United States Patent 19 Konishi et al. A AA 'USOOSSIODITA, Patent Number: 5,410,011 Date of Patent: Apr. 25, 1995 a 13) [54] ONE-COMPONENT POLYURETHANE TYPE, ADHESIVE, AND USE THEREOF Inventors: Shin Konishi, Fujisawa; Shinji ‘Hirayama, Hadano; Takao Hidai, ‘Anjo; Yukihiro Morikawa; Koichi ‘Uchara, both of Yokohama; Sadako ‘Hashimoto, Hadano, all of Japan Inoae Corp; Nippon Polyurethane Industry Co., Ltd. 109,099 py Aug. 19, 1993 [30] Foreign Application Priority Data Dee. 4, 1992 UP] ve 4350068 fs] mas [2] Us.c. 75) [73] Assignees: [21] Appl. No. Filed: Japan GoaG 18/79 vue 528/735 528/45; 528/67, 528/905 528/73, 45, 67, 905, [58] Field of Search. 4 References Cited US. PATENT DOCUMENTS $04,171 8/197T Malle et on ane 4480874 2/1984 Sehmursch Gt a won 824/590 44442280 4/1984. Grogler etal. ‘24/56 S46R158 7/1984 Disteldoe et 518/85 445201186 5/1985 Hess eral. 5/73 $801,668 1/1989 Ucyanagi et al. 5/08 53143994 9/1992 Laas etal 528/45 FOREIGN PATENT DOCUMENTS (0120813 7/1983. Japan - 2-620 1/1990 Japan Primary Examiner—Jobn Kight, 11 ‘Assistant Examiner—R. F. Johnson ‘Attorney, Agent, or Firm—Davis Hoxie Faithfull & Hapgood [1] ABSTRACT ‘A one-component type polyurethane adhesive: com- prising, as a main component, a polyurethane precursor ‘Prepared by reaction of apolyisocyanate component (3) Containing one or more polyisocyanate compounds (el) mention below and optionally one or more poly- ‘isocyanates (@-2) mention below with an active hydro- ‘gen compound (b) having a molecular weight of from 18 to 20,000 and having two or more active hydrogen ‘groups in the molecule, at an equivalent ratio of the active hydrogen group of the active hydrogen com- ‘pound component (b) to the isocyanate group of the polyisooyanate component (@) of more than 1.0; the polyurethane precursor containing a uretdione group and the active hydrogen group at an equivalent ratio of. the uretdione group to the active hydrogen groups of from 0.25 to 1.0, (e1): a polyisocyanate compound having at least a turetdione group in the molecule thereof, and (22): 2 polyisocyanate having two or more isocyanate groups in the molecule thereof. 38 Claims, No Drawings5,410,011 1 (ONE-COMPONENT POLYURETHANE TYPE ADHESIVE, AND USE THEREOF BACKGROUND OF THE INVENTION 5 1. Field of the Invention ‘The present invention relates to a one-component type polyurethane adhesive, more particularly, 10 a ‘one-component type polyurethane adhesive which Comprises a polyurethane precursor as a main compo- nent having uretdione groups and active hydrogen ‘groups at a prescribed ratio and which cures by chain extension and crosslinking on simple heating without evolution of a free polyisocysnate monomer, and is excellent in operability and safety, and the use thereof. 2. Related Background Art Polyurethane type adhesives used for general pur- pose are mostly of solvent types from the standpoint of cease of operation. Polyurethane adhesives are roughly clasified into the following three classes according to the curing mechanism, ‘The first clas of the adhesives are two-component type polyurethane adhesives, in which a first compo- nent of @ polyisocyanste and/or an isocyanateer- ‘inated prepolymer with a second component of a Tow-moleeular-weight polyol and/or urethane-modi- fied polyol having molecular weight of less than 10,000, and are mixed immediately before application, and ap- plied to a base material (adherend) to be cured. The second clas ofthe adhesives are moisture-curing, type polyurethane adhesives, which contain an isocya- nate-erminated prepolymer and cure by reaction with active hydrogen groups ofa base material or moisture in the air. This group includes non-solvent type reactive hot-melt adhesives which are melted ata temperature of 100° C. or higher, applied to a base material and cooled to solidify to exhibit initial adhesive force, and later react with active hydrogens on the base material or moisture in sir to be cured by polymerization and cross- 40 0 1s 20 3s ‘Te third clas of adhesives are one-can lacquer type polyurethane adhesives, which are a solution or disper- Sion ofa high-molecular-weight thermoplastic polyare- thane resin in a solvent of Water, and the slation is 45 applied to a base material. The high-molecular-weight polyarethane resin having high cohesive energy forms adhesive layer to exhibit adhesive force by simple evap- Oration of the solvent or the water. ‘The respective classes of adhesives have advantages and disadvantages as described below. ‘The two-component type polyurethane adhesive forms an adhesive layer which has generally a cross linked structure and is superior in heat-resstance and durability. However, its pot life is limited because the liquid formulation of the two components becomes viscous due to the reaction of the isocyanate group With the hydroxy group in the system, and gels finaly. ‘The moifurecuring type polyarcthane adhesive forms an adhesive layer which gives final adhesive force weaker than a two-component type polyurethane adhesive but are superior in heat resistance and other properties. Since the adhesive force is usually caused by {he eaction with moisture on the base material orn ir the adhesive has disadvantages that the reaction pro- ceeds slowly andthe initial adhesive force is exhibited slowiy, and the adhesiveness depends on external condi- tions such as low temperature and low humicity in ss 2 winter, and high temperature and high humidity in “The above two clases of adhesives, namely the two- ‘component type polyurethane adhesives and the mois ture-coring type polyurethane adhesives, contain a free polyisocyanate monomer in a slight amount in the sys- fem. The fre polysocyanate monomer tends to agara- ‘ate working environment depending onthe conditions of application ofthe adhesive, and frequently neces tates local ventilation. The one-can lacquer type poly trethane adhesive, which isa solution of higvmolect- Jar-weight polyurethane resin such as a thermoplastic polyurethane solution, has a semipermanent pot life Unless the solvent isnot evaporated, and sexily han- dle. This type of adhesive, however, forms an adhesive layer which has themmopiasety and a low melting point duc to no erossinked structure, and therefor the featresitance is low since the adhesion strength thereot falls a «temperature exceeding the softening temperate. ‘Many proposals have been presented regarding im- provement of polyurethane adhesives. For example, fegnrding the one component Iaequer type polyare: thane adhesives, «proposal s presented that a polyso- cyanate curing agent add thereto ((o-pack type). ‘Regarding the two component type polyurchuane adhe. sive, composition of «blocked focyanate is proposed ‘whichis seomingly a one component sytem and com- prises an isocyanate caring gent blocked witha block- ing agent that generates cyanate groups by disocia tion and evaporation ofthe blocking agent in heating higher than 120° C. and a low-molecular-weight polyol ani/or a urethane-modified polyol. Use ofthis compo- Sition sil involves problems of adhesive layer foaming cased bythe blocking agent, pollution eaused by evap- cation of the blocking agent, drop of adhesive force resulting from residual blocking agent, and so forth. ‘Therefore, this composition rarely used for adhesives, although tis used asa one-pak pant system in some of pant application elds, Regarding moisture-curing type polyurethane adhesive, there i proposed a formulation ‘hich i es affected by external conditions asthe re Jus of incorporation ofa hygroscopic composition or a catalyst; a seemingly one component system which Gontanh a curing agent sich af Kermine compound (Schiff base) and aldimine compound to generate an Sino group in contact with modtore, and an cya. tateerminated prepolymer system; and s0 forth. No complete one component type adhesive as not been obtained whichis storable for along time. Therefore, the development thereof is strongly demanded st the moment. Furthermore, from the global environmental prob- Jems, VOC (Volatile Organic Compound) regulation is being tightened, and movements toward resource com. servation, son-pollition and higher safety ae require in the fils of paints, adhesives, and inks. fn view ofthe decreasing polltion,achesives snd prints of high-solid {ype powder coating type, water-borne type, and hot rel type are attracting attention. At presen, however, any hipisolid type or nonsolvent type polyurethane adhesive for general purpose has not been developed ‘which satisfy both the ease of handling and the excellent Characersics of the solvent type polyurethane adhe- Sive containing a large amount ofa solvent. Therefore, the development thereof is strongly demanded. More- over, development of a polyurethane adhesive which5,410,011 3 satisfies the VOC regulation and contains no free isocy- ‘nate monomer is strongly demanded. ‘On the other hand, uretdione group-containing poly. urethane resins are already known (See: Kunststoff- hhanébuch, Volum VIL, pages 17 to 37 (1966). Itis also 5 Known that a uretdione group-containing compound ‘opens the uretdione group which is a dimer of isocya- nate group to regenerate two isocyanate groups (J. H. Saunders, K. C. Frisch: Polyurethanes, Chemistry and ‘technology, Part 1, p. 113 (1962), Interscience Publish- es) Further, uretdione group-containing polyisocyanate compounds and related application techniques are Known as shown in U.S. Pat. Nos. 4,044,171, 4.430.474, 4,442,280 and 4,801,663; and Japanese Patent Applica. tion Laid-open No. Hei-2-620; and so forth. The tech- niques relating to toluene diisocyanate dimer have long ‘been known in the field of powder coating and millable rubber hardeners, Uretdione group-containing polyure- ‘thane resins of isophorone diisocyanate type and diphe- nylmethane diisocyanate type have come to be known, recently. ‘The features of the novel polyurethane adhesive of the present invention to meet the above demands are: () sufficient adhesiveness to various base materials and excellent film properties owing to high cohesive energy ‘characteristic of conventional polyurethane adhesives, (@ ease of handling in coating and spraying owing to Tow viscosity which is achieved by two-component type polyurethane adhesives, (3) excellent heat-resist- ance and excellent durability owing to crosilinking formed by reaction at the time of adhesion, (4) semiper- manent storage stability and long pot life which are achievable by lacquer type adhesives and blocked iso ‘eyanate systems, (5) no liberation of no evaporation of free polyisocyanate monomer during formulation and heating, and reduction of the amount of a solvent to ‘meet the VOC regulation for environment protection, and (6) high-solid type, non-solvent type, oF solid type of adhesive SUMMARY OF THE INVENTION ‘The present invention intends to provide a one-com- ponent type polyurethane adhesive which has the fea- tures of (1) high adhesiveness to base materials and ‘excellent film properties, (2) low viscosity and resulting superiority of handling in coating, spraying, and other processes, (3) excellent heatresistance and durability ‘owing to crosslinked structure, ($) semipermanent stor- age stability and po life, (5) no liberation or no evapora- 50 tion of free polyisocyanate during operation and (6) the possibilty of development of not only high solid type Dut also of non-solvent type, and solid type. ‘The one-component type polyurethane adhesive ac- cording to the present invention comprises, as a main ‘component, a polyurethane precursor prepared by reac: tion of @ polyisocyanate component (8) containing one or more polyisocyanate compounds (a-1) mentioned below and optionally one or more polyisocyanates (@-2) mentioned below with an active hydrogen compound 60 (©) having 2 molecular weight of from 18 to 20,000 and having two or more active hydrogen groups in the ‘molecule, at an equivalent ratio of the active hydrogen _group of the active hydrogen compound component () to the isocyanate group of the polyisocyanate compo- nent (2) of more than 1.0; the polyurethane precursor ‘containing a ureidione group and the active hydrogen ‘groups at an equivalent ratio of the uretdione group to 10 2» 2 20 35 6s 4 the active hydrogen group of from 0.25 to 1.0; (@-1):a polyisocyanate compound having at least a uretdione ‘eroup in the molecule thereof; and (3-2) a polyisooya- nate having two or more isocyanate groups in the mole- cale thereof. ‘The aforementioned polyisocyanate compound (2-1) is preferably the one which has a uretdione group, and an isocyanurate group, and if desired, another group derived from an isocyanate group. ‘Another embodiment of the one-component type polyurethane adhesive according to the present inven- tion contains forther another active hydrogen com- pound having a molecular weight of from 18 to 20,000 and having two or more active hydrogens in the mole- cule additionally in such an amount that the equivalent ratio of the uretdione group to the total of the active hydrogen groups ofthe polyurethane precursor and the active hydrogen groups of the additional active hydro- gen compound is in the range of from 0.25 to 1.0. ‘In practical use the adhesive ofthe present invention, ‘the one-component type polyurethane adhesive is ap- plied to an adherend at a temperature lower than the dissociation temperature of the uretdione group and then heated to a temperature higher than the dissocia- tion temperature to cause reaction and curing, or other- ‘wise the one-component type polyurethane adhesive is heated to a temperature higher than the dissociation ‘temperature of the uretdione and then applied to an adherend to cause reaction and curing, BRIEF DESCRIPTION OF THE PREFERRED EMBODIMENT ‘The present invention provides a one-component type polyurethane adhesive, which comprises a poly- urethane precursor as a main component containing. uretdione groups and active hydrogen groups at a pre= scribed ratio. ‘The polyisocyanate compound (a-1) inthe polyisocy- ‘anate component (a) has at least a uretdione group in the ‘molecule, and, if necessary, may have an isocyanurate {group and further a group which is derived from an fsocyanate group and is different from the above two groups (uretone-imine group and isocyanurate group). ‘This group which is derived from an isocyanate group and is diferent from a uretdione group and an socyanu- rate group includes a urethane group, a carbodiimide group, a uretone-imine group, oxazolidone group, a hydantoin group and the like. One or more kinds of the polyisocyanate compound (a-1) may be used. For exam- ple, the polyisocyanate compound (2-1) may be a mix- ture of a polyisocyanate compound having a uretdione {group and another polyisocyanate compound having. both a uretdione group and an isoeyanurate compound. ‘The polyisocyanate compound (@-2) in the polyisocy- nate component (a) has two or more isocyanate groups in the molecule. The polyisocyanate compound (2-2) ‘may be a combination of two or more thereof. ‘The polyisocyanate for forming the aforementioned polyisocyanate compound (a-1), or 2 polyisocyanate (@-2) includes not only free polyisocyanate monomers ‘but polymeric forms thereof. The polyisocyanate monomer specifically includes aromatic diisocyanates such as known 2y¢-tolylene di- isocyanate (hereinafter referred to as “TDI"), 2,6-1oly- lene diisocyanate, xylene-1,4-diisocyanate, xylene-1,3- isocyanate, 4,4-diphenylmethane disocyanate (here inafter referred to as “MDI"), 44" Gelation oocurring within oe day: Gelatin oocurring for 1 to 3 days: & Viscosity rising by 10% oF les after 7 days: © Stable for 21 days or more: @) @ Measurement of Working Environment ‘The free poyisocyanate monomer in the working environment was detected by GC measuremeat ofthe Smple taken fom the atmosphere inthe adhesive-for rulating step 23" C) and the drying step (160" C). (@) Coating Properties and Coating Appearance ‘The coming properties were evaluated daring sppli cation, and the appearance (Foaming or non-faming) of the coating fim was evaluated immediately after drying ‘on the bass ofthe evalation standard belo: “ Excelent ©)>0> Ax Poor @ ital Adhesivenes ‘The inital adhesiveness was evaluated by measuring the tensile shear strength immediately after the bonding under the aforementioned conditions (@) Shear Strength, HeatResistance, and Water Resistance “The shear strength, the hes resistance, and the water resistance of the bonded matter was measured With a completely cured sample afer the standing at room temperature. The shea strength was evaluated by ten- sie shearing est. The heat-resitance was evalusied by the heating bonding test (C) under «load of 1 for 25 mm breadth. The water restance. was evaluated from the retention ratio (9) ofthe bonding strength of the bonded sample afer kept standing in water t $0" C. for 3 hours, “ Excellent > 0>A>x Poor ‘The one-component type polyurethane ofthe present invention, s desorbed above, has the strong adhesive- nes, which san advantage of conventional two-com- ponent type polyurethane adhesives, aswell as satisac- tory easy in osing long pot life and storage stability, ‘which are advantages of blocked isocyanate type adhe. Sives. The adhesive ofthe present invention has semi permanent storage stability and pot lie since i's of @ Snecomponent type. This adhesive is cured on hesting up to the ring-opening tempersuce of the uretdione troup by reaction with an active hydrogen group to five excellent heatresitance and excellent durability. By suitable selection ofthe skeleton structure and the active hydrogen compound, the adhesive ofthe present invention is expable of exhibiting strong adhesiveness and excellent fm characteristics on various base mate- Fal. Moreover, the adhesive ofthe present fvention in ordinary temperate doesnot contain a free polyisocy" ante monomer which causes environmental problems, and it doesnot generate a free poyisoeyanate monomer ven at coating proces at «high temperature, unlike Some blocked isoeyanate. Therefore, the adbesve ofthe present invention is haneabiesfely without aggravas fon of working environment5,410,011 a7 18 TABLE 1 nmple! Erne? Bumps Eamples Eames ocmiaton Rata of Adio Mais component Fa) Syuthess SyuthssSyutbeeSyetbede Synthesis Euimple! Etmple? Enmple} Eumples Example 5 1. ee ae ary 1% Astin (gt) as ost acs as as ‘Sotvent (etene MEK) (pars) ° ° ° 2 ° Pedormance of Adpve fees eee = 2 8 8 8 8 8 8 8 8 8 @ oO Q @ oO 2 8 8 8 & ener rn ‘Sheat strength”) (kef/em?) 280,20" 280, 21% 290, 18* 240, 19* 288, 21% loo 3.8 joo @ 6 2a aus or seek ight alas or ste/PET, TABLE2 ‘Congaratve Comparative Conpanive ‘Eample! “Example? “Example ‘Main component ars) Comparative Comparative Comparative Syuibas Sys Sys Ezimple! Example? Buamale Assis (pas) os as os Sotvent aes (pars) o ° 6 Pevlormasce of Adhesive Vscosty (225°C) o so 20 sob asc) x 8 @ Goo) x x 3 Datecen of ee 05ppm ot ot palaocyanste monomer 25°C) Coaing properties a Q @ ‘Appearance (eaming or zon fans) a 3° Bg Beka otf oitpm mt ppm ‘olvsccyanttemosomer (10° C) Tnvaladhervenes een) a5 59 15,2 Shear engi tem") 52 se Hewressatee @ A x Waterernce 6 4 a eth efor, are ees aaa renee a coh aoe = porte Paes a eS 8 ee yo3 2 ome ce cae oa 2 con 8 8 8 en aoe oo Eecinwee 8 8 8 palyboeyanate monomer 180 C)5,410,011 19 20 TABLE 3-contiued Eranpe ¢ Fag Eamgiet aterm 2 aa m9 Ser een oeseah ae ae ibe Wacabe 8 § 8 et aes forsee ig ates se PE, What is claimed is: 1. A one-component polyurethane adhesive compris- ing, as a main component, a polyurethane precursor Prepared by reaction of a polyisocyanate component (a) ‘comprising at leat one polyisocyanate compound (a-1) ‘with an active hydrogen compound selected from the group consisting of water and a compound having a molecular weight of les than 20,000 and having two or ‘more active hydrogen groups, at an equivalent ratio of the active hydrogen group of the ative hydrogen com- ‘pound to the isocyanate group of the polyisocyanate ‘component (a) of more than 1.0; the polyurethane pre- ‘cursor containing uretdione group and the active hydrogen group at an equivalent ratio of the uretdione _gToup to the active hydrogen groups of from 0.25 to 1.0, where (a-1) is a polyisooyanate compound having at least a uretdione group and an isocyanurate group and is formed from hexamethylene diisocyanate or polymeric forms of hexamethylene diisocyanate. 2. A one-component polyurethane adhesive accord- ing to claim 1, wherein the polyisocyanate compound (1) comprises a uretdione group, an isocyanurate group, and further groups, other than uretdione and isocyanurate groups, derived from an isocyanate group. 3. The one-component polyurethane adhesive of claim 1 where the polyisocyanate component (a) further ‘comprises at least one additional polyisocyanate (a-2) having at least two isocyanate groups. ‘4. The one-component polyurethane adhesive ac- ‘cording to claim 2 wherein the further groups compris- ing the polyisocyanate compound (@-1) are selected from the group consisting of a urethane group, carbodi- ‘mide group, uretoneimine group, oxazolidone group and a ydantoin group. ‘5. The one-component polyurethane adhesive ac- ‘cording to claim 3 wherein the polyisocyanate (#2) is formed from polyisocyanate monomer selected from the group consisting of 2,4tolylene diisocyanate, 4,4 diphenylmethane diisocyanate, hexamethylene disocy- nate, polymeric forms of 2,4-tolylene diisocyanate, polymeric forms of 4,4~-diphenylmethane diisocyanate, ‘and polymeric forms of hexamethylene diisocyanate. 6. The one-component polyurethane adhesive of claim 1, further comprising another active hydrogen, ‘compound having two or more active hydrogen groups in the molecule in such an amount that the equivalent ratio of the uretdione group to the total of the active hydrogen groups of the polyurethane precursor and the active hydrogen groups of the additionally contained. active hydrogen compound is inthe range of from 0.25 wo 10, 7. The one-component polyurethane adhesive ac- cording to claim 1 wherein the active hydrogen com- pound is selected from the group consisting of polyols, lea resins, melamine resins, epoxy resins, polyester resins, acrylic resins and polyvinyl resins 8. The one-component polyurethane adhesive ac- cording to clsim 7 wherein the polyols have a function: ality of 2 to prevent gelation in the polyurethane pre- » 3s 0 45 0 6 9. A one-component polyurethane adhesive compris- ing, 8 a main component, a polyurethane precursor prepared by reaction ofa polyisooyanate component (a) ‘Comprising a first polyisocyanate and a second polyiso- ‘cyanate with an active hydrogen compound (b) at an ‘equivalent ratio of the active hydrogen group of the active hydrogen compound component (b) tothe isocy- ‘nate group of the polyisocyanate component (a) of ‘more than 1.0; the polyurethane precursor containing a luretdione group and the active hydrogen group at an equivalent ratio of the uretdione group to the active hydrogen groups of from 025 to 1.0, where the first polyisocyanate has at least a uretdione group and an ‘socyanurate group and is formed from hexamethylene diisocyanate or polymeric forms of hexamethylene di- ‘isocyanate and the second polvisocyanate has at least ‘wo isocyanate groups; and further where the one-com- ponent type polyurethane adhesive has neither a free polysoeyanate monomer or free isocyanate group at 25°C. 410. A method of use of the one-component adhesive according to claim 1 comprising applying the one-com- [ponent adhesive to an adherend ata temperature below the ring-opening temperature of the uretdione group nd then heating the one-component adhesive above the ring-opening temperature. IL. A method of use of the one-component adhesive according to claim 1 comprising heating the one-com- ponent adhesive above the ring-opening temperature of the uretdione group and then applying the one-compo- nent adhesive to an adherend. 12, A method of use of the one-component adhesive according to claim 2 comprising applying the one-com- ponent adhesive to an adherend at a temperature below the ring-opening temperature of the uretdione group ‘and then heating the one-component adhesive above the ring-opening temperature, 13, A method of use of the one-component adhesive according to claim 2 comprising heating the one-com- ‘ponent adhesive above the ring-opening temperature of the uretdione group and then applying the one-compo- neat adhesive to an adherend. 14. A method of use of the one-component adhesive of claim 3 comprising applying the one-component adhesive to an adherend at a temperature below the ring-opening temperature of the uretdione group and ‘then heating the one-component adhesive above the ring-opening temperature, 15, A method of use of the one-component adhesive of claim 3 comprising heating the one-component adhe sive above the ring-opening temperature of the uretd~ fone group and then applying the one-component adhe- sive to an adherend. 16. The one-component adhesive according to claim 1 which includes a plasticizer. 17. The one-component adhesive according to claim 16 which includes filler. 18, The one-component adhesive according to claim 17 which includes an antioxidant