすることが好ましい。また、亜硫酸水素ナトリウム等を仕込み、分散させた後、不飽和カルボン酸等の添加前に、各種の界面活性剤を添加することもできる。これにより、粘性や重合安定性を微調整することができる。 Furthermore, the temperature of water as a medium is room temperature (for example, 25 to 35 ° C.) when unsaturated carboxylic acid and the like are added in the initial polymerization step, and then heated to promote the polymerization reaction. Although the reaction temperature set by heating is not particularly limited, it is preferably 50 to 90 ° C., particularly preferably 70 to 85 ° C. in consideration of the fact that the medium is water and that the reaction is sufficiently promoted. In addition, various surfactants may be added after the sodium bisulfite and the like are charged and dispersed, and before the addition of the unsaturated carboxylic acid and the like. Thereby, the viscosity and the polymerization stability can be finely adjusted.
不飽和カルボン酸は水溶性の重合体が得られる限り特に限定されず、各種の不飽和カルボン酸を用いることができる。この不飽和カルボン酸としては、アクリル酸、メタクリル酸、クロトン酸、イタコン酸、マレイン酸、フマル酸等が挙げられ、アクリル酸及びメタクリル酸が好ましい。不飽和カルボン酸は1種のみでもよく、2種以上を併用(併用する場合、実用上、通常、2種)して共重合体とすることもできる。また、アクリル酸とメタクリル酸とを併用する場合、アクリル酸を100質量部としたときに、メタクリル酸が3〜50質量部、特に10〜30質量部であることが好ましい。メタクリル酸が3〜50質量部であれば、接着強度をより高めることができ、接着時の条件設定の許容幅も同等とすることができる。 The unsaturated carboxylic acid is not particularly limited as long as a water-soluble polymer can be obtained, and various unsaturated carboxylic acids can be used. As this unsaturated carboxylic acid, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid etc. may be mentioned, with preference given to acrylic acid and methacrylic acid. The unsaturated carboxylic acid may be used alone or in combination of two or more kinds (when used in combination, usually two kinds in practice) to form a copolymer. When acrylic acid and methacrylic acid are used in combination, the amount of methacrylic acid is preferably 3 to 50 parts by mass, and more preferably 10 to 30 parts by mass, based on 100 parts by mass of acrylic acid. If it is 3-50 mass parts of methacrylic acid, adhesive strength can be raised more and the tolerance | permissible width of the condition setting at the time of adhesion | attachment can also be made equivalent.
更に、水性接着剤組成物には、ラッピング用の接着剤の用途に一般に用いられる各種の添加剤等を配合することができる。この添加剤等としては、増粘剤、界面活性剤、充填材、顔料、消泡剤、保存剤及び防錆剤などが挙げられる。但し、水性接着剤組成物は、不飽和カルボン酸が水媒体中で重合されて得られる水溶性の重合体を主成分とするものである。この主成分とは、水性接着剤組成物を100質量%とした場合(但し、水性接着剤組成物に他の水溶性又は水に難溶若しくは不溶の重合体が含有されるときは、それらの重合体は除く。)に、不飽和カルボン酸を重合させてなる水溶性の重合体が80質量%以上、特に90質量%以上、更に95質量%以上であることを意味する。不飽和カルボン酸を重合させてなる水溶性の重合体が80質量%以上であれば、本発明のラッピング水性接着剤組成物が本来有する前述の特性が損なわれることがない。 Furthermore, various additives and the like generally used for adhesive applications for wrapping can be added to the aqueous adhesive composition. As this additive etc., a thickener, surfactant, a filler, a pigment, an antifoamer, a preservative, an antirust agent etc. are mentioned. However, the aqueous adhesive composition is based on a water-soluble polymer obtained by polymerizing unsaturated carboxylic acid in an aqueous medium. When the aqueous adhesive composition is 100% by mass (provided that the aqueous adhesive composition contains another water-soluble or poorly soluble or insoluble polymer in the aqueous adhesive composition), the main component is It means that the water-soluble polymer obtained by polymerizing the unsaturated carboxylic acid with 80% by mass or more, particularly 90% by mass or more, further 95% by mass or more, excluding the polymer. If the water-soluble polymer obtained by polymerizing the unsaturated carboxylic acid is 80% by mass or more, the above-mentioned properties inherent to the wrapping aqueous adhesive composition of the present invention are not impaired.
水性接着剤組成物には、重合時に、不飽和カルボン酸の重合体を除く他の水溶性の重合体を併存させることができる。このような水溶性の重合体が併存する状態で重合させることで、十分な初期接着強度が得られ、且つ水性接着剤組成物そのものの破壊強度等の物性が向上する。この他の水溶性の重合体としては、ポリビニルアルコールの他、イソブチレン/無水マレイン共重合体、カルボキシメチルセルロース及びヒドロキシエチルセルロース等のセルロース類などが挙げられる。また、他の水溶性の重合体の配合量は、不飽和カルボン酸の重合体を100質量部とした場合に、1〜30質量部、特に3〜20質量であることが好ましい。他の水溶性の重合体の配合量が1〜30質量部でれば、水性接着剤組成物の初期接着強度及び物性が十分に向上する。 The water-based adhesive composition can coexist with other water-soluble polymers other than the unsaturated carboxylic acid polymer during polymerization. By polymerizing in a state in which such a water-soluble polymer coexists, sufficient initial adhesive strength can be obtained, and physical properties such as the breaking strength of the aqueous adhesive composition itself can be improved. Examples of other water-soluble polymers include polyvinyl alcohol and cellulose such as isobutylene / maleic anhydride copolymer, carboxymethyl cellulose and hydroxyethyl cellulose. The amount of the other water-soluble polymer is preferably 1 to 30 parts by mass, and more preferably 3 to 20 parts by mass, based on 100 parts by mass of the unsaturated carboxylic acid polymer. When the amount of the other water-soluble polymer is 1 to 30 parts by mass, the initial adhesive strength and physical properties of the aqueous adhesive composition are sufficiently improved.
更に、重合時に、不飽和カルボン酸エステルが併用され、不飽和カルボン酸と不飽和カルボン酸エステルとの共重合体とすることもできる。この共重合体も水溶性である必要があり、不飽和カルボン酸を100質量部とした場合に、不飽和カルボン酸エステルは0.01〜30質量部、特に0.01〜20質量部、更に0.01〜10質量部であることが好ましい。更に、不飽和カルボン酸エステルとしては、炭素数の少ないアルキルエステルであることが好ましく、例えば、(メタ)アクリル酸メチル、(メタ)アクリル酸エチル及び(メタ)アクリル酸ブチル等を用いることができる[(メタ)アクリル酸は、アクリル酸又はメタクリル酸を意味する。]。 Furthermore, at the time of polymerization, an unsaturated carboxylic acid ester may be used in combination to form a copolymer of an unsaturated carboxylic acid and an unsaturated carboxylic acid ester. This copolymer also needs to be water-soluble, and when the amount of unsaturated carboxylic acid is 100 parts by mass, the amount of unsaturated carboxylic acid ester is 0.01 to 30 parts by mass, particularly 0.01 to 20 parts by mass, and further It is preferable that it is 0.01-10 mass parts. Furthermore, the unsaturated carboxylic acid ester is preferably an alkyl ester having a small number of carbon atoms. For example, methyl (meth) acrylate, ethyl (meth) acrylate and butyl (meth) acrylate can be used. [(Meth) acrylic acid means acrylic acid or methacrylic acid. ].
また、水性接着剤組成物には、アミノエチル化アクリル重合体、エチレン−酢酸ビニル樹脂系エマルジョン、アクリル樹脂系エマルジョン、合成ゴム系ラテックス及びウレタン樹脂ディスパージョンのうちの少なくとも1種を配合することもできる。配合量は、不飽和カルボン酸を100質量部とした場合に、60〜120質量部、特に80〜100質量部であることが好ましい。配合量が60〜120質量部であれば、接着強度をより高めることができ、接着時の条件設定の許容幅も同等である。尚、エマルジョン、ラテックス又はディスパージョンであるときは、配合量は、媒体である水と、水に分散し、含有されている樹脂量又はゴム量との合計量、即ち、水と含有されている樹脂量又はゴム量との合計量であるとする。また、これらの重合体、エマルジョン等の添加時期は特に限定されないが、不飽和カルボン酸の重合反応液を熟成させた後、室温にまで冷却させる過程で、又は冷却後に配合することが好ましい。 In addition, at least one of an aminoethylated acrylic polymer, an ethylene-vinyl acetate resin emulsion, an acrylic resin emulsion, a synthetic rubber latex, and a urethane resin dispersion may be added to the aqueous adhesive composition. it can. The blending amount is preferably 60 to 120 parts by mass, particularly 80 to 100 parts by mass, based on 100 parts by mass of the unsaturated carboxylic acid. If the compounding amount is 60 to 120 parts by mass, the adhesive strength can be further enhanced, and the allowable range of setting of conditions at the time of adhesion is also equal. In addition, when it is an emulsion, a latex, or a dispersion, the compounding amount is the total amount of water as a medium and the amount of resin or rubber dispersed in water and contained, that is, water It is assumed that the total amount with the resin amount or the rubber amount. Further, the addition time of these polymers, emulsions and the like is not particularly limited, but it is preferable to add them in the process of cooling to room temperature after ripening the polymerization reaction solution of unsaturated carboxylic acid or after cooling.
水性接着剤組成物には、架橋剤を配合することもできる。架橋剤は不飽和カルボン酸の重合体を架橋させることができる限り、特に限定されない。この架橋剤としては、イソシアネート系化合物、カルボジイミド系化合物、オキサゾリン系化合物及びヒドラジン系化合物から選ばれる少なくとも1種の化合物を用いることができる。架橋剤は、架橋剤配合前の水性接着剤組成物を調製した後、配合することができ、配合量は、架橋剤配合前の水性接着剤組成物を100質量部とした場合に、1〜30質量部、特に3〜20質量部とすることができる。架橋剤の配合量が1〜30質量部であれば、作業性の良い状態で接着強度を更に大きく向上させることができ、耐熱性も向上させることができる。 A crosslinker can also be incorporated into the aqueous adhesive composition. The crosslinking agent is not particularly limited as long as the polymer of unsaturated carboxylic acid can be crosslinked. As the crosslinking agent, at least one compound selected from an isocyanate compound, a carbodiimide compound, an oxazoline compound and a hydrazine compound can be used. The crosslinking agent can be blended after preparing the aqueous adhesive composition before blending the crosslinking agent, and the blending amount is 1 to 10 parts by mass when the aqueous adhesive composition before blending the crosslinking agent is 100 parts by mass. It can be 30 parts by weight, in particular 3 to 20 parts by weight. If the compounding quantity of a crosslinking agent is 1-30 mass parts, adhesive strength can be further greatly improved in the state with favorable workability, and heat resistance can also be improved.
本発明の木質建材は、本発明のラッピング用水性接着剤組成物を用いて製造される。この木質建材は、例えば、中密度繊維板(MDF)等からなる幅木、廻縁、窓枠等の建材として幅広く用いられている木質基材であるラッピング部材と、ポリオレフィンシート等からなり、意匠材となる表面部材とを本発明の水性接着剤組成物を用いて接着することにより製造される。本発明の木質建材では、木質基材と表面部材とは十分な強度で接着され、耐熱性に優れるとともに、従前の溶剤系接着剤等で製造した建材よりも強固に接合された建材を得ることができる。更に、水溶性の重合体を主成分とする接着剤により接合されているにもかかわらず、十分な耐水性をも併せて有する。 The wood building material of the present invention is manufactured using the aqueous adhesive composition for wrapping of the present invention. This wood building material comprises, for example, a lapping member which is a wood base material widely used as a building material such as medium density fiber board (MDF) or the like, lumber edge, window frame, etc., polyolefin sheet etc. It is manufactured by bonding with a surface member to be a material using the aqueous adhesive composition of the present invention. In the wood building material of the present invention, the wood base material and the surface member are bonded with sufficient strength, and they are excellent in heat resistance, and obtain a building material joined more firmly than the building material manufactured with the conventional solvent-based adhesive etc. Can. Furthermore, despite being bonded by a water-soluble polymer-based adhesive, it also has sufficient water resistance.
以下、実施例により本発明を具体的に説明する。
尚、下記の実施例、比較例における「部」は全て「質量部」であり、「%」は全て「質量%」である。また、粘度は30℃で測定した値である。
実施例1
ガラス製重合容器中に、水500部、亜硫酸水素ナトリウム1部を仕込み、均一に分散させた後、攪拌しながらアクリル酸モノマー40部、15%濃度の過硫酸アンモニウム水溶液6部を添加し、80℃まで加温して重合反応を行った。次いで、アクリル酸モノマー190部及び15%濃度の過硫酸アンモニウム水溶液24部を、液温を80℃に保ったまま2時間かけて均一に連続して滴下しながら重合させ、滴下終了から1時間熟成を行ない、不揮発分31.0%、粘度6.5Pa・sの水性接着剤組成物を得た。
尚、この水性接着剤組成物の温度を25℃に調温し、目視で観察したところ、透明であり、重合体が水溶性であることが確認された。
Hereinafter, the present invention will be specifically described by way of examples.
In the following Examples and Comparative Examples, all “parts” are “parts by mass”, and “%” is all “% by mass”. Moreover, the viscosity is a value measured at 30 ° C.
Example 1
In a glass polymerization vessel, 500 parts of water and 1 part of sodium bisulfite are charged and dispersed uniformly, then 40 parts of acrylic acid monomer and 6 parts of 15% aqueous ammonium persulfate solution are added while stirring, The polymerization reaction was carried out by heating to the end. Then, 190 parts of acrylic acid monomer and 24 parts of aqueous solution of ammonium persulfate at 15% concentration are polymerized while continuously dropping uniformly over 2 hours while maintaining the liquid temperature at 80 ° C., and aging is performed for 1 hour from the end of the dropping The aqueous adhesive composition having a nonvolatile content of 31.0% and a viscosity of 6.5 Pa · s was obtained.
The temperature of the aqueous adhesive composition was adjusted to 25 ° C. and visually observed. As a result, it was confirmed that the aqueous adhesive composition was transparent and the polymer was water soluble.
実施例2
ガラス製重合容器中に、水500部、亜硫酸水素ナトリウム3部を仕込み、均一に分散させた後、界面活性剤(花王株式会社製、商品名「エマルゲン147」)5部を添加し、攪拌しながらアクリル酸モノマー40部、15%濃度の重合開始剤(和光純薬工業株式会社製、商品名「V−50」)の水溶液6部を添加し、80℃まで加温して重合反応を行った。次いで、アクリル酸モノマー260部及び上記濃度の上記重合開始剤の水溶液24部を、液温を80℃に保ったまま2時間かけて均一に連続して滴下しながら重合させ、滴下終了から1時間熟成を行ない、不揮発分37.0%、粘度2.6Pa・sの水性接着剤組成物を得た。
Example 2
In a glass polymerization vessel, 500 parts of water and 3 parts of sodium bisulfite are charged and dispersed uniformly, then 5 parts of a surfactant (manufactured by Kao Corp., trade name "Emulgen 147") is added and stirred. Add 40 parts of acrylic acid monomer, 6 parts of aqueous solution of 15% concentration polymerization initiator (Wako Pure Chemical Industries, Ltd., trade name "V-50"), and heat to 80 ° C for polymerization reaction. The Next, 260 parts of an acrylic acid monomer and 24 parts of an aqueous solution of the above-mentioned polymerization initiator with the above concentration are polymerized while being continuously and uniformly dropped over 2 hours while maintaining the liquid temperature at 80 ° C. Aging was performed to obtain an aqueous adhesive composition having a nonvolatile content of 37.0% and a viscosity of 2.6 Pa · s.
実施例3
実施例2の界面活性剤を花王株式会社製、商品名「ラテムルE−118B」に変更した以外は同様にして、不揮発分37.0%、粘度18Pa・s/30℃の水性接着剤組成物を得た。
Example 3
An aqueous adhesive composition having a non-volatile content of 37.0% and a viscosity of 18 Pa · s / 30 ° C., except that the surfactant in Example 2 was changed to Kao Corp., trade name “Latemul E-118B”. I got
実施例4
ガラス製重合容器中に、水500部を仕込み、ポリビニルアルコール(株式会社クラレ製、商品名「205」)15部を加え、攪拌しながら加熱溶解させた。その後、亜硫酸水素ナトリウム3部を仕込み、均一に分散させた後、アクリル酸モノマー40部、15%濃度の過硫酸アンモニウム水溶液6部を添加し、80℃まで加温して重合反応を行った。次いで、アクリル酸モノマー130部及び15%濃度の過硫酸アンモニウム水溶液24部を、液温を80℃に保ったまま2時間かけて均一に連続して滴下しながら重合させ、滴下終了から1時間熟成を行ない、不揮発分30.4%、粘度2.8Pa・sの水性接着剤組成物を得た。
実施例5
ガラス製重合容器中に、水500部を仕込み、実施例4で用いたポリビニルアルコール15部を加え、攪拌しながら加熱溶解させた。その後、亜硫酸水素ナトリウム3部を仕込み、均一に分散させた後、アクリル酸モノマー40部、15%濃度の過硫酸アンモニウム水溶液6部を添加し、80℃まで加温して重合反応を行った。次いで、アクリル酸モノマー130部及び15%濃度の過硫酸アンモニウム水溶液24部を、液温を80℃に保ったまま2時間かけて均一に連続して滴下しながら重合させ、滴下終了から1時間熟成を行なった。その後、冷却しながらアミノエチル化アクリル重合体(日本触媒株式会社製、商品名「ポリメントNK−100PM」)150部と水75部とを添加し、不揮発分31.0%、粘度9.3Pa・sの水性接着剤組成物を得た。
Example 4
In a glass polymerization vessel, 500 parts of water was charged, 15 parts of polyvinyl alcohol (manufactured by Kuraray Co., Ltd., trade name "205") was added, and the mixture was heated and dissolved while stirring. Thereafter, 3 parts of sodium bisulfite was charged and uniformly dispersed, 40 parts of acrylic acid monomer and 6 parts of a 15% aqueous ammonium persulfate solution were added, and the mixture was heated to 80 ° C. to carry out a polymerization reaction. Then, 130 parts of an acrylic acid monomer and 24 parts of a 15% aqueous ammonium persulfate solution are polymerized while being continuously dropped uniformly over 2 hours while maintaining the liquid temperature at 80 ° C., and aging is performed for 1 hour from the end of the dropping The aqueous adhesive composition having a nonvolatile content of 30.4% and a viscosity of 2.8 Pa · s was obtained.
Example 5
In a glass polymerization vessel, 500 parts of water was charged, 15 parts of polyvinyl alcohol used in Example 4 was added, and the mixture was heated and dissolved while stirring. Thereafter, 3 parts of sodium bisulfite was charged and uniformly dispersed, 40 parts of acrylic acid monomer and 6 parts of a 15% aqueous ammonium persulfate solution were added, and the mixture was heated to 80 ° C. to carry out a polymerization reaction. Then, 130 parts of an acrylic acid monomer and 24 parts of a 15% aqueous ammonium persulfate solution are polymerized while being continuously dropped uniformly over 2 hours while maintaining the liquid temperature at 80 ° C., and aging is performed for 1 hour from the end of the dropping I did. Thereafter, while cooling, 150 parts of aminoethylated acrylic polymer (manufactured by Nippon Shokubai Co., Ltd., trade name "Polyment NK-100 PM") and 75 parts of water are added, and the nonvolatile content 31.0%, viscosity 9.3 Pa. An aqueous adhesive composition of s was obtained.
実施例6
実施例1の水性接着剤組成物100部に対し、実施例5で用いたアミノエチル化アクリル重合体5部を添加した以外は同様にして、不揮発分33.0%、粘度10Pa・s/30℃の水性接着剤組成物を得た。
Example 6
A nonvolatile content of 33.0% and a viscosity of 10 Pa · s / 30 are similarly prepared except that 5 parts of the aminoethylated acrylic polymer used in Example 5 is added to 100 parts of the aqueous adhesive composition of Example 1. An aqueous adhesive composition of ° C was obtained.
実施例7
ガラス製重合容器中に、水500部を仕込み、ポリビニルアルコール(株式会社日本酢ビポバール製、商品名「JF−17L」)20部を加え、攪拌しながら加熱溶解させた。その後、亜硫酸水素ナトリウム5部を仕込み、均一に分散させた後、アクリル酸モノマー60部、15%濃度の過硫酸アンモニウム水溶液9部を添加し、80℃まで加温して重合反応を行った。次いで、アクリル酸モノマー240部及び15%濃度の過硫酸アンモニウム水溶液51部を、液温を80℃に保ったまま2時間かけて均一に連続して滴下しながら重合させ、滴下終了から1時間熟成を行なった。その後、冷却し、エチレン−酢酸ビニル樹脂系エマルジョン(接着剤)(住友化学株式会社製、商品名「スミカフレックス400HQ」)90部を添加し、不揮発分34.6%、粘度6.8Pa・s℃の水性接着剤組成物を得た。
Example 7
In a glass polymerization vessel, 500 parts of water was charged, 20 parts of polyvinyl alcohol (manufactured by Nippon Kayaku Bipobar Co., Ltd., trade name "JF-17L") was added, and the mixture was heated and dissolved while stirring. Thereafter, 5 parts of sodium bisulfite was charged and uniformly dispersed, 60 parts of acrylic acid monomer and 9 parts of a 15% aqueous ammonium persulfate solution were added, and the mixture was heated to 80 ° C. to carry out a polymerization reaction. Then, 240 parts of an acrylic acid monomer and 51 parts of a 15% aqueous ammonium persulfate solution are polymerized while continuously dropping uniformly over 2 hours while maintaining the liquid temperature at 80 ° C., and aging is performed for 1 hour from the end of the dropping I did. After cooling, 90 parts of ethylene-vinyl acetate resin emulsion (adhesive agent) (manufactured by Sumitomo Chemical Co., Ltd., trade name "Sumikaflex 400 HQ") is added, and the non-volatile matter 34.6%, viscosity 6.8 Pa · s An aqueous adhesive composition of ° C was obtained.
実施例8
ガラス製重合容器中に、水360部を仕込み、ポリビニルアルコール(電気化学工業株式会社製、「B−33」)20部を加え、攪拌しながら加熱溶解させた。その後、亜硫酸水素ナトリウム5部を仕込み、均一に分散させた後、アクリル酸モノマー50部、15%濃度の実施例2で用いた重合開始剤の水溶液9部を添加し、80℃まで加温して重合反応を行った。次いで、アクリル酸モノマー250部とメタクリル酸モノマー30部の混合液、及び上記濃度の上記重合開始剤の水溶液81部を、液温を80℃に保ったまま2時間かけて均一に連続して滴下しながら重合させ、滴下終了から1時間熟成を行ない、不揮発分44.5%、粘度8.8Pa・sの水性接着剤組成物を得た。
Example 8
In a glass polymerization vessel, 360 parts of water was charged, 20 parts of polyvinyl alcohol ("B-33" manufactured by Denki Kagaku Kogyo Co., Ltd.) was added, and the mixture was heated and dissolved while stirring. Then, 5 parts of sodium bisulfite is charged and uniformly dispersed, 50 parts of acrylic acid monomer and 9 parts of an aqueous solution of the polymerization initiator used in Example 2 at 15% concentration are added and heated to 80 ° C. The polymerization reaction was carried out. Then, a mixed solution of 250 parts of acrylic acid monomer and 30 parts of methacrylic acid monomer, and 81 parts of an aqueous solution of the above-mentioned polymerization initiator with the above concentration are dropped continuously continuously for 2 hours while maintaining the liquid temperature at 80 ° C. The mixture was polymerized while aging was carried out for 1 hour from the end of dropwise addition to obtain an aqueous adhesive composition having a nonvolatile content of 44.5% and a viscosity of 8.8 Pa · s.
実施例9
ガラス製重合容器中に、水470重量部に、亜硫酸水素ナトリウム3部、粘着付与剤(東亞合成株式会社製、商品名「アルフォンUP−1000」)10.5部を仕込み分散させた後、攪拌しながらアクリル酸モノマー50部、15%の過硫酸アンモニウムの水溶液9部を添加して80℃まで加温して重合反応を行った。続いて、アクリル酸モノマー250部およびメタクリル酸モノマー30部の混合液、および15%の過硫酸アンモニウム水溶液81部を、液温80℃に保ったまま2時間かけて均一に連続して滴下しながら重合させ、滴下終了から1時間熟成を行ない、不揮発分37.1%、粘度、20Pa・s/30℃の水性接着剤組成物を得た。
Example 9
In a glass polymerization vessel, 3 parts of sodium hydrogen sulfite and 10.5 parts of a tackifier (trade name "Alfon UP-1000" manufactured by Toagosei Co., Ltd.) are added to and dispersed in 470 parts by weight of water and then stirred. While adding 50 parts of acrylic acid monomer and 9 parts of a 15% aqueous solution of ammonium persulfate, the mixture was heated to 80 ° C. to carry out a polymerization reaction. Subsequently, a mixed solution of 250 parts of acrylic acid monomer and 30 parts of methacrylic acid monomer, and 81 parts of a 15% aqueous solution of ammonium persulfate are continuously and uniformly dropped over 2 hours while maintaining the solution temperature at 80 ° C. The mixture was aged for 1 hour from the end of dropwise addition to obtain an aqueous adhesive composition having a nonvolatile content of 37.1% and a viscosity of 20 Pa · s / 30 ° C.
実施例10
実施例8のメタクリル酸を、メタクリル酸メチルに変更し、熟成の後、水50部を添加した以外は同様にして、不揮発分42.0%、粘度18.6Pa・sの水性接着剤組成物を得た。
Example 10
An aqueous adhesive composition having a nonvolatile content of 42.0% and a viscosity of 18.6 Pa · s in the same manner as in Example 8 except that the methacrylic acid was changed to methyl methacrylate and, after aging, 50 parts of water was added. I got
実施例11
実施例8のメタクリル酸を、アクリル酸ブチルに変更した以外は同様にして、不揮発分44.0%、粘度12.3Pa・sの水性接着剤組成物を得た。
Example 11
An aqueous adhesive composition having a nonvolatile content of 44.0% and a viscosity of 12.3 Pa · s was obtained in the same manner as in Example 8 except that the methacrylic acid was changed to butyl acrylate.
実施例12
実施例2の水性接着剤組成物100部に、架橋剤として、イソシアネート系化合物(住友林業クレスト株式会社製、商品名「H−60」)15部を添加し、接着剤組成物を得た。
Example 12
To 100 parts of the aqueous adhesive composition of Example 2 was added 15 parts of an isocyanate compound (manufactured by Sumitomo Forestry Crest Co., Ltd., trade name "H-60") as a crosslinking agent to obtain an adhesive composition.
実施例13
実施例7の水性接着剤組成物100部に、架橋剤として、実施例12で用いたイソシアネート系化合物15部を添加し、水性接着剤組成物を得た。
Example 13
To 100 parts of the aqueous adhesive composition of Example 7 was added 15 parts of the isocyanate compound used in Example 12 as a crosslinking agent to obtain an aqueous adhesive composition.
実施例14
実施例8の水性接着剤組成物100部に、架橋剤として、実施例12で用いたイソシアネート系化合物10部、及びオキサゾリン系化合物(日本触媒株式会社製、商品名「WS−700」)5部を添加し、水性接着剤組成物を得た。
Example 14
To 100 parts of the aqueous adhesive composition of Example 8, 10 parts of the isocyanate compound used in Example 12 as a crosslinking agent, and 5 parts of an oxazoline compound (trade name "WS-700" manufactured by Nippon Shokubai Co., Ltd.) Were added to obtain an aqueous adhesive composition.
実施例15
実施例8の水性接着剤組成物100部に、架橋剤として、実施例12で用いたイソシアネート系化合物15部、及びヒドラジン系化合物(株式会社日本ファインケム製、商品名「アジピン酸ジヒドラジド」)の5%濃度の水溶液5部を添加し、水性接着剤組成物を得た。
Example 15
In 100 parts of the aqueous adhesive composition of Example 8, 15 parts of the isocyanate compound used in Example 12 as a crosslinking agent, and 5 of a hydrazine compound (trade name "Adipic acid dihydrazide" manufactured by Nippon Finechem Co., Ltd.) 5 parts of a% concentration aqueous solution was added to obtain an aqueous adhesive composition.
実施例16
実施例8の水性接着剤組成物100部に、架橋剤として、実施例12で用いたイソシアネート系化合物10部、及びカルボジイミド系化合物(日清紡ケミカル株式会社製、商品名「カルボジライトV−03A」)5部を添加し、水性接着剤組成物を得た。
Example 16
To 100 parts of the aqueous adhesive composition of Example 8, 10 parts of the isocyanate compound used in Example 12 as a crosslinking agent, and a carbodiimide compound (Nisshinbo Chemical Co., Ltd., trade name "Carbodilite V-03A") 5 Parts were added to obtain an aqueous adhesive composition.
比較例1
有機溶剤としてジクロロメタンを用いた溶剤型2液タイプの市販のラッピング[プロフィールラミネート(異型巻き込み接着)]加工用ウレタン接着剤を使用した。尚、この接着剤は、主剤(溶剤型ウレタン系接着剤)100部に対して、専用硬化剤であるイソシアネート系化合物5部を添加し、均一に攪拌混合した後に使用した。
Comparative Example 1
A commercially available solvent-based, two-component type of commercially available wrapping adhesive for processing a profile (profile wrap-up bonding) using dichloromethane as an organic solvent was used. In addition, this adhesive was used after adding 5 parts of isocyanate type compounds which are exclusive curing agents to 100 parts of main ingredients (solvent type urethane type adhesives), stirring uniformly and mixing it.
比較例2
MDFとポリオレフィンシートとの接着に好適な水性エマルジョン型接着剤(住友林業クレスト株式会社製、商品名「KU−6300」)を使用した。尚、この接着剤は、通常の冷圧接着等で用いた場合に、高い常態ピーリング強度及び耐熱クリープ性能を有する水性エマルジョン型接着剤である。
Comparative example 2
An aqueous emulsion adhesive (manufactured by Sumitomo Forestry Crest Co., Ltd., trade name "KU-6300") suitable for bonding MDF to a polyolefin sheet was used. This adhesive is an aqueous emulsion adhesive having high normal-state peeling strength and heat-resistant creep performance when used in ordinary cold pressure bonding or the like.
以下の接着性を評価するための試験を行った。
[1]ラッピング接着試験(その1)
プライマー処理を施した120μm厚のポリオレフィンシート(大日本印刷株式会社製)に、実施例1〜13及び比較例1、2の接着剤を塗布し、80℃に調温された恒温乾燥機中に20〜40秒間静置して乾燥させた後、直ちに3mm厚のMDFと重ね合わせ、ハンドロールにて1回パスし貼り合わせた。また、貼り合わせた直後に、初期接着力試験を行った。また、同様にして接着を行った試験片を1日養生後、常態ピーリング試験、及び耐熱クリープ試験を行った。
The following tests were conducted to evaluate adhesion.
[1] Lapping adhesion test (1)
The adhesive of Examples 1 to 13 and Comparative Examples 1 and 2 is applied to a 120 μm thick polyolefin sheet (made by Dainippon Printing Co., Ltd.) which has been subjected to primer treatment, and the temperature is controlled at 80 ° C. in a thermostatic dryer. After leaving to stand and dry for 20 to 40 seconds, they were immediately superposed on 3 mm thick MDF and pasted once with a hand roll. Immediately after bonding, an initial adhesion test was conducted. In addition, after curing for 1 day on a test piece adhered in the same manner, a normal peeling test and a heat creep test were conducted.
(1)初期接着力試験
試験体を貼り合わせた直後に、試験片の幅が25mmなるようにポリオレフィンシートに切り込みを入れて10mm捲り、23℃、50%RHの雰囲気下において、オートグラフ(株式会社島津製作所製)を使用して、剥離速度200mm/minで90°はく離強度を測定した。
(1) Initial Adhesion Test Immediately after bonding the test pieces, the polyolefin sheet is cut so that the width of the test piece is 25 mm, and it is turned around 10 mm, under an atmosphere of 23 ° C., 50% RH, autograph (stock The 90 ° peel strength was measured at a peeling speed of 200 mm / min using Shimadzu Corporation).
(2)粘着幅試験
上記(1)の接着の過程において、80℃に調温された恒温乾燥機中で20秒、30秒、40秒放置後に、それぞれ指触で粘着性を確認した。全ての条件において強い粘着により指から離れ難くなるものを「〇」、粘着が弱く容易に指から剥離するもの若しくは指に粘着しないもの、又は強い粘着性が発現される条件がある一部の乾燥条件に限られるものを「×」とした。
(2) Adhesion width test In the adhesion process of the above (1), after being left for 20 seconds, 30 seconds, and 40 seconds in a thermostatic dryer adjusted to 80 ° C., the adhesion was confirmed by finger touch. In all conditions, those that become difficult to separate from the finger due to strong adhesion are "○", those with weak adhesion that are easily peeled off from the finger or those that do not adhere to the finger, or some dry conditions that exhibit strong adhesion The thing limited to conditions was made into "x."
(3)常態ピーリング強度
試験片を25mm幅に切断し、23℃、50%RHの雰囲気下において、オートグラフ(株式会社島津製作所製)を使用して、剥離速度200mm/minで180°剥離強度を測定した。また、材破率(%)を測定した。
(3) Normal State Peeling Strength The test piece was cut into 25 mm width and 180 ° peeling strength at a peeling speed of 200 mm / min using an autograph (made by Shimadzu Corporation) under an atmosphere of 23 ° C. and 50% RH. Was measured. Also, the material breakage rate (%) was measured.
(4)80℃耐熱クリープ試験
試験片を25mm幅に切断し、試験片のポリオレフィンシートの一端に500gの荷重をかけ、80℃に調温された恒温乾燥機中に24時間静置した後、ポリオレフィンシートの剥離長さ(mm)を測定した。
試験結果を表1に記載する。
(4) 80 ° C. heat resistance creep test A test piece is cut to a width of 25 mm, a load of 500 g is applied to one end of the polyolefin sheet of the test piece, and left for 24 hours in a thermostatic dryer thermostated at 80 ° C. The peel length (mm) of the polyolefin sheet was measured.
The test results are listed in Table 1.
[2]ラッピング接着試験(その2)
水性である実施例10、11及び比較例2の接着剤と、溶剤系である比較例1の接着剤を使用して、ラッピングマシン(プロフィールラミネーターマシン)を使用して、ラッピング建材(木質建材)の作製を行った。
具体的には、丸仲商事株式会社製の、溶剤系接着剤用のラッピングマシンを使用して、プライマー処理を施した150μm厚のポリオレフィンシート(大日本印刷株式会社製)に、実施例10、11及び比較例2の接着剤の場合は、塗布厚さが0.2mmなるように、比較例1の接着剤の場合は、塗布厚さが0.35mmとなるように、ラッピングマシンに付随の開閉式アプリケーターにて接着剤を塗布した。また、塗布後、直ちに40〜45℃に調温された乾燥路を通過させ、次いで、溝等を含む角度90度の屈折箇所を12箇所設けたMDFにロールを各部に当てながら貼り合わせを行った。その後、接合させた木質建材について、常態ピーリング試験、耐熱クリープ試験、2類浸漬はく離試験を行った。更に、ラッピングマシンでの作業性に関して、塗布工程の作業性試験、接着作業後の水洗性試験を行った。
[2] Lapping adhesion test (Part 2)
Lapping building materials (wood building materials) using a lapping machine (profile laminator machine) using the adhesives of Examples 10 and 11 and Comparative Example 2 which are aqueous and the adhesive of Comparative Example 1 which is solvent based Was made.
Specifically, Example 10 was applied to a 150 μm thick polyolefin sheet (made by Dainippon Printing Co., Ltd.) which was subjected to primer treatment using a lapping machine for solvent-based adhesive manufactured by Marunaka Shoji Co., Ltd. In the case of the adhesive of 11 and Comparative Example 2, the coating thickness is 0.2 mm, and in the case of the adhesive of Comparative Example 1, the coating thickness is 0.35 mm. The adhesive was applied with a retractable applicator. After application, immediately pass through a drying path adjusted to 40-45 ° C, and then bond the MDF with 12 refracted points with an angle of 90 degrees including grooves etc. while applying the roll to each part The Thereafter, the normal wood peeling test, the heat creep test, and the two-class immersion test were performed on the joined wood building materials. Furthermore, with regard to the workability with a lapping machine, the workability test of the coating process and the water washability test after bonding were conducted.
(1)常態ピーリング試験及び(2)耐熱クリープ試験は、前記[1]ラッピング接着試験(その1)と同様にして行った。
(3)2類浸漬剥離試験
木質建材を、そのままの形態で長さ75mmなるように切削し、70℃の温水中に2時間浸漬した。その後、60℃に調温された恒温乾燥機中で3時間乾燥し、剥離の有無を目視で確認した。
(4)塗布工程の作業性試験
4時間の間、ラインを稼働させつつアプリケーターの開閉を20回行い、開閉がスムーズに行えるかどうかを確認した。スムーズに開閉ができて不具合を生じなかったものを「〇」、次第に開閉の動きが悪化し、最終的には開閉できなくなったものを「×」とした。
(5)水洗性試験
使用開始から4時間経過後、アプリケーターを水で洗浄した。容易に洗浄できたものを「〇」、洗浄が困難であったものを「×」とした。尚、比較例1の接着剤は溶剤系であるため、水での洗浄は不可能であり、洗浄には多量の有機溶剤を必要とした。
試験の結果を表3に記載する。
The (1) normal-state peeling test and the (2) heat-resistant creep test were performed in the same manner as the above-mentioned [1] lapping adhesion test (Part 1).
(3) Class 2 immersion peeling test The wood building material was cut so as to be 75 mm in length in the same form, and was immersed in hot water at 70 ° C. for 2 hours. Thereafter, it was dried for 3 hours in a constant temperature dryer adjusted to 60 ° C., and the presence or absence of peeling was visually confirmed.
(4) Operability test of coating process The applicator was opened and closed 20 times while operating the line for 4 hours to check whether the opening and closing could be performed smoothly. The ones that could be opened and closed smoothly without problems were rated as "o", and the movement of opening and closing gradually worsened, and those that could not be opened and closed eventually were designated as "x".
(5) Water washability test The applicator was washed with water after 4 hours from the start of use. Those that could be easily cleaned were rated as "o", and those that were difficult to clean were designated as "x". In addition, since the adhesive of Comparative Example 1 was a solvent type, washing with water was impossible, and a large amount of organic solvent was required for washing.
The results of the test are described in Table 3.
以上の試験結果によれば、アクリル酸等の不飽和カルボン酸を水媒体中で重合してなる水溶性の重合体を主成分とする水性接着剤組成物は、木質基材の接着において、有機溶剤を用いた溶剤型接着剤と同等以上の優れた接着性能を有していることが分かる。また、MDF等の木質基材とポリオレフィンシートとの接着においては、溶剤系ウレタン接着剤より優れた接着強度を有し、高い材破率が発現される接着剤であり、且つ耐熱性、耐水性ともに良好な接着剤であるため、木質建材の製造に好適な接着剤であると言える。更に、水溶性の重合体を主成分とする非エマルジョン型の接着剤であるため、急速に乾燥が進むことがなく、ドライラミネートする接着工程において、粘着幅が広く優れている。 According to the above test results, the aqueous adhesive composition containing as a main component a water-soluble polymer formed by polymerizing an unsaturated carboxylic acid such as acrylic acid in an aqueous medium is an organic adhesive in adhesion of a wood substrate. It can be seen that it has the same or better adhesion performance as a solvent-based solvent-based adhesive. In addition, in the adhesion between a wood base such as MDF and a polyolefin sheet, it is an adhesive which has an adhesive strength superior to that of a solvent-based urethane adhesive and in which a high material breakage rate is expressed, and which is heat resistant and water resistant Since both are good adhesives, it can be said that they are suitable adhesives for manufacture of a wood building material. Furthermore, since the adhesive is a non-emulsion type adhesive comprising a water-soluble polymer as a main component, the drying does not proceed rapidly, and the adhesion width is excellent widely in the adhesion step of dry laminating.
また、溶剤型接着剤仕様のラッピングマシンをそのまま用いることができるため、ポリウレタン系ホットメルト接着剤等のような多額な設備投資を伴わずに、低コストの製造設備で接着剤を使用することができる。更に、水溶性の重合体を主成分とする非エマルジョン型の接着剤とすることで、接着剤の乾燥や反応が緩やかに進み、塗工するアプリケーション部分での不具合が生じず、接着剤が塗工容器部分等に強く付着するようなこともないため、水洗性にも優れている。また、発ガン性のリスクが大きい有機溶剤、特に揮発性の高い有機溶剤を含有しないため、木質建材製造時の作業環境が著しく改善されるとともに、製造された木質建材は、VOC等の発生が抑えられ、人体及び環境に及ぼす悪影響が極めて少ないという優位点もある。 In addition, since a lapping machine with a solvent-based adhesive specification can be used as it is, the adhesive can be used in a low-cost manufacturing facility without a large investment in facilities such as a polyurethane-based hot melt adhesive and the like. it can. Furthermore, by using a non-emulsion type adhesive composed mainly of a water-soluble polymer, drying and reaction of the adhesive proceed gradually, and problems in the application part to be coated do not occur, and the adhesive is coated Since it does not adhere strongly to a work container part etc., it is excellent also in water washing nature. In addition, since it does not contain an organic solvent that has a large risk of carcinogenicity, especially a highly volatile organic solvent, the working environment at the time of producing wood building materials is significantly improved, and the produced wood building materials generate VOC and the like. It has the advantage of being suppressed and having very little adverse impact on the human body and the environment.
本発明は、幅木、廻縁、窓枠等の建材として幅広く用いられているラッピング部材の接着の技術分野において利用することができる。また、MDF等の木質基材をラッピング接着してなる木質建材の技術分野において利用することができる。 The present invention can be used in the technical field of bonding of wrapping members widely used as building materials such as baseboards, edges and windows. In addition, it can be used in the technical field of wood building materials formed by wrapping and bonding a wood base such as MDF.
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JP2014266129A Active JP6425999B2 (en) | 2014-12-26 | 2014-12-26 | Aqueous adhesive composition for wrapping and wood building material using the same |
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JP2021107149A (en) * | 2019-12-27 | 2021-07-29 | ダウ・東レ株式会社 | Laminate and electronic part formed of the same |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
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JPH0890508A (en) * | 1994-09-29 | 1996-04-09 | Mitsui Toatsu Chem Inc | Manufacture of veneer decorative plate |
JPH09157626A (en) * | 1995-12-07 | 1997-06-17 | Toppan Printing Co Ltd | Adhesive for lapping and lapping member using the same adhesive |
JP2001277445A (en) * | 2000-03-30 | 2001-10-09 | Idemitsu Petrochem Co Ltd | Polyolefin sheet, and display sheet, packaging sheet, transparent sheet for recording, decorative sheet, and sheet for emblem using it |
JP2001311066A (en) * | 2000-04-27 | 2001-11-09 | Showa Highpolymer Co Ltd | Water-resistant adhesive for laminated wood |
JP2003292918A (en) * | 2002-04-01 | 2003-10-15 | Aron Ever-Grip Ltd | Adhesive composition for lapping use |
JP2005179471A (en) * | 2003-12-18 | 2005-07-07 | Chuo Rika Kogyo Corp | Aqueous emulsion-based adhesive |
JP5118306B2 (en) * | 2006-02-10 | 2013-01-16 | 旭ファイバーグラス株式会社 | Aqueous binder for heat insulating sound absorbing material for inorganic fiber and heat insulating sound absorbing material for inorganic fiber |
JP5283349B2 (en) * | 2007-04-18 | 2013-09-04 | アイカ工業株式会社 | Water-based adhesive composition |
JP6091860B2 (en) * | 2011-11-29 | 2017-03-08 | 三洋化成工業株式会社 | Aqueous binder for mineral fiber |
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2014
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