JPH10195413A - Moisture-curable reactive hot melt adhesive composition - Google Patents
Moisture-curable reactive hot melt adhesive compositionInfo
- Publication number
- JPH10195413A JPH10195413A JP8358077A JP35807796A JPH10195413A JP H10195413 A JPH10195413 A JP H10195413A JP 8358077 A JP8358077 A JP 8358077A JP 35807796 A JP35807796 A JP 35807796A JP H10195413 A JPH10195413 A JP H10195413A
- Authority
- JP
- Japan
- Prior art keywords
- moisture
- manufactured
- parts
- adhesive composition
- melt adhesive
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 44
- 239000004831 Hot glue Substances 0.000 title claims description 42
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims abstract description 38
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims abstract description 38
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229920005862 polyol Polymers 0.000 claims abstract description 35
- 150000003077 polyols Chemical class 0.000 claims abstract description 35
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 20
- 125000000524 functional group Chemical group 0.000 claims abstract description 18
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 16
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 16
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 15
- 229920000570 polyether Polymers 0.000 claims abstract description 15
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 150000003505 terpenes Chemical class 0.000 claims abstract description 13
- 235000007586 terpenes Nutrition 0.000 claims abstract description 13
- 229920006026 co-polymeric resin Polymers 0.000 claims abstract description 12
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229920005906 polyester polyol Polymers 0.000 claims abstract description 10
- 229920001577 copolymer Polymers 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims 1
- 239000005977 Ethylene Substances 0.000 claims 1
- 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 abstract description 33
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 abstract description 24
- 230000001070 adhesive effect Effects 0.000 abstract description 15
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 14
- 239000000853 adhesive Substances 0.000 abstract description 12
- 239000005038 ethylene vinyl acetate Substances 0.000 abstract 2
- 230000001747 exhibiting effect Effects 0.000 abstract 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 28
- 239000000126 substance Substances 0.000 description 28
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 26
- 239000012975 dibutyltin dilaurate Substances 0.000 description 26
- 238000013008 moisture curing Methods 0.000 description 24
- 239000004814 polyurethane Substances 0.000 description 20
- 229920002635 polyurethane Polymers 0.000 description 20
- 239000003054 catalyst Substances 0.000 description 15
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 14
- 229910052757 nitrogen Inorganic materials 0.000 description 14
- 239000002253 acid Substances 0.000 description 10
- 238000002844 melting Methods 0.000 description 10
- 230000008018 melting Effects 0.000 description 10
- 238000002156 mixing Methods 0.000 description 10
- 230000001133 acceleration Effects 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000007711 solidification Methods 0.000 description 7
- 230000008023 solidification Effects 0.000 description 7
- 238000009849 vacuum degassing Methods 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- -1 polymethylene Polymers 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 4
- 239000012948 isocyanate Substances 0.000 description 4
- 150000002513 isocyanates Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- 238000001723 curing Methods 0.000 description 3
- 238000007872 degassing Methods 0.000 description 3
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 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 3
- GRWFGVWFFZKLTI-IUCAKERBSA-N (-)-α-pinene Chemical compound CC1=CC[C@@H]2C(C)(C)[C@H]1C2 GRWFGVWFFZKLTI-IUCAKERBSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000011120 plywood Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- WTARULDDTDQWMU-RKDXNWHRSA-N (+)-β-pinene Chemical compound C1[C@H]2C(C)(C)[C@@H]1CCC2=C WTARULDDTDQWMU-RKDXNWHRSA-N 0.000 description 1
- WTARULDDTDQWMU-IUCAKERBSA-N (-)-Nopinene Natural products C1[C@@H]2C(C)(C)[C@H]1CCC2=C WTARULDDTDQWMU-IUCAKERBSA-N 0.000 description 1
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- WTARULDDTDQWMU-UHFFFAOYSA-N Pseudopinene Natural products C1C2C(C)(C)C1CCC2=C WTARULDDTDQWMU-UHFFFAOYSA-N 0.000 description 1
- 239000004823 Reactive adhesive Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- XCPQUQHBVVXMRQ-UHFFFAOYSA-N alpha-Fenchene Natural products C1CC2C(=C)CC1C2(C)C XCPQUQHBVVXMRQ-UHFFFAOYSA-N 0.000 description 1
- MVNCAPSFBDBCGF-UHFFFAOYSA-N alpha-pinene Natural products CC1=CCC23C1CC2C3(C)C MVNCAPSFBDBCGF-UHFFFAOYSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- HIFVAOIJYDXIJG-UHFFFAOYSA-N benzylbenzene;isocyanic acid Chemical class N=C=O.N=C=O.C=1C=CC=CC=1CC1=CC=CC=C1 HIFVAOIJYDXIJG-UHFFFAOYSA-N 0.000 description 1
- 229930006722 beta-pinene Natural products 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 229930004069 diterpene Natural products 0.000 description 1
- 125000000567 diterpene group Chemical group 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- LCWMKIHBLJLORW-UHFFFAOYSA-N gamma-carene Natural products C1CC(=C)CC2C(C)(C)C21 LCWMKIHBLJLORW-UHFFFAOYSA-N 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 235000001510 limonene Nutrition 0.000 description 1
- 229940087305 limonene Drugs 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229930003658 monoterpene Natural products 0.000 description 1
- 150000002773 monoterpene derivatives Chemical class 0.000 description 1
- 235000002577 monoterpenes Nutrition 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- GRWFGVWFFZKLTI-UHFFFAOYSA-N rac-alpha-Pinene Natural products CC1=CCC2C(C)(C)C1C2 GRWFGVWFFZKLTI-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
Landscapes
- Adhesives Or Adhesive Processes (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明はホットメルト型およ
び反応型の両接着特性を有する湿気硬化型反応性ホット
メルト接着剤組成物に関する。The present invention relates to a moisture-curable reactive hot-melt adhesive composition having both hot-melt and reactive adhesive properties.
【０００２】[0002]
【従来の技術】湿気硬化型反応性ホットメルト接着剤
は、ホットメルト接着剤の瞬間接着性と、接着後の反応
によって得られる高い耐熱性を併せ持つ接着剤として関
心を集め、これまでに多くの研究がなされている。ウレ
タン系の湿気硬化型反応性ホットメルト接着剤として
は、ポリエステルポリオールと過剰のポリイソシアネー
ト化合物の反応で得られる活性イソシアネート基含有ウ
レタンプレポリマーからなる湿気硬化型反応性ホットメ
ルト接着剤が知られているが、初期接着力が低いといっ
た問題があった。2. Description of the Related Art Moisture-curable reactive hot-melt adhesives have attracted attention as adhesives having both the instantaneous adhesive properties of hot-melt adhesives and the high heat resistance obtained by a reaction after bonding. Research is being done. As a urethane-based moisture-curable reactive hot-melt adhesive, a moisture-curable reactive hot-melt adhesive comprising an active isocyanate group-containing urethane prepolymer obtained by a reaction between a polyester polyol and an excess of a polyisocyanate compound is known. However, there was a problem that the initial adhesive strength was low.
【０００３】そこで、初期接着性を改善する目的で、ポ
リエステルポリオールと過剰のポリイソシアネート化合
物の反応で得られるウレタンプレポリマーにエチレン−
酢酸ビニル共重合体（以下ＥＶＡと略す）を混合するこ
とが試みられているが（特開平５−２１４３１２号公
報、特開平５−２７１６３９号公報、特公平６−１０２
７８０号公報）、ウレタンプレポリマーとＥＶＡの相溶
性が悪く、また、ＥＶＡ系ホットメルト接着剤並の瞬間
接着性が得られない難点がある。[0003] Therefore, in order to improve the initial adhesion, a urethane prepolymer obtained by the reaction of a polyester polyol with an excess of a polyisocyanate compound is added to ethylene-polyurethane.
Attempts have been made to mix a vinyl acetate copolymer (hereinafter abbreviated as EVA) (Japanese Patent Application Laid-Open (JP-A) Nos. 5-214312, 5-271639 and 5-102).
780), the compatibility between the urethane prepolymer and EVA is poor, and the instantaneous adhesive property comparable to that of an EVA-based hot melt adhesive cannot be obtained.
【０００４】また、ＥＶＡに水酸基を導入してＥＶＡ自
身に反応性を持たせる試みもあるが（特公平６−４９８
５９号公報）、溶融粘度が高く、作業性が悪いという問
題がある。There is also an attempt to introduce a hydroxyl group into EVA to make EVA itself reactive (Japanese Patent Publication No. Hei 6-498).
No. 59), there is a problem that the melt viscosity is high and the workability is poor.
【０００５】さらに、初期接着性を改善する目的で、ポ
リエステルポリオールおよび分子内にロジン骨格を有す
るポリエステルポリオールもしくはポリエーテルポリオ
ールを過剰のポリイソシアネート化合物と反応させて得
られるウレタンプレポリマーの報告例があるが（特開平
３−２５２４９０号公報、特開平５−２６３０５９号公
報、特開平７−１２６６００号公報、特開平７−１７９
５５９号公報、特開平７−２２８８５５号公報）、やは
り、ＥＶＡ系ホットメルト接着剤並の瞬間接着性が得ら
れない難点がある。Further, there is a report of a urethane prepolymer obtained by reacting a polyester polyol and a polyester polyol or a polyether polyol having a rosin skeleton in the molecule with an excess of a polyisocyanate compound for the purpose of improving initial adhesion. (JP-A-3-252490, JP-A-5-263059, JP-A-7-126600, JP-A-7-179)
559, JP-A-7-228855), but also has the disadvantage that instantaneous adhesiveness comparable to that of an EVA hot melt adhesive cannot be obtained.
【０００６】瞬間接着性を得るための試みとして、ウレ
タンプレポリマーとイソシアネート基と反応しうる官能
基を有するワックスを反応させて固化速度を向上させる
試みもあるが（特開平４−２２６５８２号公報、特開平
６−２８７５３２号公報）、ワックスの配合量に制限が
あり、十分な固化速度が得られていない。As an attempt to obtain instant adhesiveness, there is an attempt to increase the solidification rate by reacting a urethane prepolymer with a wax having a functional group capable of reacting with an isocyanate group (Japanese Patent Application Laid-Open No. 4-226852, JP-A-6-287532), the amount of wax is limited, and a sufficient solidification rate has not been obtained.
【０００７】この様に現状では、市場の要求を十分に満
たした湿気硬化型反応性ホットメルト接着剤組成物は見
あたらない。市場では、固化速度が速く、接着直後から
強い接着力と凝集力を示し、加熱溶融時の熱安定性が良
好で、かつ最終的には十分な耐熱性を発揮しうる湿気硬
化型反応性ホットメルト接着剤組成物が強く切望されて
いるのが現状である。As described above, at present, there is no moisture-curable reactive hot-melt adhesive composition which sufficiently satisfies the requirements of the market. In the market, a moisture-curing reactive hot that has a fast solidification rate, exhibits strong adhesive and cohesive strength immediately after bonding, has good thermal stability during heating and melting, and can eventually exhibit sufficient heat resistance At present, there is a strong desire for a melt adhesive composition.
【０００８】[0008]
【発明が解決しようとする課題】本発明は上記問題を解
決するものであり、その目的とするところは、固化速度
が速く、接着直後から強い接着力と凝集力を示す接着剤
組成物であり、加熱溶融時の熱安定性が良好で、かつ最
終的には十分な耐熱性を発揮しうる湿気硬化型反応性ホ
ットメルト接着剤組成物を提供することにある。An object of the present invention is to solve the above-mentioned problems, and an object of the present invention is to provide an adhesive composition which has a high solidification rate and exhibits strong adhesive strength and cohesive strength immediately after bonding. Another object of the present invention is to provide a moisture-curable reactive hot-melt adhesive composition which has good thermal stability at the time of heating and melting and which can finally exhibit sufficient heat resistance.
【０００９】[0009]
【課題を解決するための手段】本発明者は上記課題を解
決するために鋭意検討を重ねた結果、湿気硬化型反応性
ホットメルト接着剤組成物の主成分であるウレタンプレ
ポリマーを合成する際に用いられるポリエステルポリオ
ール、ポリエーテルポリオールの代わりに、（Ａ）分子
内にロジン骨格を有するポリエステルポリオール、分子
内にロジン骨格を有するポリエーテルポリオール、テル
ペンフェノール共重合樹脂のうち１種以上を用いると、
（Ｂ）酢酸ビニル含有量２５〜６０％のＥＶＡおよび
（Ｃ）分子内にイソシアネート基と反応しうる官能基を
有するワックスとの相溶性が非常に良くなり、これら
（Ａ）＋（Ｂ）＋（Ｃ）、あるいは（Ａ）＋（Ｃ）の組
み合わせにより上記課題をことごとく解決できることを
見いだした。即ち、本発明のうち第一の発明は以下のと
おりである。ポリイソシアネートからなる第１成分と、
分子内にロジン骨格を有するポリエステルポリオール、
分子内にロジン骨格を有するポリエーテルポリオール、
テルペンフェノール共重合樹脂の中の少なくとも１種か
らなる第２成分と、分子内にイソシアネート基と反応し
うる官能基を有するワックスからなる第３成分と、酢酸
ビニル含有量が２５〜６０重量％であるＥＶＡからなる
第４成分の４成分を必須成分として配合してなる湿気硬
化型反応性ホットメルト接着剤組成物である。また、本
発明のうち第二の発明は以下のとおりである。ポリイソ
シアネートからなる第１成分と、分子内にロジン骨格を
有するポリエーテルポリオールからなる第２成分と、分
子内にイソシアネート基と反応しうる官能基を有するワ
ックスからなる第３成分の３成分を必須成分として配合
してなる湿気硬化型反応性ホットメルト接着剤組成物で
ある。The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have found that when synthesizing a urethane prepolymer which is a main component of a moisture-curable reactive hot melt adhesive composition. When one or more of (A) a polyester polyol having a rosin skeleton in the molecule, a polyether polyol having a rosin skeleton in the molecule, and a terpene phenol copolymer resin are used instead of the polyester polyol and the polyether polyol used in the above. ,
The compatibility with (B) EVA having a vinyl acetate content of 25 to 60% and (C) a wax having a functional group capable of reacting with an isocyanate group in the molecule becomes very good, and these (A) + (B) + It has been found that all the above problems can be solved by the combination of (C) or (A) + (C). That is, the first invention of the present invention is as follows. A first component comprising a polyisocyanate;
Polyester polyol having a rosin skeleton in the molecule,
Polyether polyol having a rosin skeleton in the molecule,
A second component composed of at least one of terpene phenol copolymer resins, a third component composed of a wax having a functional group capable of reacting with an isocyanate group in the molecule, and a vinyl acetate content of 25 to 60% by weight. It is a moisture-curable reactive hot melt adhesive composition comprising four components, a fourth component consisting of a certain EVA, as essential components. The second invention of the present invention is as follows. Indispensable are a first component composed of a polyisocyanate, a second component composed of a polyether polyol having a rosin skeleton in the molecule, and a third component composed of a wax having a functional group capable of reacting with an isocyanate group in the molecule. It is a moisture-curable reactive hot melt adhesive composition formulated as a component.
【００１０】本発明において用いられるポリイソシアネ
ート化合物としては、芳香族、脂肪族または脂環族の各
種公知のポリイソシアネート類を使用することができ
る。例えば、ジフェニルメタンジイソシアネート（ＭＤ
Ｉ）、トリレンジイソシアネート（ＴＤＩ）、ナフチレ
ンジイソシアネート、キシリレンジイソシアネート、ポ
リメチレンポリフェニルポリイソシアネート（ポリメリ
ックＭＤＩ）、ヘキサメチレンジイソシアネート（ＨＤ
Ｉ）、イソホロンジイソシアネート（ＩＰＤＩ）、水添
ジフェニルメタンジイソシアネート（ＨＭＤＩ）、水添
トリレンジイソシアネート等が挙げられる。安全性の面
から、ＭＤＩが好ましく用いられる。As the polyisocyanate compound used in the present invention, various known aromatic, aliphatic or alicyclic polyisocyanates can be used. For example, diphenylmethane diisocyanate (MD
I), tolylene diisocyanate (TDI), naphthylene diisocyanate, xylylene diisocyanate, polymethylene polyphenyl polyisocyanate (polymeric MDI), hexamethylene diisocyanate (HD)
I), isophorone diisocyanate (IPDI), hydrogenated diphenylmethane diisocyanate (HMDI), hydrogenated tolylene diisocyanate, and the like. From the viewpoint of safety, MDI is preferably used.
【００１１】本発明において用いられる分子内にロジン
骨格を有するポリエステルポリオールまたはポリエーテ
ルポリオール（以下、分子内にロジン骨格を有するポリ
オールと称す）は、主に粘着性（タック）と湿気硬化後
の十分な耐熱性を与えるもので、ポリエステルの酸成分
として重合ロジンを使用し、グリコールと反応させて得
るか（特開平３−２５２４９０号公報）、分子中にグリ
シジル基を有する化合物とロジンを反応させて得る（特
開平５−１５５９７２号公報、特開平５−２６３０５９
号公報、特開平７−１７９５５９号公報）ことができ
る。上記分子内にロジン骨格を有するポリオールはすで
に市販されている。例えば、荒川化学工業社製の商品名
ＫＥ−６０１，ＫＥ−６１５−３，ＫＥ−６２２，ＫＥ
−６２４，ＫＥ−６２４改がある。The polyester polyol or polyether polyol having a rosin skeleton in the molecule (hereinafter, referred to as a polyol having a rosin skeleton in the molecule) used in the present invention is mainly composed of tackiness (tack) and sufficient tackiness after moisture curing. A polymerized rosin is used as an acid component of the polyester, and is obtained by reacting with glycol (Japanese Patent Application Laid-Open No. 3-252490) or by reacting a compound having a glycidyl group in the molecule with rosin. (Japanese Unexamined Patent Publication (KOKAI) Hei 5-155972, Japanese Patent Laid-Open Publication No. H5-263059)
JP-A-7-179559). The polyol having a rosin skeleton in the molecule is already commercially available. For example, trade names KE-601, KE-615-3, KE-622, and KE manufactured by Arakawa Chemical Industries, Ltd.
-624, KE-624.
【００１２】本発明において用いられるテルペンフェノ
ール共重合樹脂は、上記分子内にロジン骨格を有するポ
リオールと同じく主に粘着性（タック）と湿気硬化後の
十分な耐熱性を与えるもので、粗製物を用いることもで
きる。テルペンの好ましい例としては、炭素数１０のモ
ノテルペン、即ちα−ピネン、β−ピネン、リモネン
等、及び炭素数２０のジテルペン等が挙げられる。分子
内のフェノール性水酸基の数は特に限定されないが、１
個または２個が好ましい。３個以上の場合は架橋するこ
とにより、ゲル化を起こし易くなる。上記テルペンフェ
ノール共重合樹脂はすでに市販されている。例えば、ヤ
スハラケミカル社製の商品名ＹＰ−９０，ＹＰ−９０
Ｌ，マイティーエースがある。The terpene phenol copolymer resin used in the present invention mainly provides tackiness (tack) and sufficient heat resistance after moisture curing similarly to the above-mentioned polyol having a rosin skeleton in the molecule. It can also be used. Preferred examples of terpenes include monoterpenes having 10 carbon atoms, such as α-pinene, β-pinene, limonene, and diterpenes having 20 carbon atoms. The number of phenolic hydroxyl groups in the molecule is not particularly limited.
Or two are preferred. In the case of three or more, gelation is easily caused by crosslinking. The terpene phenol copolymer resin is already commercially available. For example, YP-90 and YP-90 (trade names, manufactured by Yashara Chemical Co., Ltd.)
L, Mighty Ace.
【００１３】本発明において用いられるイソシアネート
基と反応しうる官能基を有するワックスには、固化速度
を速くし、溶融粘度を下げ、また、湿気硬化反応によっ
て耐熱性を上げる効果がある。該イソシアネート基と反
応しうる官能基としては、水酸基、カルボキシル基、ア
ミノ基、メルカプト基、アミド基等が挙げられ、中でも
イソシアネート基との反応性、入手の容易さ、臭気等の
面から水酸基が好ましい。分子内の官能基の数は特に限
定されないが、１個または２個が好ましい。３個以上の
場合は架橋することにより、ゲル化を起こし易くなる。
上記、水酸基を有するワックスは、固体ワックスであれ
ば、いずれでもよい。例えば、日本精蝋社製の商品名Ｎ
ＰＳ−９２１０，ＯＸ−１９４９や東洋ペトロライト社
製の商品名ユニリン４２５がある。The wax having a functional group capable of reacting with an isocyanate group used in the present invention has the effects of increasing the solidification rate, lowering the melt viscosity, and increasing the heat resistance by a moisture curing reaction. Examples of the functional group capable of reacting with the isocyanate group include a hydroxyl group, a carboxyl group, an amino group, a mercapto group, an amide group and the like. Among them, a hydroxyl group is preferred in view of reactivity with the isocyanate group, availability, and odor. preferable. The number of functional groups in the molecule is not particularly limited, but is preferably one or two. In the case of three or more, gelation is easily caused by crosslinking.
The above wax having a hydroxyl group may be any solid wax. For example, a product name N manufactured by Nippon Seiro
There are PS-9210, OX-1949 and Unilin 425 manufactured by Toyo Petrolite Co., Ltd.
【００１４】本発明の請求項１において用いられるＥＶ
Ａは、得られるウレタンプレポリマーへのゴム弾性付与
に寄与するもので、酢酸ビニル含有量が２５〜６０重量
％、好ましくは３０〜５０重量％のものを使用する。酢
酸ビニル含有量が２５％未満ではウレタンプレポリマー
との相溶性が悪くなり、酢酸ビニル含有量が６０％を越
えると、ＥＶＡ特有のゴム的な性質が不十分となる。Ｅ
ＶＡの配合割合は、多すぎると湿気硬化後の耐熱性が低
下し、少なすぎると十分なゴム弾性が得られないので、
分子内にロジン骨格を有するポリオール、テルペンフェ
ノール共重合樹脂、イソシアネート基と反応しうる官能
基を有するワックスおよびＥＶＡの合計に対して１．０
〜５０重量％、より好ましくは２０〜４０重量％の範囲
で配合するのが好ましい。なお本発明において用いられ
るＥＶＡは、本発明の効果を阻害しない範囲において、
イソシアネート基と反応しうる官能基を有しても良い。[0014] EV used in claim 1 of the present invention
A contributes to imparting rubber elasticity to the obtained urethane prepolymer, and has a vinyl acetate content of 25 to 60% by weight, preferably 30 to 50% by weight. If the vinyl acetate content is less than 25%, the compatibility with the urethane prepolymer becomes poor, and if the vinyl acetate content exceeds 60%, the rubber-like properties unique to EVA become insufficient. E
If the mixing ratio of VA is too large, the heat resistance after moisture curing is reduced, and if it is too small, sufficient rubber elasticity cannot be obtained.
1.0 to the total of a polyol having a rosin skeleton in the molecule, a terpene phenol copolymer resin, a wax having a functional group capable of reacting with an isocyanate group, and EVA.
It is preferable to mix in a range of 50 to 50% by weight, more preferably 20 to 40% by weight. EVA used in the present invention is within a range that does not inhibit the effects of the present invention.
It may have a functional group capable of reacting with an isocyanate group.
【００１５】本発明の請求項２は、分子内にロジン骨格
を有するポリエーテルポリオールにおいて、分子内にロ
ジン骨格を有するポリエーテルポリオールとポリイソシ
アネートを反応させて得られるウレタンプレポリマーの
湿気硬化後のガラス転移点（以下Ｔｇと略す）が特に低
いものを用いることにより、ＥＶＡを用いなくても接着
直後から強い接着力と凝集力を示し、かつ湿気硬化後も
適度なゴム弾性を得ることが可能になる。上記分子内に
ロジン骨格を有するポリエーテルポリオールとポリイソ
シアネートを〔ＮＣＯ〕／〔ＯＨ〕＝２．０（モル比）
の比率で反応して得られるウレタンプレポリマーの場
合、湿気硬化後（６０℃、５０％ＲＨ、７日間養生後）
のＴｇは−７０℃〜０℃である。この請求項２のウレタ
ンプレポリマーの湿気硬化後のＴｇとしては、好ましく
は−７０℃〜−１０℃、さらにより好ましくは−７０℃
〜−２０℃である。このような、ウレタンプレポリマー
の湿気硬化後のＴｇが低いロジン骨格を有するポリエー
テルポリオールとして、荒川化学工業社の商品名ＫＥ−
６２４，ＫＥ−６２４改があり、これらのウレタンプレ
ポリマーの湿気硬化後のＴｇは−３２℃である。A second aspect of the present invention relates to a polyether polyol having a rosin skeleton in the molecule, wherein the urethane prepolymer obtained by reacting the polyether polyol having a rosin skeleton in the molecule with a polyisocyanate after moisture curing. By using a material having a particularly low glass transition point (hereinafter abbreviated as Tg), a strong adhesive force and a cohesive force can be obtained immediately after bonding without using EVA, and a suitable rubber elasticity can be obtained even after moisture curing. become. [NCO] / [OH] = 2.0 (molar ratio) by mixing the polyether polyol having a rosin skeleton in the molecule with the polyisocyanate
In the case of urethane prepolymer obtained by reacting at a ratio of, after moisture curing (after curing at 60 ° C., 50% RH for 7 days)
Has a Tg of -70 ° C to 0 ° C. The Tg of the urethane prepolymer of claim 2 after moisture curing is preferably -70 ° C to -10 ° C, and more preferably -70 ° C.
~ -20 ° C. As such a polyether polyol having a rosin skeleton having a low Tg after moisture curing of the urethane prepolymer, Arakawa Chemical Industry Co., Ltd., trade name KE-
624, KE-624, and the Tg of these urethane prepolymers after moisture curing is -32 ° C.
【００１６】本発明におけるポリイソシアネートの添加
量としては、イソシアネート基と反応しうる官能基に対
するイソシアネート基の比率（以下、イソシアネート比
と称す）が１．０〜５．０、好ましくは１．５〜３．０
となるようにする。イソシアネート比が１．０未満で
は、末端が水酸基のウレタン樹脂となり湿気硬化型反応
性ホットメルト接着剤組成物が得られず、イソシアネー
ト比が５．０を越えると、組成物中に残存する余過剰の
イソシアネートモノマーによって凝集力の低下や固化速
度の低下、湿気硬化時の発泡等の問題が生じる。In the present invention, the ratio of the isocyanate group to the functional group capable of reacting with the isocyanate group (hereinafter referred to as isocyanate ratio) is 1.0 to 5.0, preferably 1.5 to 5.0. 3.0
So that When the isocyanate ratio is less than 1.0, the terminal becomes a urethane resin having a hydroxyl group, and a moisture-curable reactive hot melt adhesive composition cannot be obtained. When the isocyanate ratio exceeds 5.0, the residual excess remaining in the composition is obtained. The isocyanate monomer causes problems such as a decrease in cohesive force, a decrease in solidification rate, and foaming during moisture curing.
【００１７】本発明の湿気硬化型反応性ホットメルト接
着剤組成物は、上述した分子内にロジン骨格を有するポ
リオール、テルペンフェノール共重合樹脂、イソシアネ
ート基と反応しうる官能基を有するワックスおよびＥＶ
Ａを混合することにより得られるが、本発明の作用効果
を阻害しない範囲で、例えば炭酸カルシウム、酸化チタ
ン、硫酸バリウム、タルク、クレー、カーボンブラック
等の充填剤、３級アミン、有機金属化合物等の触媒、ヒ
ンダードフェノール類等の老化防止剤、酸化防止剤、紫
外線吸収剤、難燃剤、着色剤、可塑剤またはオイル等の
添加剤を配合することができる。これら添加剤は特に限
定されるものではなく、通常反応性ホットメルト接着剤
組成物に用いられる従来より公知のものが使用される。The moisture-curable reactive hot melt adhesive composition of the present invention comprises the above-mentioned polyol having a rosin skeleton in its molecule, a terpene phenol copolymer resin, a wax having a functional group capable of reacting with an isocyanate group, and EV.
A can be obtained by mixing A, but a filler such as calcium carbonate, titanium oxide, barium sulfate, talc, clay, or carbon black, a tertiary amine, an organometallic compound, or the like is used as long as the effect of the present invention is not impaired. , An antioxidant such as hindered phenols, an antioxidant, an ultraviolet absorber, a flame retardant, a colorant, a plasticizer, or an oil. These additives are not particularly limited, and conventionally known additives usually used for a reactive hot melt adhesive composition are used.
【００１８】本発明の湿気硬化型反応性ホットメルト接
着剤組成物を製造するためには、上述したポリイソシア
ネートに、分子内にロジン骨格を有するポリオール、テ
ルペンフェノール共重合樹脂、イソシアネート基と反応
しうる官能基を有するワックスおよびＥＶＡを加えて反
応させてもよいし、分子内にロジン骨格を有するポリオ
ール、テルペンフェノール共重合樹脂、イソシアネート
基と反応しうる官能基を有するワックスおよびＥＶＡを
先に混合溶融しておいてからポリイソシアネートと反応
させてもよい。In order to produce the moisture-curable reactive hot melt adhesive composition of the present invention, the above-mentioned polyisocyanate is reacted with a polyol having a rosin skeleton in the molecule, a terpene phenol copolymer resin, and an isocyanate group. Or a wax having a functional group capable of reacting with an isocyanate group, and a polyol having a rosin skeleton in the molecule, and an EVA may be mixed first. After melting, it may be reacted with the polyisocyanate.
【００１９】[0019]
【発明の実施の態様】以下に製造例および実施例を挙げ
て本発明をさらに詳しく説明するが、本発明はこれらの
実施例のみに限定されるものではない。以下、部および
％は特記しない限り重量基準である。BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail with reference to production examples and examples, but the present invention is not limited to these examples. Hereinafter, parts and% are by weight unless otherwise specified.
【００２０】実施例１ ロジン骨格含有ポリオール（荒川化学工業社製ＫＥ−６
２２（水酸基価９４．１、酸価４．４））２０．００
部、アルコール型ワックス（日本精蝋社製ＮＰＳ−９２
１０（水酸基価８０、酸価１０））２０．００部、ＥＶ
Ａ（三井・デュポンポリケミカル社製ＥＶ４５Ｘ（酢酸
ビニル含有量４６％、メルトフローレート９５））２
０．００部および湿気硬化促進触媒（和光純薬社製ジブ
チルチンジラウレート（ＤＢＴＤＬ））０．０３９４部
を１３０℃にて混合溶融し、４５分間真空脱泡した後、
窒素気流下でジフェニルメタンジイソシアネート（日本
ポリウレタン工業社製ミリオネートＭＴ（ＭＤＩ））１
８．６９部を加え、１３０℃で４５分間反応を行い湿気
硬化型反応性ホットメルト接着剤組成物を得た。結果は
表１に示す。Example 1 A rosin skeleton-containing polyol (KE-6 manufactured by Arakawa Chemical Industries, Ltd.)
22 (hydroxyl value 94.1, acid value 4.4)) 20.00
Part, alcohol-type wax (NPS-92, manufactured by Nippon Seiro)
10 (hydroxyl value 80, acid value 10)) 20.00 parts, EV
A (EV45X manufactured by DuPont-Mitsui Polychemicals, Inc. (vinyl acetate content 46%, melt flow rate 95)) 2
After mixing and melting 0.00 parts and 0.0394 parts of a moisture curing acceleration catalyst (dibutyltin dilaurate (DBTDL) manufactured by Wako Pure Chemical Industries, Ltd.) at 130 ° C. and defoaming for 45 minutes,
Under a nitrogen stream, diphenylmethane diisocyanate (Millionate MT (MDI) manufactured by Nippon Polyurethane Industry Co., Ltd.) 1
8.69 parts were added and reacted at 130 ° C. for 45 minutes to obtain a moisture-curable reactive hot melt adhesive composition. The results are shown in Table 1.
【００２１】実施例２ ロジン骨格含有ポリエーテルポリオール（荒川化学工業
社製ＫＥ−６２４改、水酸基価３３．９、酸価０．１）
３０．００部、アルコール型ワックス（日本精蝋社製Ｎ
ＰＳ−９２１０）３０．００部および湿気硬化促進触媒
（和光純薬社製ジブチルチンジラウレート（ＤＢＴＤ
Ｌ））０．０３９３部を１３０℃にて混合溶融し、４５
分間真空脱泡した後、窒素気流下でジフェニルメタンジ
イソシアネート（日本ポリウレタン工業社製ミリオネー
トＭＴ（ＭＤＩ））１８．５５部を加え、１３０℃で４
５分間反応を行い湿気硬化型反応性ホットメルト接着剤
組成物を得た。結果は表１に示す。Example 2 Polyether polyol having a rosin skeleton (KE-624, modified by Arakawa Chemical Industries, hydroxyl value 33.9, acid value 0.1)
30.00 parts, alcohol-type wax (Nippon Seiwa Co., Ltd. N
PS-9210) and 30.00 parts of a moisture curing accelerating catalyst (dibutyltin dilaurate (DBTD manufactured by Wako Pure Chemical Industries, Ltd.)
L)) 0.0393 parts were mixed and melted at 130 ° C.
After vacuum degassing for 1 minute, 18.55 parts of diphenylmethane diisocyanate (Millionate MT (MDI) manufactured by Nippon Polyurethane Industry Co., Ltd.) was added under a nitrogen stream, and the mixture was added at 130 ° C. for 4 minutes.
The reaction was carried out for 5 minutes to obtain a moisture-curable reactive hot melt adhesive composition. The results are shown in Table 1.
【００２２】実施例３ ロジン骨格含有ポリオール（荒川化学工業社製ＫＥ−６
２２）２０．００部、アルコール型ワックス（日本精蝋
社製ＮＰＳ−９２１０）２０．００部、ＥＶＡ（三井・
デュポンポリケミカル社製ＥＬＶＡＸ１４０Ｗ（酢酸ビ
ニル含有量３３％、メルトフローレート４００））２
０．００部および湿気硬化促進触媒（和光純薬社製ジブ
チルチンジラウレート（ＤＢＴＤＬ））０．０３９４部
を１３０℃にて混合溶融し、４５分間真空脱泡した後、
窒素気流下でジフェニルメタンジイソシアネート（日本
ポリウレタン工業社製ミリオネートＭＴ（ＭＤＩ））１
８．６９部を加え、１３０℃で４５分間反応を行い湿気
硬化型反応性ホットメルト接着剤組成物を得た。結果は
表１に示す。Example 3 A rosin skeleton-containing polyol (KE-6 manufactured by Arakawa Chemical Industries, Ltd.)
22) 20.00 parts, alcohol-type wax (NPS-9210 manufactured by Nippon Seiro) 20.00 parts, EVA (Mitsui
ELVAX140W manufactured by DuPont Polychemicals (vinyl acetate content 33%, melt flow rate 400)) 2
After mixing and melting 0.00 parts and 0.0394 parts of a moisture curing acceleration catalyst (dibutyltin dilaurate (DBTDL) manufactured by Wako Pure Chemical Industries, Ltd.) at 130 ° C. and defoaming for 45 minutes,
Under a nitrogen stream, diphenylmethane diisocyanate (Millionate MT (MDI) manufactured by Nippon Polyurethane Industry Co., Ltd.) 1
8.69 parts were added and reacted at 130 ° C. for 45 minutes to obtain a moisture-curable reactive hot melt adhesive composition. The results are shown in Table 1.
【００２３】実施例４ ロジン骨格含有ポリオール（荒川化学工業社製ＫＥ−６
２２）２０．００部、アルコール型ワックス（日本精蝋
社製ＮＰＳ−９２１０）２０．００部、ＥＶＡ（三井・
デュポンポリケミカル社製ＥＬＶＡＸ４３１０（酸価
５．６、メタクリル酸含有量１％、酢酸ビニル含有量２
５％、メルトフローレート５００））２０．００部およ
び湿気硬化促進触媒（和光純薬社製ジブチルチンジラウ
レート（ＤＢＴＤＬ））０．０３９６部を１３０℃にて
混合溶融し、４５分間真空脱泡した後、窒素気流下でジ
フェニルメタンジイソシアネート（日本ポリウレタン工
業社製ミリオネートＭＴ（ＭＤＩ））１９．２４部を加
え、１３０℃で４５分間反応を行い湿気硬化型反応性ホ
ットメルト接着剤組成物を得た。結果は表２に示す。Example 4 A rosin skeleton-containing polyol (KE-6 manufactured by Arakawa Chemical Industries, Ltd.)
22) 20.00 parts, alcohol-type wax (NPS-9210 manufactured by Nippon Seiro) 20.00 parts, EVA (Mitsui
ELVAX4310 manufactured by DuPont Polychemicals (acid value 5.6, methacrylic acid content 1%, vinyl acetate content 2
5%, melt flow rate 500)) 20.00 parts and moisture curing accelerating catalyst (dibutyltin dilaurate (DBTDL) 0.0396 parts, manufactured by Wako Pure Chemical Industries, Ltd.) were mixed and melted at 130 ° C., and vacuum degassing was performed for 45 minutes. Thereafter, 19.24 parts of diphenylmethane diisocyanate (Millionate MT (MDI) manufactured by Nippon Polyurethane Industry Co., Ltd.) was added under a nitrogen stream, and the mixture was reacted at 130 ° C. for 45 minutes to obtain a moisture-curable reactive hot melt adhesive composition. The results are shown in Table 2.
【００２４】実施例５ ロジン骨格含有ポリエーテルポリオール（荒川化学工業
社製ＫＥ−６２４（水酸基価３８．６、酸価２．１））
３０．００部、テルペンフェノール共重合樹脂（ヤスハ
ラケミカル社製ＹＰ−９０Ｌ（水酸基価２９１．３、酸
価４８．２））７．５０部、アルコール型ワックス（日
本精蝋社製ＮＰＳ−９２１０）２２．５０部および湿気
硬化促進触媒（和光純薬社製ジブチルチンジラウレート
（ＤＢＴＤＬ））０．０３４８部を１３０℃にて混合溶
融し、４５分間真空脱泡した後、窒素気流下でジフェニ
ルメタンジイソシアネート（日本ポリウレタン工業社製
ミリオネートＭＴ（ＭＤＩ））１６．７７部を加え、１
３０℃で４５分間反応を行い湿気硬化型反応性ホットメ
ルト接着剤組成物を得た。結果は表２に示す。Example 5 Rosin skeleton-containing polyether polyol (KE-624, manufactured by Arakawa Chemical Industry Co., Ltd. (hydroxyl value 38.6, acid value 2.1))
30.00 parts, 7.50 parts of terpene phenol copolymer resin (YP-90L (hydroxyl value 291.3, acid value 48.2) manufactured by Yashara Chemical Co., Ltd.), alcohol type wax (NPS-9210 manufactured by Nippon Seirosu Co., Ltd.) 22 .50 parts and 0.0348 parts of a moisture hardening promoting catalyst (dibutyltin dilaurate (DBTDL) manufactured by Wako Pure Chemical Industries, Ltd.) were mixed and melted at 130 ° C., vacuum degassed for 45 minutes, and then diphenylmethane diisocyanate (Japan) under a nitrogen stream. 16.77 parts of Millionate MT (MDI) manufactured by Polyurethane Industry Co., Ltd.
The reaction was carried out at 30 ° C. for 45 minutes to obtain a moisture-curable reactive hot melt adhesive composition. The results are shown in Table 2.
【００２５】実施例６ ロジン骨格含有ポリオール（荒川化学工業社製ＫＥ−６
０１（水酸基価１１３．５、酸価０．１））１０．００
部、ロジン骨格含有ポリオール（荒川化学工業社製ＫＥ
−６２４改）１５．００部、アルコール型ワックス（日
本精蝋社製ＮＰＳ−９２１０）２０．００部、ＥＶＡ
（三井・デュポンポリケミカル社製ＥＶ４５Ｘ）２０．
００部および湿気硬化促進触媒（和光純薬社製ジブチル
チンジラウレート（ＤＢＴＤＬ））０．０４１１部を１
３０℃にて混合溶融し、４５分間真空脱泡した後、窒素
気流下でジフェニルメタンジイソシアネート（日本ポリ
ウレタン工業社製ミリオネートＭＴ（ＭＤＩ））１７．
１１部を加え、１３０℃で４５分間反応を行い湿気硬化
型反応性ホットメルト接着剤組成物を得た。結果は表２
に示す。Example 6 A rosin skeleton-containing polyol (KE-6 manufactured by Arakawa Chemical Industries, Ltd.)
01 (hydroxyl value 113.5, acid value 0.1)) 10.00
Part, rosin skeleton-containing polyol (KE from Arakawa Chemical Co., Ltd.)
-624) 15.00 parts, alcohol-type wax (NPS-9210 manufactured by Nippon Seiro) 20.00 parts, EVA
(EV45X manufactured by DuPont-Mitsui Polychemicals) 20.
00 parts and 0.0411 parts of a moisture curing acceleration catalyst (dibutyltin dilaurate (DBTDL) manufactured by Wako Pure Chemical Industries, Ltd.)
After mixing and melting at 30 ° C. and vacuum degassing for 45 minutes, diphenylmethane diisocyanate (Millionate MT (MDI) manufactured by Nippon Polyurethane Industry Co., Ltd.) under a nitrogen stream.
11 parts were added and reacted at 130 ° C. for 45 minutes to obtain a moisture-curable reactive hot melt adhesive composition. Table 2 shows the results
Shown in
【００２６】実施例７ ロジン骨格含有ポリオール（荒川化学工業社製ＫＥ−６
２２）２０．００部、アルコール型ワックス（日本精蝋
社製ＮＰＳ−９２１０）２０．００部、ＥＶＡ（三井・
デュポンポリケミカル社製ＥＬＶＡＸ１４０Ｗ）３０．
００部および湿気硬化促進触媒（和光純薬社製ジブチル
チンジラウレート（ＤＢＴＤＬ））０．０４４４部を１
３０℃にて混合溶融し、４５分間真空脱泡した後、窒素
気流下でジフェニルメタンジイソシアネート（日本ポリ
ウレタン工業社製ミリオネートＭＴ（ＭＤＩ））１８．
６９部を加え、１３０℃で４５分間反応を行い湿気硬化
型反応性ホットメルト接着剤組成物を得た。結果は表３
に示す。Example 7 Rosin skeleton-containing polyol (KE-6 manufactured by Arakawa Chemical Industries, Ltd.)
22) 20.00 parts, alcohol-type wax (NPS-9210 manufactured by Nippon Seiro) 20.00 parts, EVA (Mitsui
ELVAX140W manufactured by DuPont Polychemicals) 30.
00 parts and 0.0444 parts of a moisture curing acceleration catalyst (dibutyltin dilaurate (DBTDL) manufactured by Wako Pure Chemical Industries, Ltd.)
After mixing and melting at 30 ° C. and degassing in vacuo for 45 minutes, diphenylmethane diisocyanate (Millionate MT (MDI) manufactured by Nippon Polyurethane Industry Co., Ltd.) under a nitrogen stream.
69 parts were added and reacted at 130 ° C. for 45 minutes to obtain a moisture-curable reactive hot melt adhesive composition. Table 3 shows the results
Shown in
【００２７】比較例１ ポリヘキサメチレンアジペート（日本ポリウレタン工業
社製Ｎ−１３６（水酸基価４２．４、酸価０．２））６
０．００部と湿気硬化促進触媒（和光純薬社製ジブチル
チンジラウレート（ＤＢＴＤＬ））０．０３６３部を１
３０℃にて混合溶融し、４５分間真空脱泡した後、窒素
気流下でジフェニルメタンジイソシアネート（日本ポリ
ウレタン工業社製ミリオネートＭＴ（ＭＤＩ））１２．
５３部を加え、１３０℃で４５分間反応を行い湿気硬化
型反応性ホットメルト接着剤組成物を得た。得られた湿
気硬化型反応性ホットメルト接着剤組成物は、初期接着
力が不十分で基材と界面剥離した。結果は表３に示す。Comparative Example 1 Polyhexamethylene adipate (N-136, Nippon Polyurethane Industry Co., Ltd. (hydroxyl value 42.4, acid value 0.2)) 6
0.00 parts and 0.0363 parts of a moisture curing acceleration catalyst (dibutyltin dilaurate (DBTDL) manufactured by Wako Pure Chemical Industries, Ltd.)
After mixing and melting at 30 ° C. and degassing in vacuo for 45 minutes, diphenylmethane diisocyanate (Millionate MT (MDI) manufactured by Nippon Polyurethane Industry Co., Ltd.) under a nitrogen stream 12.
53 parts were added and reacted at 130 ° C. for 45 minutes to obtain a moisture-curable reactive hot melt adhesive composition. The resulting moisture-curable reactive hot melt adhesive composition had insufficient initial adhesive strength and peeled off at the interface with the substrate. The results are shown in Table 3.
【００２８】比較例２ ポリヘキサメチレンアジペート（日本ポリウレタン工業
社製Ｎ−１３６）４０．００部、ＥＶＡ（三井・デュポ
ンポリケミカル社製ＥＶ４５Ｘ）２０．００部および湿
気硬化促進触媒（和光純薬社製ジブチルチンジラウレー
ト（ＤＢＴＤＬ））０．０３４２部を１３０℃にて混合
溶融し、４５分間真空脱泡した後、窒素気流下でジフェ
ニルメタンジイソシアネート（日本ポリウレタン工業社
製ミリオネートＭＴ（ＭＤＩ））８．３６部を加え、１
３０℃で反応を行ったが、相溶性が悪く用に供し得なか
った。結果は表３に示す。Comparative Example 2 40.00 parts of polyhexamethylene adipate (N-136, manufactured by Nippon Polyurethane Industry Co., Ltd.), 20.00 parts of EVA (EV45X, manufactured by DuPont-Mitsui Polychemicals) and a catalyst for accelerating moisture curing (Wako Pure Chemical Industries, Ltd.) 0.0342 parts of dibutyltin dilaurate (DBTDL)) was mixed and melted at 130 ° C., degassed in vacuum for 45 minutes, and then diphenylmethane diisocyanate (Millionate MT (MDI) manufactured by Nippon Polyurethane Industry Co., Ltd.) 8.36 under a nitrogen stream. Add one part
The reaction was carried out at 30 ° C., but the compatibility was poor and could not be used. The results are shown in Table 3.
【００２９】比較例３ ポリヘキサメチレンアジペート（日本ポリウレタン工業
社製Ｎ−１３６）４０．００部、アルコール型ワックス
（日本精蝋社製ＮＰＳ−９２１０）２０．００部および
湿気硬化促進触媒（和光純薬社製ジブチルチンジラウレ
ート（ＤＢＴＤＬ））０．０３８７部を１３０℃にて混
合溶融し、４５分間真空脱泡した後、窒素気流下でジフ
ェニルメタンジイソシアネート（日本ポリウレタン工業
社製ミリオネートＭＴ（ＭＤＩ））１７．３９部を加
え、１３０℃で４５分間反応を行い湿気硬化型反応性ホ
ットメルト接着剤組成物を得た。結果は表４に示す。Comparative Example 3 40.00 parts of polyhexamethylene adipate (N-136, manufactured by Nippon Polyurethane Industry Co., Ltd.), 20.00 parts of alcohol-type wax (NPS-9210, manufactured by Nippon Seiwa Co., Ltd.) and a catalyst for accelerating moisture hardening (Wako Pure Chemical Industries, Ltd.) 0.0387 parts of dibutyltin dilaurate (DBTDL) manufactured by Yakuhin Co., Ltd. were mixed and melted at 130 ° C., degassed under vacuum for 45 minutes, and then diphenylmethane diisocyanate (Millionate MT (MDI) manufactured by Nippon Polyurethane Industry Co., Ltd.) 17 under a nitrogen stream. After adding 39 parts, the mixture was reacted at 130 ° C. for 45 minutes to obtain a moisture-curable reactive hot melt adhesive composition. The results are shown in Table 4.
【００３０】比較例４ ポリヘキサメチレンアジペート（日本ポリウレタン工業
社製Ｎ−１３６）４０．００部、ロジン骨格含有ポリオ
ール（荒川化学工業社製ＫＥ−６２２（水酸基価９７．
３、酸価３．７））２０．００部および湿気硬化促進触
媒（和光純薬社製ジブチルチンジラウレート（ＤＢＴＤ
Ｌ））０．０３９２部を１３０℃にて混合溶融し、４５
分間真空脱泡した後、窒素気流下でジフェニルメタンジ
イソシアネート（日本ポリウレタン工業社製ミリオネー
トＭＴ（ＭＤＩ））１８．２７部を加え、１３０℃で４
５分間反応を行い湿気硬化型反応性ホットメルト接着剤
組成物を得た。結果は表４に示す。Comparative Example 4 40.00 parts of polyhexamethylene adipate (N-136 manufactured by Nippon Polyurethane Industry Co., Ltd.) and a rosin skeleton-containing polyol (KE-622 manufactured by Arakawa Chemical Industry Co., Ltd.
3, acid value 3.7)) 20.00 parts and a moisture-curing acceleration catalyst (dibutyltin dilaurate (DBTD manufactured by Wako Pure Chemical Industries, Ltd.)
L)) 0.0392 parts were mixed and melted at 130 ° C.
After vacuum degassing for 1 minute, 18.27 parts of diphenylmethane diisocyanate (Millionate MT (MDI) manufactured by Nippon Polyurethane Industry Co., Ltd.) was added under a nitrogen stream, and the mixture was added at 130 ° C. for 4 minutes.
The reaction was carried out for 5 minutes to obtain a moisture-curable reactive hot melt adhesive composition. The results are shown in Table 4.
【００３１】比較例５ アルコール型ワックス（日本精蝋社製ＮＰＳ−９２１
０）２０．００部、ＥＶＡ（三井・デュポンポリケミカ
ル社製ＥＶ４５Ｘ）２０．００部および湿気硬化促進触
媒（和光純薬社製ジブチルチンジラウレート（ＤＢＴＤ
Ｌ））０．０２４５部を１３０℃にて混合溶融し、４５
分間真空脱泡した後、窒素気流下でジフェニルメタンジ
イソシアネート（日本ポリウレタン工業社製ミリオネー
トＭＴ（ＭＤＩ））９．０３部を加え、１３０℃で４５
分間反応を行い湿気硬化型反応性ホットメルト接着剤組
成物を得た。得られた湿気硬化型反応性ホットメルト接
着剤組成物は、基材と界面剥離しやすく、硬化後の耐熱
性も低下していた。結果は表４に示す。Comparative Example 5 Alcohol-type wax (NPS-921 manufactured by Nippon Seiro Co., Ltd.)
0) 20.00 parts, EVA (EV45X manufactured by DuPont-Mitsui Polychemicals Co., Ltd.) 20.00 parts and a moisture-curing acceleration catalyst (dibutyltin dilaurate (DBTD manufactured by Wako Pure Chemical Industries, Ltd.)
L)) 0.0245 parts were mixed and melted at 130 ° C.
After defoaming in vacuo for one minute, 9.03 parts of diphenylmethane diisocyanate (Millionate MT (MDI) manufactured by Nippon Polyurethane Industry Co., Ltd.) was added under a nitrogen stream,
The reaction was carried out for 1 minute to obtain a moisture-curable reactive hot melt adhesive composition. The obtained moisture-curable reactive hot-melt adhesive composition was liable to peel off at the interface with the substrate, and the heat resistance after curing was also reduced. The results are shown in Table 4.
【００３２】比較例６ ロジン骨格含有ポリオール（荒川化学工業社製ＫＥ−６
２２）２０．００部、ＥＶＡ（三井・デュポンポリケミ
カル社製ＥＶ４５Ｘ）２０．００部および湿気硬化促進
触媒（和光純薬社製ジブチルチンジラウレート（ＤＢＴ
ＤＬ））０．０２５０部を１３０℃にて混合溶融し、４
５分間真空脱泡した後、窒素気流下でジフェニルメタン
ジイソシアネート（日本ポリウレタン工業社製ミリオネ
ートＭＴ（ＭＤＩ））９．９１部を加え、１３０℃で反
応を行なったが、溶融粘度が高く用に供し得なかった。
結果は表５に示す。Comparative Example 6 A rosin skeleton-containing polyol (KE-6 manufactured by Arakawa Chemical Industries, Ltd.)
22) 20.00 parts, EVA (EV45X manufactured by DuPont-Mitsui Polychemicals Co., Ltd.) 20.00 parts and a moisture hardening accelerating catalyst (dibutyltin dilaurate (DBT manufactured by Wako Pure Chemical Industries, Ltd.)
DL)) 0.0250 parts were mixed and melted at 130 ° C.
After vacuum degassing for 5 minutes, 9.91 parts of diphenylmethane diisocyanate (Millionate MT (MDI) manufactured by Nippon Polyurethane Industry Co., Ltd.) was added under a nitrogen stream, and the reaction was carried out at 130 ° C., but the melt viscosity was high and could be used. Did not.
The results are shown in Table 5.
【００３３】比較例７ ロジン骨格含有ポリオール（荒川化学工業社製ＫＥ−６
２２）２０．００部、アルコール型ワックス（日本精蝋
社製ＮＰＳ−９２１０）２０．００部および湿気硬化促
進触媒（和光純薬社製ジブチルチンジラウレート（ＤＢ
ＴＤＬ））０．０２９５部を１３０℃にて混合溶融し、
４５分間真空脱泡した後、窒素気流下でジフェニルメタ
ンジイソシアネート（日本ポリウレタン工業社製ミリオ
ネートＭＴ（ＭＤＩ））１８．９４部を加え、１３０℃
で４５分間反応を行い湿気硬化型反応性ホットメルト接
着剤組成物を得た。得られた湿気硬化型反応性ホットメ
ルト接着剤組成物は、硬化後に脆くなり耐熱性も低下し
ていた。結果は表５に示す。Comparative Example 7 Rosin skeleton-containing polyol (KE-6 manufactured by Arakawa Chemical Industries, Ltd.)
22) 20.00 parts, alcohol-type wax (Nippon Seiro Co., Ltd. NPS-9210) 20.00 parts and moisture curing accelerating catalyst (Wako Pure Chemical Industries dibutyltin dilaurate (DB)
TDL)) mixing and melting 0.0295 parts at 130 ° C.
After vacuum degassing for 45 minutes, 18.94 parts of diphenylmethane diisocyanate (Millionate MT (MDI) manufactured by Nippon Polyurethane Industry Co., Ltd.) was added under a nitrogen stream, and 130 ° C.
For 45 minutes to obtain a moisture-curable reactive hot melt adhesive composition. The resulting moisture-curable reactive hot melt adhesive composition was brittle after curing and had reduced heat resistance. The results are shown in Table 5.
【００３４】比較例８ ロジン骨格含有ポリオール（荒川化学工業社製ＫＥ−６
２４改）３０．００部と湿気硬化促進触媒（和光純薬社
製ジブチルチンジラウレート（ＤＢＴＤＬ））０．０１
７５部を１３０℃にて混合溶融し、４５分間真空脱泡し
た後、窒素気流下でジフェニルメタンジイソシアネート
（日本ポリウレタン工業社製ミリオネートＭＴ（ＭＤ
Ｉ））５．００部を加え、１３０℃で４５分間反応を行
い湿気硬化型反応性ホットメルト接着剤組成物を得た。
結果は表５に示す。Comparative Example 8 Rosin skeleton-containing polyol (KE-6 manufactured by Arakawa Chemical Industries, Ltd.)
24) 30.00 parts and moisture curing acceleration catalyst (dibutyltin dilaurate (DBTDL) manufactured by Wako Pure Chemical Industries, Ltd.) 0.01
After mixing and melting 75 parts at 130 ° C. and degassing in vacuo for 45 minutes, diphenylmethane diisocyanate (Millionate MT (MD manufactured by Nippon Polyurethane Industry Co., Ltd.)
I)) 5.00 parts was added and reacted at 130 ° C. for 45 minutes to obtain a moisture-curable reactive hot melt adhesive composition.
The results are shown in Table 5.
【００３５】上記湿気硬化型反応性ホットメルト接着剤
組成物を下記の方法で評価を行った。結果を表１〜５に
示す。 イ） 相溶性 目視により相溶性を確認した（○：透明、○〜△：曇り
あり（透明感あり）、△：曇りあり（透明感なし）、△
〜×：白濁、×：相分離）。 ロ） セッティングタイム 湿気硬化型反応性ホットメルト接着剤組成物をハンドガ
ンで２５ｍｍ幅のＫライナー紙に２ｍｍφで片面塗布し
て２秒後に貼り合わせ、１ｋｇ荷重で所定時間圧着し、
その後直ちにはがす。このときの材料破壊率が８０％以
上になる圧着時間をセッティングタイムとした。 ハ） せん断接着力、昇温せん断破壊温度 湿気硬化型反応性ホットメルト接着剤組成物をハンドガ
ンで２５ｍｍ幅の基材に２ｍｍφで片面塗布して２秒後
に貼り合わせ、１ｋｇ荷重で２秒間圧着し、 その後２
３℃／４５〜６０％ＲＨで所定時間養生し、せん断接着
力（合板／合 板、引っ張り速度１００ｍｍ／ｍｉｎ）
および昇温せん断破壊温度（Ｋライナ ー紙／Ｋライナ
ー紙、荷重１ｋｇ、昇温速度０．４℃／ｍｉｎ）を、１
２６℃ まで昇温し、測定実施（Ａ：界面剥離、Ｃ：凝
集破壊、Ｓ：材料破壊）。The moisture-curable reactive hot melt adhesive composition was evaluated by the following method. The results are shown in Tables 1 to 5. B) Compatibility Compatibility was visually confirmed (○: transparent, ○ to Δ: cloudy (transparency), Δ: cloudy (no transparency), Δ
-X: cloudy, x: phase separation). B) Setting time The moisture-curable reactive hot melt adhesive composition is applied to a 25 mm wide K liner paper with a hand gun at 2 mmφ on one side, then bonded 2 seconds later, and pressed with a 1 kg load for a predetermined time.
Remove immediately afterwards. The pressing time at which the material destruction rate at this time was 80% or more was defined as the setting time. C) Shear adhesive strength, elevated temperature Shear breaking temperature The moisture-curable reactive hot melt adhesive composition was applied to a 25 mm-wide base material with a hand gun at 2 mmφ on one side, and after 2 seconds, bonded together and pressed at 1 kg load for 2 seconds. , Then 2
Cured at 3 ° C./45-60% RH for a predetermined time, shear adhesive strength (plywood / plywood, pulling speed 100 mm / min)
And the heating shear fracture temperature (K liner paper / K liner paper, load 1 kg, heating rate 0.4 ° C / min)
The temperature was raised to 26 ° C., and the measurement was performed (A: interfacial peeling, C: cohesive failure, S: material fracture).
【００３６】[0036]
【表１】 [Table 1]
【００３７】[0037]
【表２】 [Table 2]
【００３８】[0038]
【表３】 [Table 3]
【００３９】[0039]
【表４】 [Table 4]
【００４０】[0040]
【表５】 [Table 5]
【００４１】[0041]
【発明の効果】本発明の湿気硬化型反応性ホットメルト
接着剤組成物は、従来より公知の湿気硬化型反応性ホッ
トメルト接着剤組成物と比較して、固化速度が非常に速
く、接着直後から強い接着力と凝集力を示すので、作業
工程の大幅な短縮が可能である。さらに、本発明で用い
られる分子内にロジン骨格を有するポリオール、テルペ
ンフェノール共重合樹脂、分子内にイソシアネート基と
反応しうる官能基を有するワックスおよび酢酸ビニル含
有量２５〜６０％のＥＶＡは、互いに相溶性が優れてい
るため、多数の異なる用途や使用条件に対して広範囲の
性能のグレードを選別使用でき、微妙な物性の調整にも
適合できる。EFFECT OF THE INVENTION The moisture-curable reactive hot melt adhesive composition of the present invention has a very high solidification rate as compared with the conventionally known moisture-curable reactive hot melt adhesive composition, Since it exhibits strong adhesive and cohesive strength, the working process can be significantly reduced. Furthermore, the polyol having a rosin skeleton in the molecule, the terpene phenol copolymer resin, the wax having a functional group capable of reacting with an isocyanate group in the molecule, and the EVA having a vinyl acetate content of 25 to 60% used in the present invention are mutually compatible. Due to its excellent compatibility, a wide range of performance grades can be selected and used for many different applications and use conditions, and can be adapted to fine adjustment of physical properties.
【００４２】また、本発明において、テルペンフェノー
ル共重合樹脂、イソシアネート基と反応しうる官能基を
有するワックスおよびＥＶＡは、従来の湿気硬化型反応
性ホットメルト接着剤組成物の主な原料であるポリエス
テルポリオールと比較して安価であり、本発明の作用効
果を発揮するだけでなくコストダウンにも寄与する。In the present invention, a terpene phenol copolymer resin, a wax having a functional group capable of reacting with an isocyanate group and EVA are polyesters which are the main raw materials of the conventional moisture-curable reactive hot melt adhesive composition. It is inexpensive as compared with polyols and contributes not only to the effect of the present invention but also to cost reduction.
Claims (2)
と、分子内にロジン骨格を有するポリエステルポリオー
ル、分子内にロジン骨格を有するポリエーテルポリオー
ル、テルペンフェノール共重合樹脂の中の少なくとも１
種からなる第２成分と、分子内にイソシアネート基と反
応しうる官能基を有するワックスからなる第３成分と、
酢酸ビニル含有量が２５〜６０重量％であるエチレン−
酢酸ビニル共重合体からなる第４成分の４成分を必須成
分として配合してなる湿気硬化型反応性ホットメルト接
着剤組成物。1. A first component comprising a polyisocyanate, at least one of a polyester polyol having a rosin skeleton in a molecule, a polyether polyol having a rosin skeleton in a molecule, and a terpene phenol copolymer resin
A second component comprising a seed, a third component comprising a wax having a functional group capable of reacting with an isocyanate group in the molecule,
Ethylene having a vinyl acetate content of 25 to 60% by weight
A moisture-curable reactive hot melt adhesive composition comprising, as essential components, four components, a fourth component comprising a vinyl acetate copolymer.
と、分子内にロジン骨格を有するポリエーテルポリオー
ルからなる第２成分と、分子内にイソシアネート基と反
応しうる官能基を有するワックスからなる第３成分の３
成分を必須成分として配合してなる湿気硬化型反応性ホ
ットメルト接着剤組成物。2. A first component comprising a polyisocyanate, a second component comprising a polyether polyol having a rosin skeleton in the molecule, and a third component comprising a wax having a functional group capable of reacting with an isocyanate group in the molecule. 3
A moisture-curable reactive hot melt adhesive composition comprising the components as essential components.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP35807796A JP4055216B2 (en) | 1996-12-28 | 1996-12-28 | Moisture curable reactive hot melt adhesive composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP35807796A JP4055216B2 (en) | 1996-12-28 | 1996-12-28 | Moisture curable reactive hot melt adhesive composition |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| JPH10195413A true JPH10195413A (en) | 1998-07-28 |
| JPH10195413A5 JPH10195413A5 (en) | 2004-07-08 |
| JP4055216B2 JP4055216B2 (en) | 2008-03-05 |
Family
ID=18457424
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP35807796A Expired - Fee Related JP4055216B2 (en) | 1996-12-28 | 1996-12-28 | Moisture curable reactive hot melt adhesive composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4055216B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6525162B1 (en) | 1999-06-11 | 2003-02-25 | Eastman Chemical Resins, Inc. | Polyols, polyurethane systems and polyurethane reactive hot melt adhesives produced therefrom |
| JP2003515637A (en) * | 1999-12-01 | 2003-05-07 | エイチ・ビー・フラー・ライセンシング・アンド・ファイナンシング・インコーポレイテッド | Improved reactive hot melt adhesive |
| JP2016113552A (en) * | 2014-12-16 | 2016-06-23 | Dic株式会社 | Moisture-curable hot-melt urethane composition and adhesive |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017029075A1 (en) | 2015-08-19 | 2017-02-23 | Unilever Plc | Apparatus and process for handling food packaging |
-
1996
- 1996-12-28 JP JP35807796A patent/JP4055216B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6525162B1 (en) | 1999-06-11 | 2003-02-25 | Eastman Chemical Resins, Inc. | Polyols, polyurethane systems and polyurethane reactive hot melt adhesives produced therefrom |
| JP2003515637A (en) * | 1999-12-01 | 2003-05-07 | エイチ・ビー・フラー・ライセンシング・アンド・ファイナンシング・インコーポレイテッド | Improved reactive hot melt adhesive |
| JP2016113552A (en) * | 2014-12-16 | 2016-06-23 | Dic株式会社 | Moisture-curable hot-melt urethane composition and adhesive |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4055216B2 (en) | 2008-03-05 |
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