JPH0234994B2 - TAKOSHITSUZAINOSEKISOSEIKEIKAKOHO - Google Patents
TAKOSHITSUZAINOSEKISOSEIKEIKAKOHOInfo
- Publication number
- JPH0234994B2 JPH0234994B2 JP15041781A JP15041781A JPH0234994B2 JP H0234994 B2 JPH0234994 B2 JP H0234994B2 JP 15041781 A JP15041781 A JP 15041781A JP 15041781 A JP15041781 A JP 15041781A JP H0234994 B2 JPH0234994 B2 JP H0234994B2
- Authority
- JP
- Japan
- Prior art keywords
- water
- urethane prepolymer
- curing agent
- seconds
- molding method
- 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
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 40
- 239000003795 chemical substances by application Substances 0.000 claims description 24
- -1 ether polyol Chemical class 0.000 claims description 21
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 15
- 229920001281 polyalkylene Polymers 0.000 claims description 15
- 239000011148 porous material Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 229920005862 polyol Polymers 0.000 claims description 14
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 238000000465 moulding Methods 0.000 claims description 8
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 7
- 238000010030 laminating Methods 0.000 claims description 6
- 229920001228 polyisocyanate Polymers 0.000 claims description 6
- 239000005056 polyisocyanate Substances 0.000 claims description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N aminothiocarboxamide Natural products NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 5
- 239000000123 paper Substances 0.000 claims description 5
- 239000010454 slate Substances 0.000 claims description 5
- 239000004202 carbamide Substances 0.000 claims description 4
- 239000007809 chemical reaction catalyst Substances 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 3
- 150000001413 amino acids Chemical class 0.000 claims description 3
- 150000007514 bases Chemical class 0.000 claims description 3
- 239000004744 fabric Substances 0.000 claims description 3
- 239000002984 plastic foam Substances 0.000 claims description 3
- 239000002023 wood Substances 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 239000002075 main ingredient Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 description 27
- 239000000853 adhesive Substances 0.000 description 15
- 230000001070 adhesive effect Effects 0.000 description 15
- 238000003825 pressing Methods 0.000 description 14
- 239000000463 material Substances 0.000 description 13
- 239000006260 foam Substances 0.000 description 9
- 238000002156 mixing Methods 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 230000001988 toxicity Effects 0.000 description 3
- 231100000419 toxicity Toxicity 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 239000011120 plywood Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- JUXXCHAGQCBNTI-UHFFFAOYSA-N 1-n,1-n,2-n,2-n-tetramethylpropane-1,2-diamine Chemical compound CN(C)C(C)CN(C)C JUXXCHAGQCBNTI-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- 239000004831 Hot glue Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004823 Reactive adhesive Substances 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000012972 dimethylethanolamine Substances 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000002648 laminated material Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Adhesives Or Adhesive Processes (AREA)
- Laminated Bodies (AREA)
Description
本発明は少なくとも一方が多孔質材である被着
体の積層成形加工法に関する。
現在、木材、スレート、紙、布、フエルトおよ
びプラスチツクフオーム等の多孔質材どおしまた
はかかる多孔質材と金属、プラスチツクシートの
ような非多孔質材とを積層成形加工するに種々の
接着剤が使用されているが、近年、特に工場生産
ラインにおいては、脱溶剤化により安全衛生の向
上、環境汚染の防止を図るとともに省資源、熱利
用に対する省エネルギー化および設備合理化を図
るため、熱硬化型接着剤、２液反応型接着剤、熱
可塑性樹脂ホツトメルト型接着剤、溶剤揮散型接
着剤に代え、水性接着剤が使用されるに至つてい
る。
しかしながら、水性接着剤は一般に接着スピー
ドに難点があり、生産性の向上を図るとともに製
品の品質保証および信頼性の向上を図るには充分
なものとはいいがたい。
そこで、本発明者らは、上記社会的要請に合致
する積層成形加工法を提供すべく、鋭意研究を重
ねた結果、少なくとも一方が多孔質材である被着
体を積層成形する場合、従来接着剤用途に展開さ
れていなかつた水溶性ウレタンプレポリマー、特
にそのポリアルキレンエーテルポリオールのエチ
レンオキサイドモル比を特定化したものを主剤と
し、水を主成分とする硬化剤を用いると、接着作
業スピードがきわめて速く、生産性向上に寄与で
きること、さらにかかる主剤と硬化剤を同時噴霧
することにより作業性がより一層向上しうること
を見い出し、本発明を完成するに至つた。
すなわち、本発明は少なくとも一方が多孔質材
である被着体を積層成形するにあたり、被着体の
一方または双方の接合面に水溶性ウレタンプレポ
リマーからなる主剤と水を主成分とする硬化剤を
空中混合にて同時噴霧した後、両者を重ね合せ、
押圧接合することから成り、上記水溶性ウレタン
プレポリマーが、エチレンオキサイドのモル比30
〜90％のポリアルキレンエーテルポリオールと過
剰のポリイソシアネートとの反応生成物であるこ
とを特徴とする多孔質材の積層成形加工法を提供
することを目的とする。
多孔質材としては木材、スレート、紙、布、フ
エルトまたはプラスチツクフオーム等の気孔を有
するものであればよい。他方の被着体は多孔質材
であつてもよいが、金属、プラスチツクシート等
の非多孔質材であつてもよい。
本発明において用いる水溶性ウレタンプレポリ
マーは通常接着剤として用いられるウレタン系接
着剤と同様、硬軟物性の設計が容易であり、耐
熱、耐久性に富み、かつ無溶剤化も容易である利
点を有するが、水との相溶性に富み、水を主成分
とする硬化剤を用いて優れた接着速度が発揮され
る特徴を有する点で従来のウレタン系接着剤と区
別される。したがつて、通常ポリオール、アミン
等を硬化剤として用いる二液硬化型の場合のよう
に、二液混合、硬化速度、毒性等に難点はなく、
また、空気中の湿気あるいは被着体中の含有水分
による硬化を利用する一液硬化型の場合のような
硬化速度、温湿気依存性および貯蔵安定性等に問
題もない。
かかる水溶性ウレタンプレポリマーは特定のポ
リアルキレンエーテルポリオールと過剰のポリイ
ソシアネートと反応させて製造されるが、ポリア
ルキレンエーテルポリオール中のエチレンオキサ
イドのモル比は30〜90％である。かかるポリアル
キレンエーテルポリオールは通常、２個以上のヒ
ドロキシル基を含む化合物に分子中エチレンオキ
サイドをモル比で30〜90％含むように付加して製
造される。たとえば２個以上の活性水素を含む化
合物として、エチレングリコール、プロピレング
リコール、ジプロピレングリコール、グリセリ
ン、トリメチロールプロパン、ペンタエリストー
ル、ソルビトール、シヨ糖等を用い、公知の方法
でエチレンオキサイドまたは他のプロピレンオキ
サイド、ブチレンオキサイド等のアルキレンオキ
サイドを付加反応あるいは共付加反応させて製造
される。親水性、作業性から考えてポリアルキレ
ンエーテルポリオールの分子量は1000〜20000、
特に1000〜5000の範囲のものが好ましく、また、
ポリアルキレンエーテルポリオールのうち、ポリ
アルキレンエーテルジオールが望ましい。ポリイ
ソシアネートとしては、通常のウレタンプレポリ
マーの製造に用いられるものが使用でき、例え
ば、トルエンジイソシアネートおよびジフエニル
メタン−４，4′−ジイソシアネートの精製品及び
粗製品等が使用される。特に、臭気、作業性、硬
化性、接着性、毒性等の物性およびコストの点よ
り、ジフエニルメタン−４，4′−ジイソシアネー
トが適する。
ポリイソシアネートに対するポリアルキレンエ
ーテルポリオールの使用割合は、NCO／OH＝
3.0〜6.0当量の範囲に応じて決定されてよく、得
られるウレタンプリポリマーは残留活性イソシア
ネート基４〜13％、粘度3000〜10000cpsのものが
反応性、作業性、性能等の点で好ましい。もちろ
ん、かかるウレタンプレポリマーには充填剤、老
化防止剤、着色顔料、反応触媒、密着付与剤、溶
剤、可塑剤が必要に応じて配合されてよい。
本発明で用いられる水を主成分とする硬化剤と
は、ウレタンプレポリマーの活性イソシアネート
基と反応する活性水素をもつ水を主成分とし、各
種の反応触媒を添加して噴霧可能な水溶液状態に
するのが好ましい。この触媒には有機アミン類の
トリエチレンジアミン、トリエチルアミン、ジメ
チルエタノールアミン、テトラメチルプロピレン
ジアミン、テトラメチレントリアミン、さらにホ
ウ砂、水酸化ナトリウムなどの無機塩基性化合
物、尿素、チオ尿素、アミノ酸塩または塩基性ア
ミノ酸など多数のものが使用できるが、毒性、臭
気、水溶性、経済性などの観点から特に無機塩基
性化合物、尿素、チオ尿素、アミノ酸塩、塩基性
アミノ酸の１種または２種以上の混合物を用いる
のが好ましい。硬化剤には必要に応じ、密着付与
剤、染顔料、充填剤、界面活性剤などが添加され
てよい。特に、界面活性剤の添加により、ウレタ
ンプレポリマーに対する相溶性が改善され、染顔
料の添加によつて噴霧面の混合、塗付量などの確
認が可能である。また、充填剤および水溶性樹脂
の添加により、多孔質へのしみ込み防止・低コス
ト化が図れる。
以下、本発明を具体例に基づき、さらに詳細に
説明する。
製造例 １
（ウレタンプレポリマーの製造）
平均分子量3000のポリアルキレンエーテルジオ
ール（商品名アデカポリエーテルPR3007、旭電
化(株)製、エチレンオキサイド70％モル比）200重
量部に対しジフエニルメタン−４，4′−ジイソシ
アネート100重量部（NCO／OH比＝6.0）を加熱
保温用ジヤケツトをもつ攪拌可能な容器に添加、
混合し、80℃昇温下で３時間反応させ、残留活性
イソシアネート基が9.33％、粘度が4000cpsの水
溶性ウレタンプレポリマーを得る。
製造例 ２〜８
（ウレタンプレポリマーの製造）
下記第１表に示すポリアルキレンエーテルポリ
オールに対し、下記第１表に示すジイソシアネー
トを用い、製造例１と同様にして下記第１表に示
す水溶性ウレタンプレポリマーを得る。
The present invention relates to a method for laminating and processing adherends, at least one of which is a porous material. Currently, various adhesives are used for laminating and forming porous materials such as wood, slate, paper, cloth, felt, and plastic foam, or for laminating and forming such porous materials and non-porous materials such as metal and plastic sheets. However, in recent years, especially in factory production lines, thermosetting type Water-based adhesives have come to be used in place of adhesives, two-component reactive adhesives, thermoplastic resin hot melt adhesives, and solvent volatilization adhesives. However, water-based adhesives generally have a drawback in adhesion speed, and cannot be said to be sufficient for improving productivity, as well as ensuring product quality and improving reliability. Therefore, the present inventors have conducted extensive research in order to provide a laminated molding processing method that meets the above social demands, and have found that when laminating an adherend in which at least one side is a porous material, conventional adhesive bonding Adhesive work speed can be increased by using water-soluble urethane prepolymers that have not yet been developed as adhesives, especially polyalkylene ether polyols with specific ethylene oxide molar ratios, and using water-based curing agents. The present inventors have now completed the present invention by discovering that the method can contribute to improved productivity extremely quickly, and that workability can be further improved by simultaneously spraying the main agent and curing agent. That is, in laminating and molding an adherend in which at least one of the adherends is a porous material, the present invention provides a base material made of a water-soluble urethane prepolymer and a curing agent mainly composed of water on one or both bonding surfaces of the adherend. After mixing in the air and spraying at the same time, overlap the two,
The water-soluble urethane prepolymer has a molar ratio of ethylene oxide of 30.
The object of the present invention is to provide a method for laminated molding of a porous material characterized by being a reaction product of ~90% polyalkylene ether polyol and an excess of polyisocyanate. The porous material may be any material having pores such as wood, slate, paper, cloth, felt or plastic foam. The other adherend may be a porous material, but may also be a non-porous material such as metal or plastic sheet. The water-soluble urethane prepolymer used in the present invention has the advantages of being easily designed to have hard and soft properties, being heat resistant and durable, and being easily made solvent-free, similar to urethane adhesives commonly used as adhesives. However, it is distinguished from conventional urethane adhesives in that it is highly compatible with water and exhibits excellent adhesion speed using a curing agent whose main component is water. Therefore, there are no problems with two-component mixing, curing speed, toxicity, etc., as in the case of two-component curing types that normally use polyols, amines, etc. as curing agents.
In addition, there are no problems with curing speed, temperature/humidity dependence, storage stability, etc., as in the case of a one-component curing type that utilizes curing by moisture in the air or moisture contained in the adherend. Such water-soluble urethane prepolymers are produced by reacting specific polyalkylene ether polyols with excess polyisocyanate, and the molar ratio of ethylene oxide in the polyalkylene ether polyols is from 30 to 90%. Such polyalkylene ether polyols are usually produced by adding ethylene oxide to a compound containing two or more hydroxyl groups in a molar ratio of 30 to 90%. For example, using ethylene glycol, propylene glycol, dipropylene glycol, glycerin, trimethylolpropane, pentaerythol, sorbitol, sucrose, etc. as a compound containing two or more active hydrogen atoms, ethylene oxide or other propylene It is produced by addition reaction or co-addition reaction of oxide, alkylene oxide such as butylene oxide. Considering hydrophilicity and workability, the molecular weight of polyalkylene ether polyol is 1000 to 20000,
In particular, those in the range of 1000 to 5000 are preferable, and
Among polyalkylene ether polyols, polyalkylene ether diols are preferred. As the polyisocyanate, those used in the production of ordinary urethane prepolymers can be used, such as purified products and crude products of toluene diisocyanate and diphenylmethane-4,4'-diisocyanate. Particularly, diphenylmethane-4,4'-diisocyanate is suitable from the viewpoint of physical properties such as odor, workability, curability, adhesiveness, and toxicity, and cost. The ratio of polyalkylene ether polyol to polyisocyanate is NCO/OH=
It may be determined depending on the range of 3.0 to 6.0 equivalents, and the urethane prepolymer obtained preferably has 4 to 13% of residual active isocyanate groups and a viscosity of 3,000 to 10,000 cps in terms of reactivity, workability, performance, etc. Of course, fillers, anti-aging agents, coloring pigments, reaction catalysts, adhesion agents, solvents, and plasticizers may be added to the urethane prepolymer as necessary. The water-based curing agent used in the present invention is mainly water containing active hydrogen that reacts with the active isocyanate groups of the urethane prepolymer, and is made into a sprayable aqueous solution by adding various reaction catalysts. It is preferable to do so. This catalyst includes organic amines such as triethylenediamine, triethylamine, dimethylethanolamine, tetramethylpropylenediamine, and tetramethylenetriamine, as well as inorganic basic compounds such as borax and sodium hydroxide, urea, thiourea, amino acid salts, and basic A large number of amino acids can be used, but one or a mixture of two or more of inorganic basic compounds, urea, thiourea, amino acid salts, and basic amino acids are particularly preferred from the viewpoint of toxicity, odor, water solubility, economic efficiency, etc. It is preferable to use Adhesion promoters, dyes and pigments, fillers, surfactants, etc. may be added to the curing agent as necessary. In particular, the addition of a surfactant improves the compatibility with the urethane prepolymer, and the addition of dyes and pigments makes it possible to check the mixing on the spray surface, the amount of coating, etc. Furthermore, by adding a filler and a water-soluble resin, it is possible to prevent penetration into porous materials and reduce costs. Hereinafter, the present invention will be explained in more detail based on specific examples. Production Example 1 (Production of urethane prepolymer) Diphenylmethane-4,4 to 200 parts by weight of polyalkylene ether diol with an average molecular weight of 3000 (trade name ADEKA Polyether PR3007, manufactured by Asahi Denka Co., Ltd., ethylene oxide 70% molar ratio) 100 parts by weight of diisocyanate (NCO/OH ratio = 6.0) was added to a stirrable container with a heating jacket,
The mixture was mixed and reacted for 3 hours at an elevated temperature of 80°C to obtain a water-soluble urethane prepolymer having a residual active isocyanate group of 9.33% and a viscosity of 4000 cps. Production Examples 2 to 8 (Production of urethane prepolymers) Polyalkylene ether polyols shown in Table 1 below were prepared in the same manner as in Production Example 1 using diisocyanates shown in Table 1 below. Obtain a urethane prepolymer.
【表】
＊１ 旭電化(株)製、＊２ 三洋化成(株)製
製造例 ９〜14
（水を主成分とする硬化剤）
下記第２表に示す成分を所定の割合で水に溶解
し、ウレタンプレポリマーの反応触媒として用い
る硬化剤を得る。[Table] *1 Manufactured by Asahi Denka Co., Ltd. *2 Manufactured by Sanyo Kasei Co., Ltd. Manufacturing examples 9 to 14 (Curing agent whose main component is water) Dissolve the ingredients shown in Table 2 below in water at the specified ratio. Then, a curing agent used as a reaction catalyst for urethane prepolymer is obtained.
【表】【table】
【表】
実施例 １
ウレタンフオーム（寸法300×300×10mm）のい
ずれか一方に製造例１で得た水溶性ウレタンプレ
ポリマー70ｇ／m2および製造例10で得た水を主成
分とする硬化剤35ｇ／m2を同時に噴霧混合して塗
付し、これに他方のウレタンフオームを貼り合
せ、0.2Kg／cm2の圧締圧力で押圧して積層成形加
工材を得る。この積層材の圧締後室温（25℃）で
60秒放置したときの180度剥離強度は0.5Kg／in.で
あつて、90秒後では１Kg／in.でウレタンフオー
ムが材破した。
実施例 ２
他方のウレタンフオームを不織布に代える以外
は実施例１と同様にして積層成形加工材を得る。
圧締後60秒後の180゜剥離強度0.5Kg／in.90秒後
１Kg／in.でウレタンフオームは材破
実施例 ３
スレート（寸法300×300×３mm）に製造例２で
得られる水溶性ウレタンプレポリマー70ｇ／m2お
よび製造例10で得られる硬化剤35ｇ／m2を同時に
噴霧し空中混合にて塗付し、20秒放置した後、化
粧紙を貼り合せてローラーで押圧し、次いでプレ
スで圧締圧力２Kg／cm2で押圧し、積層成形加工材
を得る。圧締後30秒後の180度剥離強度は0.5Kg／
in、60秒後では1.0Kg／inであり、90秒後では1.5
〜2.0Kg／inで化粧紙の材破がみられた。
実施例 ４
合板（寸法300×300×５mm）に製造例３で得ら
れる水溶性ウレタンプレポリマー150ｇ／m2およ
び製造例10で得られる硬化剤75ｇ／m2を同時に噴
霧混合して塗付し、空気中で20秒放置後スレート
（寸法300×300×３mm）を貼り合せ、プレスによ
り圧締圧力２Kg／cm2で押圧し積層成形加工材を得
る。
圧締後室温で60秒経過した時の引張り剪断力は
５Kg／cm2であり、90秒後ではスレートが材破する
接着強度が得られた。
実施例 ５
木板（寸法300×300×９mm）のいずれか一方に
製造例３で得られる水溶性ウレタンプレポリマー
100ｇ／m2および製造例10で得られる硬化剤50
ｇ／m2を同時に噴霧混合して塗付し、空気中で20
秒放置後、これをもう一枚の木板と貼り合せ、プ
レスにより２Kg／cm2で押圧し、積層成形加工材を
得る。
圧締後室温で60秒経過後の引張剪断力は５Kg／
cm2、90秒後では10Kg／cm2、３分後ではほぼ最終強
度に近い25Kg／cm2であつた。
実施例 ６
ウレタンフオーム（寸法300×300×10mm）に製
造例２で得られる水溶性ウレタンプレポリマー
100ｇ／m2および製造例10で得られる硬化剤50
ｇ／m2を同時に噴霧混合して塗付し、ただちにこ
れをバツクコート鋼板（寸法300×300×0.8mm）
の塗面に貼り合せ、ローラで0.1Kg／cm2の下に押
圧して積層成形加工材を得る。
圧締後室温で60秒経過したときの180度剥離強
度は0.8Kg／in.であり、90秒後ではウレタンフオ
ームが材破する接着強度となつていた。
実施例 ７
実施例６において、水溶性ウレタンプレポリマ
ーとして製造例１で得られたもの、硬化剤として
製造例10で得られたものを用いる以外は同様にし
て積層成形加工材を得る。
圧締後の180度剥離試験結果は実施例６と同等
であつた。
実施例 ８
合板（寸法300×300×５mm）に製造例２で得ら
れる水溶性ウレタンプレポリマー70ｇ／m2および
製造例10で得られる硬化剤35ｇ／m2を同時に噴霧
混合して塗付し、空気中で20秒間放置し、これに
PVCシート（寸法300×300×２mm）を貼り合せ、
ローラで押圧した後、プレスにより圧締圧力２
Kg／cm2で押圧して積層成形加工材を得る。
圧締後室温で60秒経過したときの180度剥離強
度は0.5〜1.0Kg／in、120秒後では1.0〜1.5Kg／in
であり、水分乾燥後の最終強度は2.5Kg／inであ
つた。
実施例 ９
塗装鋼板（寸法300×300×0.8mm）に製造例３
で得られる水溶性ウレタンプレポリマー100ｇ／
m2および製造例10で得られる硬化剤50ｇ／m2を同
時に噴霧混合して塗付し、ただちにこれにハニカ
ムボード（寸法300×300×30mm）を貼り合せ、プ
レスにより圧締圧力0.5Kg／cm2で押圧して積層成
形加工材を得る。
圧締後室温で60秒経過すると、接着剤はほぼ硬
化しており、積層成形加工材は持ち運びが可能で
ある。５分後では、手剥離による引き裂き試験に
おいてハニカムボードが材破するに至つた。
実施例 10〜23
実施例１に記載の方法に従い、第３表に示す被
着材を種々の水溶性ウレタンプレポリマー（主
剤）と硬化剤を用いて積層成形加工を行なつた。
結果を第１表に併記する。[Table] Example 1 Curing of 70 g/m 2 of the water-soluble urethane prepolymer obtained in Production Example 1 and water obtained in Production Example 10 as main components on either side of urethane foam (dimensions 300 x 300 x 10 mm) At the same time, 35 g/m 2 of the agent was spray mixed and applied, and the other urethane foam was bonded to this and pressed with a pressing pressure of 0.2 Kg/cm 2 to obtain a laminated molded material. After pressing this laminated material, at room temperature (25℃)
The 180 degree peel strength when left for 60 seconds was 0.5 kg/in., and the urethane foam broke at 1 kg/in. after 90 seconds. Example 2 A laminated molded material was obtained in the same manner as in Example 1 except that the other urethane foam was replaced with a nonwoven fabric. 180° peel strength 0.5 kg/in. after 60 seconds after pressing. Urethane foam breaks at 1 kg/in. after 90 seconds Example 3 Water-soluble slate obtained in Production Example 2 Urethane prepolymer 70 g/m 2 and curing agent obtained in Production Example 10 35 g/m 2 were simultaneously sprayed and applied by mixing in the air, left for 20 seconds, decorative paper was pasted and pressed with a roller, and then Press with a press at a compression pressure of 2 kg/cm 2 to obtain a laminated molded material. 180 degree peel strength 30 seconds after pressing is 0.5Kg/
in, 1.0Kg/in after 60 seconds and 1.5 after 90 seconds.
Decorative paper was observed to break at ~2.0Kg/in. Example 4 150 g/m 2 of the water-soluble urethane prepolymer obtained in Production Example 3 and 75 g/m 2 of the hardening agent obtained in Production Example 10 were simultaneously spray mixed and applied to plywood (dimensions 300 x 300 x 5 mm). After leaving in air for 20 seconds, slates (dimensions 300 x 300 x 3 mm) are bonded together and pressed with a press at a pressing pressure of 2 kg/cm 2 to obtain a laminated molded material. The tensile shearing force after 60 seconds at room temperature after pressing was 5 Kg/cm 2 , and the adhesive strength was such that the slate would break after 90 seconds. Example 5 Water-soluble urethane prepolymer obtained in Production Example 3 was applied to either side of a wooden board (dimensions 300 x 300 x 9 mm).
100 g/m 2 and hardening agent 50 obtained in Production Example 10
g/m 2 at the same time by spray mixing and applying 20 g/m 2 in air.
After leaving it for a few seconds, this is pasted with another wooden board and pressed with a press at 2 kg/cm 2 to obtain a laminated molded material. The tensile shear force after 60 seconds at room temperature after pressing is 5Kg/
cm 2 , 10 Kg/cm 2 after 90 seconds, and 25 Kg/cm 2 after 3 minutes, which is almost the final strength. Example 6 Water-soluble urethane prepolymer obtained in Production Example 2 in urethane foam (dimensions 300 x 300 x 10 mm)
100 g/m 2 and hardening agent 50 obtained in Production Example 10
g/m 2 at the same time and apply it by spraying and immediately applying it to a back coated steel plate (dimensions 300 x 300 x 0.8 mm).
The material is pasted onto the painted surface and pressed with a roller to a pressure of 0.1Kg/cm 2 to obtain a laminated molded material. The 180 degree peel strength after 60 seconds at room temperature after pressing was 0.8 kg/in., and the adhesive strength was such that the urethane foam broke after 90 seconds. Example 7 A laminate molded material is obtained in the same manner as in Example 6, except that the water-soluble urethane prepolymer obtained in Production Example 1 and the curing agent obtained in Production Example 10 are used. The results of the 180 degree peel test after pressing were the same as in Example 6. Example 8 70 g/m 2 of the water-soluble urethane prepolymer obtained in Production Example 2 and 35 g/m 2 of the hardening agent obtained in Production Example 10 were simultaneously sprayed and applied to plywood (dimensions 300 x 300 x 5 mm). , leave it in the air for 20 seconds, and this
Paste PVC sheets (dimensions 300 x 300 x 2 mm),
After pressing with rollers, pressing pressure 2 is applied by press.
Press at Kg/cm 2 to obtain a laminated molded material. The 180 degree peel strength is 0.5 to 1.0 Kg/in after 60 seconds at room temperature after pressing, and 1.0 to 1.5 Kg/in after 120 seconds.
The final strength after moisture drying was 2.5 kg/in. Example 9 Manufacturing example 3 on painted steel plate (dimensions 300 x 300 x 0.8 mm)
100g of water-soluble urethane prepolymer obtained from
m 2 and 50 g/m 2 of the curing agent obtained in Production Example 10 were simultaneously spray mixed and applied, and a honeycomb board (dimensions 300 x 300 x 30 mm) was immediately bonded to this, and a pressing force of 0.5 kg/m 2 was applied using a press. Press with cm2 to obtain a laminated molded material. After 60 seconds at room temperature after pressing, the adhesive is almost cured and the laminated molded material can be carried. After 5 minutes, the honeycomb board broke in a manual tear test. Examples 10 to 23 According to the method described in Example 1, the adherends shown in Table 3 were laminated using various water-soluble urethane prepolymers (base ingredients) and curing agents.
The results are also listed in Table 1.
【表】【table】
【表】
＊２：そのときの強度および破壊状態を示す
。
なお、本発明で用いる水溶性ウレタンプレポリ
マーにおけるポリアルキレンエーテルポリオール
のEO量の有用性について、比較実験（No.１〜５）
を行つた。その手順および結果を以下に示す。
水溶性ウレタンプレポリマーの製造
下記第４表に示すポリアルキレンエーテルポリ
オールに対し、ジフエニルメタン−４，4′−ジイ
ソシアネートを用い、製造例１と同様にして第４
表に示す水溶性ウレタンプレポリマーを得る。
積層成形加工
実施例１に記載の方法に従い、ウレタンフオー
ム／ウレタンフオームの被着材に対して上記ウレ
タンプレポリマーと製造例10の硬化剤（水90／尿
素10）を用い、積層成形加工を行う。結果を第４
表に併記する。[Table] *2: Indicates the strength and fracture state at that time.
In addition, comparative experiments (Nos. 1 to 5) were conducted to examine the usefulness of the EO amount of polyalkylene ether polyol in the water-soluble urethane prepolymer used in the present invention.
I went there. The procedure and results are shown below. Production of water-soluble urethane prepolymer A prepolymer was prepared in the same manner as in Production Example 1 using diphenylmethane-4,4'-diisocyanate for the polyalkylene ether polyol shown in Table 4 below.
A water-soluble urethane prepolymer shown in the table is obtained. Laminate molding process According to the method described in Example 1, laminate molding process is performed on the urethane foam/urethane foam adherend using the above urethane prepolymer and the curing agent of Production Example 10 (90 parts water/10 parts urea). . 4th result
Also listed in the table.
【表】
考 察
上記結果から明らかなように、ポリアルキレン
エーテルポリオールにおいてそのEO量が接着強
度発現性（硬化時間）に大きく寄与し、EO量30
〜90％のものを用いることにより、所望の接着強
度がきわめて短時間に達成される。[Table] Discussion As is clear from the above results, the amount of EO greatly contributes to the adhesive strength development (curing time) in polyalkylene ether polyols, and the amount of EO 30
~90%, the desired adhesive strength is achieved in a very short time.
Claims (1)
層成形するにあたり、 被着体の一方又は双方の接合面に、エチレンオ
キサイドのモル比30〜90％のポリアルキレンエー
テルポリオールと過剰のポリイソシアネートとの
反応生成物である水溶性ウレタンプレポリマーか
らなる主剤と水を主成分とする硬化剤を空中混合
にて同時噴霧した後、両者を重ね合わせ、押圧接
合することを特徴とする多孔質材の積層成形加工
法。 ２ 多孔質材が木材、スレート、紙、布、フエル
トまたはプラスチツクフオームである第１項記載
の積層成形加工法。 ３ 水を主成分とする硬化剤が反応触媒として、
有機アミン、無機塩基性化合物、尿素、チオ尿素
アミノ酸塩および塩基性アミノ酸からなる群から
選ばれる１種または２種以上を含む第１項記載の
積層成形加工法。[Claims] 1. When laminating an adherend in which at least one of the adherends is a porous material, a polyalkylene ether polyol having an ethylene oxide molar ratio of 30 to 90% is applied to one or both joint surfaces of the adherend. The main ingredient is a water-soluble urethane prepolymer, which is a reaction product of polyisocyanate, and an excess amount of polyisocyanate, and the curing agent, which is mainly composed of water, is mixed in the air and sprayed simultaneously, and then the two are overlapped and pressure bonded. A laminated molding method for porous materials. 2. The laminate molding method according to item 1, wherein the porous material is wood, slate, paper, cloth, felt, or plastic foam. 3 A curing agent mainly composed of water acts as a reaction catalyst,
2. The laminate molding method according to item 1, which contains one or more selected from the group consisting of organic amines, inorganic basic compounds, urea, thiourea amino acid salts, and basic amino acids.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15041781A JPH0234994B2 (en) | 1981-09-21 | 1981-09-21 | TAKOSHITSUZAINOSEKISOSEIKEIKAKOHO |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15041781A JPH0234994B2 (en) | 1981-09-21 | 1981-09-21 | TAKOSHITSUZAINOSEKISOSEIKEIKAKOHO |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5852378A JPS5852378A (en) | 1983-03-28 |
| JPH0234994B2 true JPH0234994B2 (en) | 1990-08-07 |
Family
ID=15496480
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15041781A Expired - Lifetime JPH0234994B2 (en) | 1981-09-21 | 1981-09-21 | TAKOSHITSUZAINOSEKISOSEIKEIKAKOHO |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0234994B2 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4750963A (en) * | 1986-06-19 | 1988-06-14 | Sunstar Giken Kabushiki Kaisha | Method for producing laminated product of porous materials |
| TW272976B (en) * | 1993-08-06 | 1996-03-21 | Ciba Geigy Ag | |
| CN100339456C (en) * | 2005-06-21 | 2007-09-26 | 叶远鸿 | Method for preparing-environmental-protection sponge adhesive |
| WO2014017641A1 (en) * | 2012-07-26 | 2014-01-30 | 東ソー株式会社 | Amine catalyst for curing polyisocyanate compound and polyisocyanate adhesive composition containing amine catalyst for curing polyisocyanate compound |
| IT201700094824A1 (en) * | 2017-08-21 | 2019-02-21 | Tecnoform Spa | METHOD FOR THE PRODUCTION OF CURVED COMPONENTS FROM FURNITURE AND COMPONENT SO OBTAINABLE |
-
1981
- 1981-09-21 JP JP15041781A patent/JPH0234994B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5852378A (en) | 1983-03-28 |
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