JPH0252946B2 - - Google Patents
Info
- Publication number
- JPH0252946B2 JPH0252946B2 JP57206854A JP20685482A JPH0252946B2 JP H0252946 B2 JPH0252946 B2 JP H0252946B2 JP 57206854 A JP57206854 A JP 57206854A JP 20685482 A JP20685482 A JP 20685482A JP H0252946 B2 JPH0252946 B2 JP H0252946B2
- Authority
- JP
- Japan
- Prior art keywords
- adhesive
- diisocyanate
- prepolymer
- liquid
- weight
- 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
- 239000000853 adhesive Substances 0.000 claims description 39
- 230000001070 adhesive effect Effects 0.000 claims description 39
- 239000007788 liquid Substances 0.000 claims description 17
- 239000003054 catalyst Substances 0.000 claims description 10
- 238000005829 trimerization reaction Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 10
- -1 hydrogen compound Chemical class 0.000 description 8
- 239000012948 isocyanate Substances 0.000 description 7
- 150000002513 isocyanates Chemical class 0.000 description 6
- 239000012790 adhesive layer Substances 0.000 description 5
- 229910052783 alkali metal Inorganic materials 0.000 description 5
- 150000001735 carboxylic acids Chemical class 0.000 description 5
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- RXYPXQSKLGGKOL-UHFFFAOYSA-N 1,4-dimethylpiperazine Chemical compound CN1CCN(C)CC1 RXYPXQSKLGGKOL-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000013522 chelant Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000006471 dimerization reaction Methods 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229940098779 methanesulfonic acid Drugs 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 238000011417 postcuring Methods 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- FYADHXFMURLYQI-UHFFFAOYSA-N 1,2,4-triazine Chemical compound C1=CN=NC=N1 FYADHXFMURLYQI-UHFFFAOYSA-N 0.000 description 1
- LKLLNYWECKEQIB-UHFFFAOYSA-N 1,3,5-triazinane Chemical compound C1NCNCN1 LKLLNYWECKEQIB-UHFFFAOYSA-N 0.000 description 1
- MFVFDTCSVFBOTL-UHFFFAOYSA-N 1,3-diazetidine Chemical compound C1NCN1 MFVFDTCSVFBOTL-UHFFFAOYSA-N 0.000 description 1
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 description 1
- NKFIBMOQAPEKNZ-UHFFFAOYSA-N 5-amino-1h-indole-2-carboxylic acid Chemical compound NC1=CC=C2NC(C(O)=O)=CC2=C1 NKFIBMOQAPEKNZ-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical class [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000010062 adhesion mechanism Effects 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 125000004985 dialkyl amino alkyl group Chemical group 0.000 description 1
- ORICWOYODJGJMY-UHFFFAOYSA-N dibutyl(phenyl)phosphane Chemical compound CCCCP(CCCC)C1=CC=CC=C1 ORICWOYODJGJMY-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000012939 laminating adhesive Substances 0.000 description 1
- GIWKOZXJDKMGQC-UHFFFAOYSA-L lead(2+);naphthalene-2-carboxylate Chemical compound [Pb+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 GIWKOZXJDKMGQC-UHFFFAOYSA-L 0.000 description 1
- 238000000199 molecular distillation Methods 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-M octanoate Chemical compound CCCCCCCC([O-])=O WWZKQHOCKIZLMA-UHFFFAOYSA-M 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- ZUFQCVZBBNZMKD-UHFFFAOYSA-M potassium 2-ethylhexanoate Chemical compound [K+].CCCCC(CC)C([O-])=O ZUFQCVZBBNZMKD-UHFFFAOYSA-M 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- GCHCGDFZHOEXMP-UHFFFAOYSA-L potassium adipate Chemical compound [K+].[K+].[O-]C(=O)CCCCC([O-])=O GCHCGDFZHOEXMP-UHFFFAOYSA-L 0.000 description 1
- 235000011051 potassium adipate Nutrition 0.000 description 1
- 239000001608 potassium adipate Substances 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 235000010235 potassium benzoate Nutrition 0.000 description 1
- 239000004300 potassium benzoate Substances 0.000 description 1
- 229940103091 potassium benzoate Drugs 0.000 description 1
- 229940096992 potassium oleate Drugs 0.000 description 1
- BWILYWWHXDGKQA-UHFFFAOYSA-M potassium propanoate Chemical compound [K+].CCC([O-])=O BWILYWWHXDGKQA-UHFFFAOYSA-M 0.000 description 1
- 235000010332 potassium propionate Nutrition 0.000 description 1
- 239000004331 potassium propionate Substances 0.000 description 1
- MLICVSDCCDDWMD-KVVVOXFISA-M potassium;(z)-octadec-9-enoate Chemical compound [K+].CCCCCCCC\C=C/CCCCCCCC([O-])=O MLICVSDCCDDWMD-KVVVOXFISA-M 0.000 description 1
- RLEFZEWKMQQZOA-UHFFFAOYSA-M potassium;octanoate Chemical compound [K+].CCCCCCCC([O-])=O RLEFZEWKMQQZOA-UHFFFAOYSA-M 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- NESLWCLHZZISNB-UHFFFAOYSA-M sodium phenolate Chemical compound [Na+].[O-]C1=CC=CC=C1 NESLWCLHZZISNB-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Description
本発明は、プラスチツクス、金属、セラミツク
ス、あるいはセルロース系材料等の接着に適した
無溶剤接着用組成物に関する。
イソシアネートを含む接着剤は、一般に各種材
料の接着に適しており、その接着機構としては、
被着材表面の活性水素と反応し化学結合や水素結
合、あるいはその他の物理的な吸引力によつて接
合すると考えられている。
接着能は、それ故、イソシアネート基の濃度が
高いほど、また、接着界面の強度が大きいほぼ優
れると考えられるが、これらを総合的に高めるこ
とが非常に困難である。その理由としては、イソ
シアネート基濃度の高い接着剤は、一般に粘度が
低く、またその硬化物が硬く脆いため強固な接着
層を形成できない。また、硬化時の反応熱が大き
く、収縮率も大きいため、接着層に大きな残留応
力を生じるため接着力が弱い。
接着層を強靫にするため、過剰なポリイソシア
ネートと活性水素化合物との反応によりイソシア
ネート予備重合体をつくり、これを接着剤として
使用する方法も行なわれている。この方法では、
強靫な接着層を形成するが、イソシアネート基濃
度が必然的に低下し、またウレタン結合や尿素結
合のような親水性で水素結合能の強い構造が導入
されるので、液の流動性が低下し、被着材に対す
る漏れ性が著しく低下するため接着力を十分でな
く、また浸水時の接着力の低下が著しいという欠
点があつた。一方高粘度の接着剤については、溶
剤を加えて流動性を増し、被着材への漏れ性を高
める方法もとられているが、この場合十分に溶剤
を揮散させないと接着層中にボイドを生じ接着力
を著しく低下せしめるばかりでなく、溶剤が被着
材を侵食することにより接着力を低下させること
があつた。したがつて、流動し易く漏れ性のよい
無溶剤の接着剤が好ましいが、上記イソシアネー
ト予備重合体では、このような接着組成物を得る
ことが難かしかつた。
本発明者等は、従来の欠点を改善するため鋭意
研究の結果プラスチツクス、金属、セラミツク
ス、あるいはセルロース系材料等に対して非常に
優れた接着性を示す無溶剤のイソシアネート含有
接着剤を見出し本発明に至つた。
すなわち、本発明は、無溶剤の接着用組成物
で、脂肪族ジイソシアネートから製造される
NCO含量15〜30重量％の液状イソシアナトイソ
シアヌレートおよび／または、NCO含量15〜30
重量％のイソシアナトウレチジンジオン予備重合
体に三量化触媒を存在せしめたものである。
本発明を実施するために用いる脂肪族ジイソシ
アネートから製造されるNCO含量15〜30重量％
の液状イソシアナトイソシアヌレートおよび／ま
たはNCO含量15〜30重量％のイソシアナトウレ
チジンジオン予備重合体は、次のような構造を有
する。
上式中、Ｒは脂肪族ジラジカルを意味し、ｎ，
ｍは整数で好ましくは、１〜５を意味する。ここ
で、Ｒはまた、上記、液状予備重合体を製造する
ために用いる脂肪族ジイソシアネートの２つのイ
ソシアネート基を除いた残基を意味する。このよ
うな脂肪族ジイソシアネートとしては、上記予備
重合体が常温で液状のもので、例えば、テトラメ
チレン−１，４−ジイソシアネート、ペンタメチ
レン−１，５−ジイソシアネート、ヘキサメチレ
ン−１，６−ジイソシアネート、ヘプタメチレン
−１，７−ジイソシアネート、オクタメチレン−
１，８−ジイソシアネート、２，２，４−トリメ
チルヘキサメチレン−１，６−ジイソシアネー
ト、２，４，４−トリメチルヘキサメチレン−
１，６−ジイソシアネート、リジンジイソシアネ
ートメチルエステル、などの単独あるいは２種以
上の混合物である。これらの中、工業的に容易に
入手でき、流動性のよい予備重合体が得られるも
のとしては、２，２，４−トリメチルヘキサメチ
レン−１，６−ジイソシアネート、２，４，４−
トリメチルヘキサメチレン−１，６−ジイソシア
ネート、ヘキサメチレン−１，６−ジイソシアネ
ートなどが特に好ましい。
脂肪族ジイソシアネートからのNCO含量15〜
30重量％の液状イソシアナトイソシアヌレートお
よび／またはNCO含量15〜30重量％のイソシア
ナトウレチジンジオン予備重合体はは、公知の方
法で製造でき、例えば、脂肪族ジイソシアネート
中に三量化または二量化触媒を存在させてイソシ
アヌレート化、またはウレチジンジオン化を行な
い適度な重合度で触媒を失活または除去する方法
で容易に得られる。
また、本発明に用いられる三量化触媒として
は、公知のものが使用できる。例えば、炭素数が
２〜12のカルボン酸のアルカリ金属塩（酢酸カリ
ウム、プロピオン酸カリウム、カプリル酸カリウ
ム、アジピン酸カリウム、安息香酸カリウム等）、
炭素数が13以上のカルボン酸アルカリ金属塩（例
えば、オレイン酸カリウム）、ナトリウムフエノ
レートのようなカルボン酸以外の弱酸のアルカリ
金属塩で示される弱塩基性物質、ナトリウムメト
キシド、ベンジルトリメチルアンモニウムヒドロ
キシド、アルカリ金属水酸化物等の強塩基性物
質、サリチルアルデヒドとカリウムのキレート化
合物で代表されるキレート化合物、ナフテン酸カ
ルシウム、ナフテン酸鉛、カプリル酸鉛等のカル
ボン酸のアルカリ金属以外の金属塩、トリエチル
アミン、トリプロピルアミン、トリブチルアミ
ン、Ｎ−メチルモルホリン、Ｎ，N′−ジメチル
ピペラジン、２，４，６−トリス（ジメチルアミ
ノメチル）フエノール、Ｎ，N′，N″−トリス
（ジアルキルアミノアルキル）ヘキサヒドロ−Ｓ
−トリアジン等の三級アミン類、これらのイソシ
アネート三量化触媒は混合物としても使用でき
る。これらの中、特に好ましい触媒は、２，４，
６−トリス（ジメチルアミノメチル）フエノー
ル、Ｎ，N″，N″−トリス（ジメチルアミノプロ
ピル）ヘキサヒドロ−Ｓ−トリアジンのような三
級アミン、あるいは、炭素数２〜12のカルボン酸
のアルカリ金属塩があり、二量化触媒としては、
例えば、ピリジン、トリエチレンジアミンのよう
な三級アミン類、トリ−ｎ−ブチルホスフイン、
フエニル−ジ−ｎ−ブチルホスフインのようなホ
スフイン類をあげることができる。これらは、触
媒活性、配合系への相溶性等が優れている。
三量化触媒をNCO含量15〜30重量％の液状イ
ソシアナトイソシアヌレートおよび／または
NCO含量15〜30重量％のイソシアナトウレチジ
ンジオン予備重合体に混合せしめ接着に使用す
る。接着にあたつて、配合液を10Torr以下の減
圧により脱ガスすることが、接着部にボイドや残
留応力をなくすためにさらに好ましい。被着材は
表面を清浄にし、常温または常温から160℃くら
いに予熱し、しかる後、上記接着剤により接合処
理される。一般に、硬化まで接着部は静置し無理
な力がかからぬようにするのが好ましく、接着部
の圧締は不要か100Kg／cm2程度以下の圧力で十分
である。圧締は、特に繊維製品の積層接着に有効
で、10〜50Kg／cm2位で常温または加熱下に圧締を
行うと良好な積層材が得られる。
接着部の硬化後、後硬化処理を行うことにより
接着力の向上がみられる。後硬化の温度は、50〜
200℃、好ましくは70〜140℃程度である。
本発明の組成物は、例えば、金属板加工品組立
て接合用に適している。また、FRP構造部材の
接着剤としても使用できる。プラスチツクフイル
ムや金属箔の積層接着剤としても適している。電
気絶縁体またはガラス繊維で強化した積層材に使
用される含浸接着剤としても適用できる。また、
セラミツクスの接合や、鋳物砂型用の結合剤とし
ても適しており、工業的にみて極めて有用であ
る。
次に実施例によつて本発明をさらに具体的に説
明する。
尚実施例中の部および％は各々重量部、重量％
を示す。
実施例 １
撹拌機、窒素ガス送入管、温度計、パーシヤル
コンデンサーを付したフラスコにヘキサメチレン
−１，６−ジイソシアネート1000ｇを仕込み、こ
れを撹拌しながら三量化触媒ポリキヤツト42（サ
ンアボツト製）１ｇを溶解させた。この液を直ち
にサンプリングし、イソシアネート基含有率を測
定したところ49.5％であつた。以後、液を35〜40
℃に保ちながら2.5時間撹拌を継続したところイ
ソシアネート基含有率が42.7％となつた。この時
点で、メタンスルホン酸1.5ｇ添加し三量化反応
を停止させた。得られた液を減圧蒸溜し、未反応
のヘキサメチレン−１，６−ジイソシアネートを
除去したところ、液状イソシアナトイソシアヌレ
ート予備重合体が298ｇ得られた。このものは外
観、無色透明、イソシアネート基含有率22.3％、
粘度2150cps／25℃の液体であつた。
上記により得られたイソシアネートイソシアヌ
レート予備重合体100部にポリキヤツト420.5部配
合して接着剤を得た。この接着剤を用いて被着材
の接着部をトリクレンで清拭し、サンデイング
後、各々の面に約20μ厚に塗布後直ちに貼り合せ
25Kg／cm2で圧締しながら140℃で６時間キユアー
した。表１にJIS K6850に従つて測定した引張り
せん断接着強さの結果を示すが、極めて優秀な接
着力を示すことがわかる。
The present invention relates to a solvent-free adhesive composition suitable for adhering plastics, metals, ceramics, cellulose materials, etc. Adhesives containing isocyanates are generally suitable for adhering various materials, and their adhesion mechanism is as follows:
It is thought that it reacts with active hydrogen on the surface of the adherend and bonds through chemical bonds, hydrogen bonds, or other physical attraction forces. Therefore, it is considered that the higher the concentration of isocyanate groups and the greater the strength of the adhesive interface, the better the adhesive ability, but it is very difficult to improve these properties comprehensively. The reason for this is that adhesives with a high concentration of isocyanate groups generally have low viscosity, and their cured products are hard and brittle, making it impossible to form a strong adhesive layer. In addition, the heat of reaction during curing is large and the shrinkage rate is also large, resulting in large residual stress in the adhesive layer, resulting in weak adhesive strength. In order to make the adhesive layer strong, an isocyanate prepolymer is prepared by reacting excess polyisocyanate with an active hydrogen compound, and this is used as an adhesive. in this way,
Although it forms a strong adhesive layer, the concentration of isocyanate groups inevitably decreases, and hydrophilic structures with strong hydrogen bonding ability, such as urethane bonds and urea bonds, are introduced, resulting in a decrease in fluidity of the liquid. However, there were disadvantages in that the adhesive strength was not sufficient because the leakage to the adherend material was significantly reduced, and the adhesive strength was significantly decreased when submerged in water. On the other hand, for high-viscosity adhesives, a method is used to increase fluidity by adding a solvent to increase leakage to the adherend, but in this case, if the solvent is not sufficiently volatilized, voids may occur in the adhesive layer. Not only did this result in a significant decrease in adhesive strength, but the solvent also eroded the adherend, resulting in a decrease in adhesive strength. Therefore, a solvent-free adhesive that is easy to flow and has good leakage properties is preferable, but it has been difficult to obtain such an adhesive composition using the above-mentioned isocyanate prepolymer. As a result of intensive research to improve the conventional drawbacks, the present inventors discovered and published a solvent-free isocyanate-containing adhesive that exhibits excellent adhesion to plastics, metals, ceramics, cellulose materials, etc. This led to the invention. That is, the present invention is a solvent-free adhesive composition prepared from an aliphatic diisocyanate.
Liquid isocyanatoisocyanurate with NCO content 15-30% by weight and/or NCO content 15-30%
% by weight of isocyanatouretidinedione prepolymer in the presence of a trimerization catalyst. NCO content 15-30% by weight produced from aliphatic diisocyanates used to carry out the invention
The liquid isocyanatoisocyanurate and/or isocyanatouretidinedione prepolymer with an NCO content of 15 to 30% by weight has the following structure. In the above formula, R means an aliphatic diradical, n,
m is an integer, preferably 1-5. Here, R also means the residue of the aliphatic diisocyanate used for producing the liquid prepolymer, excluding the two isocyanate groups. Such aliphatic diisocyanates include those in which the prepolymer is liquid at room temperature, such as tetramethylene-1,4-diisocyanate, pentamethylene-1,5-diisocyanate, hexamethylene-1,6-diisocyanate, Heptamethylene-1,7-diisocyanate, octamethylene-
1,8-diisocyanate, 2,2,4-trimethylhexamethylene-1,6-diisocyanate, 2,4,4-trimethylhexamethylene-
1,6-diisocyanate, lysine diisocyanate methyl ester, etc. alone or in a mixture of two or more. Among these, 2,2,4-trimethylhexamethylene-1,6-diisocyanate, 2,4,4-diisocyanate, and 2,2,4-trimethylhexamethylene-1,6-diisocyanate are industrially easily available and yield prepolymers with good fluidity.
Particularly preferred are trimethylhexamethylene-1,6-diisocyanate and hexamethylene-1,6-diisocyanate. NCO content from aliphatic diisocyanates 15~
Liquid isocyanatoisocyanurates of 30% by weight and/or isocyanatouretidinedione prepolymers with an NCO content of 15-30% by weight can be prepared by known methods, for example by trimerization or dimerization in aliphatic diisocyanates. It can be easily obtained by carrying out isocyanurate formation or uretidine diionation in the presence of a catalyst, and then deactivating or removing the catalyst at an appropriate degree of polymerization. Further, as the trimerization catalyst used in the present invention, known ones can be used. For example, alkali metal salts of carboxylic acids having 2 to 12 carbon atoms (potassium acetate, potassium propionate, potassium caprylate, potassium adipate, potassium benzoate, etc.),
Weak basic substances represented by alkali metal salts of weak acids other than carboxylic acids such as alkali metal salts of carboxylic acids having 13 or more carbon atoms (e.g., potassium oleate), sodium phenolate, sodium methoxide, benzyltrimethylammonium hydroxy strong basic substances such as alkali metal hydroxides, chelate compounds such as chelate compounds of salicylaldehyde and potassium, metal salts other than alkali metals of carboxylic acids such as calcium naphthenate, lead naphthenate, and lead caprylate. , triethylamine, tripropylamine, tributylamine, N-methylmorpholine, N,N'-dimethylpiperazine, 2,4,6-tris(dimethylaminomethyl)phenol, N,N',N''-tris(dialkylaminoalkyl) ) hexahydro-S
- Tertiary amines such as triazine and these isocyanate trimerization catalysts can also be used as a mixture. Among these, particularly preferred catalysts are 2, 4,
Tertiary amines such as 6-tris(dimethylaminomethyl)phenol, N,N″,N″-tris(dimethylaminopropyl)hexahydro-S-triazine, or alkali metal salts of carboxylic acids having 2 to 12 carbon atoms As a dimerization catalyst,
For example, pyridine, tertiary amines such as triethylenediamine, tri-n-butylphosphine,
Mention may be made of phosphines such as phenyl-di-n-butylphosphine. These have excellent catalytic activity, compatibility with compounding systems, and the like. The trimerization catalyst is a liquid isocyanatoisocyanurate with an NCO content of 15-30% by weight and/or
It is used for adhesion by mixing with isocyanatouretidinedione prepolymer having an NCO content of 15-30% by weight. During bonding, it is more preferable to degas the compounded liquid by reducing the pressure to 10 Torr or less in order to eliminate voids and residual stress in the bonded portion. The surface of the adherend is cleaned, heated to room temperature or from room temperature to about 160°C, and then bonded using the adhesive described above. Generally, it is preferable to leave the bonded area still until it hardens so that no excessive force is applied to it, and there is no need to press the bonded area, or a pressure of about 100 kg/cm 2 or less is sufficient. Pressing is particularly effective for laminating and adhering textile products, and a good laminate can be obtained if pressing is performed at room temperature or under heating at about 10 to 50 kg/cm 2 . After the adhesive part is cured, the adhesive strength is improved by performing a post-curing treatment. Post-curing temperature is 50~
The temperature is 200°C, preferably about 70 to 140°C. The composition of the invention is suitable, for example, for assembling and joining metal plate workpieces. It can also be used as an adhesive for FRP structural members. It is also suitable as a laminating adhesive for plastic films and metal foils. It can also be applied as an impregnating adhesive used in electrical insulation or glass fiber reinforced laminates. Also,
It is also suitable for joining ceramics and as a binder for foundry sand molds, making it extremely useful from an industrial perspective. Next, the present invention will be explained in more detail with reference to Examples. In addition, parts and % in the examples are parts by weight and % by weight, respectively.
shows. Example 1 1000 g of hexamethylene-1,6-diisocyanate was charged into a flask equipped with a stirrer, a nitrogen gas supply tube, a thermometer, and a partial condenser, and while stirring, 1 g of trimerization catalyst Polycat 42 (manufactured by Sanabbot) was added. was dissolved. This liquid was immediately sampled and the isocyanate group content was measured and found to be 49.5%. After that, add 35 to 40 ml of liquid.
Stirring was continued for 2.5 hours while maintaining the temperature at °C, and the isocyanate group content was 42.7%. At this point, 1.5 g of methanesulfonic acid was added to stop the trimerization reaction. The resulting liquid was distilled under reduced pressure to remove unreacted hexamethylene-1,6-diisocyanate, yielding 298 g of a liquid isocyanatoisocyanurate prepolymer. This product has an appearance that is colorless and transparent, and has an isocyanate group content of 22.3%.
It was a liquid with a viscosity of 2150 cps/25°C. 420.5 parts of polycat was added to 100 parts of the isocyanate isocyanurate prepolymer obtained above to obtain an adhesive. Using this adhesive, wipe the adhesive part of the adherend with Triclean, sand it, apply it to each surface to a thickness of approximately 20μ, and then bond immediately.
It was cured at 140°C for 6 hours while being compressed at 25 kg/cm 2 . Table 1 shows the results of tensile shear adhesive strength measured according to JIS K6850, and it can be seen that extremely excellent adhesive strength is exhibited.
【表】
実施例 ２
実施例１と同様の反応容器に２，２，４−トリ
メチルヘキサメチレン−１，６−ジイソシアネー
ト1000ｇとトリ−ｎ−ブチルホスフイン４ｇを仕
込み、撹拌混合後サンプリングしてイソシアネー
ト基含有率を測定したところ39.1％であつた。90
℃で８時間撹拌を継続したところイソシアネート
基含有率は33.2％となつた。この時点でメタンス
ルホン酸2.4ｇを添加し反応を停止させた。得ら
れた液を減圧蒸溜し、未反応の２，２，４−トリ
メチルヘキサメチレン−１，６−ジイソシアネー
トを除去したところ、1Rで1770cm-1のウレチジ
ンジオンおよび1690cm-1のイソシアヌレートに基
づく吸収をもつ予備重合体256ｇが得られた。こ
のものは外観、無色透明、イソシアネート基含有
率18.1％、粘度4720cps／25℃の液体であつた。
この予備重合体100部にポリキヤツト42 0.5部
を配合して接着剤を得た。この接着剤を用いて被
着材を実施例１と同じ条件で貼り合せ、25Kg／cm2
で圧締しながら140℃で８時間キユアーした。表
２にJIS K6850に従つて測定した引張りせん断接
着強さの結果を示すが、極めて優秀な接着力を示
すことがわかる。[Table] Example 2 1000 g of 2,2,4-trimethylhexamethylene-1,6-diisocyanate and 4 g of tri-n-butylphosphine were placed in the same reaction vessel as in Example 1, and after stirring and mixing, the isocyanate was sampled. When the group content was measured, it was 39.1%. 90
When stirring was continued for 8 hours at °C, the isocyanate group content was 33.2%. At this point, 2.4 g of methanesulfonic acid was added to stop the reaction. When the obtained liquid was distilled under reduced pressure to remove unreacted 2,2,4-trimethylhexamethylene-1,6-diisocyanate, the absorption based on uretidinedione of 1770 cm -1 and isocyanurate of 1690 cm -1 at 1R was found. 256 g of prepolymer was obtained. This product was a colorless and transparent liquid with an isocyanate group content of 18.1% and a viscosity of 4720 cps/25°C. 0.5 parts of Polycat 42 was blended with 100 parts of this prepolymer to obtain an adhesive. Using this adhesive, adherends were bonded under the same conditions as in Example 1, and the adhesive was 25Kg/cm 2
It was cured at 140℃ for 8 hours while being compressed. Table 2 shows the results of tensile shear adhesive strength measured according to JIS K6850, and it can be seen that extremely excellent adhesive strength is exhibited.
【表】
実施例 ３
実施例２で得られた予備重合体を分子蒸溜し、
イソシアナトウレチジンジオン予備重合体を分別
した。このものは外観、無色透明液体、イソシア
ネート基含有率26.8％、粘度300cps／25℃の液体
であつた。この予備重合体100部にポリキヤツト
42 0.5部を配合して接着剤を得た。この接着剤を
用いて実施例１と同じ条件で貼り合せ、25Kg／cm2
で圧締しながら130℃で８時間キユアーした。表
３にJIS K6850に従つて測定した引張りせん断接
着強さの結果を示すが、極めて優秀な接着力を示
すことがわかる。[Table] Example 3 The prepolymer obtained in Example 2 was subjected to molecular distillation,
The isocyanatouretidinedione prepolymer was fractionated. This product was a colorless transparent liquid with an isocyanate group content of 26.8% and a viscosity of 300 cps/25°C. Add 100 parts of this prepolymer to Polycat.
An adhesive was obtained by blending 0.5 part of 42. Using this adhesive, bonding was carried out under the same conditions as in Example 1, and the weight was 25Kg/cm 2
It was cured at 130℃ for 8 hours while being compressed. Table 3 shows the results of tensile shear adhesive strength measured according to JIS K6850, and it can be seen that extremely excellent adhesive strength is exhibited.
【表】
実施例 ４
実施例１で得られた予備重合体100部に２−エ
チルヘキサン酸カリのポリエチレングリコール
（分子量200）溶液（70％濃度）0.2ｇを配合して
接着剤を得た。この接着剤を用いてガラス不織布
（キユムラスVH5001日本バイリーン製）に180
ｇ／m2含浸せしめた。この含浸不織布を２枚の
FRP板（不飽和ポリエステル系、３mm厚）の間
にはさみ、30Kg／cm2で圧締しながら80℃で８時間
キユアーした。JIS K6850に従つて、引張りせん
断接着強さを測定したところ33Kgｆ／cm2の良好な
値を示した。[Table] Example 4 0.2 g of a polyethylene glycol (molecular weight 200) solution (70% concentration) of potassium 2-ethylhexanoate was blended with 100 parts of the prepolymer obtained in Example 1 to obtain an adhesive. Use this adhesive to attach glass nonwoven fabric (Kyumuras VH5001 manufactured by Nippon Vilene) to
g/m 2 impregnated. Two sheets of this impregnated nonwoven fabric are
It was sandwiched between FRP plates (unsaturated polyester, 3 mm thick) and cured at 80°C for 8 hours while being compressed at 30 kg/cm 2 . The tensile shear adhesive strength was measured according to JIS K6850 and showed a good value of 33 kgf/cm 2 .
Claims (1)
〜30重量％の液状イソシアナトイソシアヌレート
および／またはNCO含量15〜30重量％のイソシ
アナトウレチジンジオン予備重合体に三量化触媒
を存在せしめてなることを特徴とする無溶剤接着
用組成物。1 NCO content from aliphatic diisocyanate15
1. A solvent-free adhesive composition characterized in that a trimerization catalyst is present in a liquid isocyanatoisocyanurate having an NCO content of 15 to 30% by weight and/or an isocyanatouretidinedione prepolymer having an NCO content of 15 to 30% by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57206854A JPS5998180A (en) | 1982-11-26 | 1982-11-26 | Solventless adhesive composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57206854A JPS5998180A (en) | 1982-11-26 | 1982-11-26 | Solventless adhesive composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5998180A JPS5998180A (en) | 1984-06-06 |
| JPH0252946B2 true JPH0252946B2 (en) | 1990-11-15 |
Family
ID=16530143
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57206854A Granted JPS5998180A (en) | 1982-11-26 | 1982-11-26 | Solventless adhesive composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5998180A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2576923B2 (en) * | 1991-10-04 | 1997-01-29 | 花王株式会社 | Container |
| FR2812653A1 (en) * | 2000-08-03 | 2002-02-08 | Michelin Soc Tech | GLUE FOR RUBBER COMPOSITIONS, PROCESS FOR PREPARING THE SAME, AND ARTICLES COMPRISING THE SAME |
| DE102004026118A1 (en) * | 2004-05-28 | 2005-12-15 | Bayer Materialscience Ag | adhesives |
| TWI572633B (en) | 2014-05-02 | 2017-03-01 | Asahi Kasei Chemicals Corp | Polyisocyanate hardening, and polyisocyanate hardening |
| EP3424975A1 (en) * | 2015-04-21 | 2019-01-09 | Covestro Deutschland AG | Polyisocyanurate polymers and process for the production of polyisocyanurate polymers |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4993469A (en) * | 1972-08-30 | 1974-09-05 |
-
1982
- 1982-11-26 JP JP57206854A patent/JPS5998180A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4993469A (en) * | 1972-08-30 | 1974-09-05 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5998180A (en) | 1984-06-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| RU2272818C2 (en) | Adhesion enhancer for monomer-free reactive polyurethanes | |
| KR101572276B1 (en) | Two part polyurethane curable composition having substantially consistent g-modulus across the range of use temperatures | |
| EP0256162B1 (en) | Polyol/polyepoxide/polyisocyanate adhesive composition and its use | |
| EP0279566B1 (en) | Structural adhesive compositions | |
| CN1245507A (en) | Polyurethane sealant compositions | |
| JPH10504350A (en) | Polyurethane composition with low monomeric diisocyanate content | |
| JP2619248B2 (en) | Two-component adhesive | |
| JPH0414113B2 (en) | ||
| EP0269119A2 (en) | Sag resistant urethane adhesives with improved antifoaming property | |
| JP2010510340A (en) | Foamable mixture containing prepolymer having alkoxysilane end groups | |
| JPH05255475A (en) | Two-component polyurethane reactive composition | |
| US6525162B1 (en) | Polyols, polyurethane systems and polyurethane reactive hot melt adhesives produced therefrom | |
| JPH0252946B2 (en) | ||
| JPS6317095B2 (en) | ||
| EP0254255A1 (en) | Sag resistant two-component urethane adhesives with improved thermal stability | |
| US4097442A (en) | Sandable polyurethane adhesive composition and laminates made therewith | |
| EP3623439A1 (en) | Structural adhesive composition having high elongation and impact resistance | |
| JPH07103354B2 (en) | Substrate adhesion method | |
| CA1166395A (en) | Composition for polyurethane adhesives | |
| JPH0252947B2 (en) | ||
| US3793253A (en) | Mixtures of 5-silamidazolidones-(2) which contain isocyanate groups and urethanes | |
| CA1107437A (en) | Polyurethane-based adhesive composition | |
| JP4062732B2 (en) | Manufacturing method of automobile interior materials | |
| JP4062730B2 (en) | Manufacturing method of automobile interior materials | |
| KR20090092726A (en) | Prepolymers |