Urethane-based adhesive for automobile

Abstract

The present invention provides an adhesive composition which is a primerless urethane-based adhesive and has high adhesive force with respect to a polyolefin-based resin. An adhesive composition according to the present invention is a two-liquid type urethane-based adhesive composition comprising: a main agent which comprises (A) a urethane prepolymer having an isocyanate group at the end thereof, (B) a polyfunctional isocyanate compound having an alkoxysilyl group which can be obtained through a reaction of a silane compound having at least two alkoxysilyl groups in one molecule and a polyisocyanate having an isocyanate group at the end thereof and (C1) a first curing catalyst; and a curing agent which comprises (D) a hydrophobic polyol and (C2) a second curing catalyst.

Claims

1. A two-liquid type urethane-based adhesive comprises at least: a main agent comprising: (A) a urethane prepolymer having an isocyanate group at the end thereof; (B) an alkoxysilyl group-containing polyfunctional isocyanate compound which is obtained through a reaction of a silane compound having two or more alkoxysilyl groups in one molecule and a polyisocyanate having an isocyanate group at the end thereof, wherein the silane compound having two or more alkoxysilyl groups in one molecule is a bissilylamine compound represented by the following chemical formula 1: ##STR00019## where: each of six R.sup.1s is independently an alkyl group having 1 to 3 carbon atoms; and each of two R.sup.2s is independently an alkylene group having 1 to 10 carbon atoms, and wherein the polyisocyanate is a polyfunctional isocyanate compound selected from a group consisting of: an isocyanurate-type polyfunctional isocyanate being a cyclic trimer of a diisocyanate, wherein the polyisocyanate is represented by the following chemical formula 4: ##STR00020## where: each of three R.sup.3s is independently a linear or cyclic alkylene group which may be substituted with an alkyl group, an alkoxysilyl group, an acyl group, an alkoxycarbonyl group or a carboxyl group; or an organic group having a phenylene group which may be substituted with an alkyl group, an alkoxysilyl group, an acyl group, an akoxycarbonyl group or a carboxyl group; a biuret-type polyfunctional isocyanate being an adduct of a diisocyanate to a urea group formed of a diisocyanate and an amine, wherein the polyisocyanate is represented by the following chemical formula 5: ##STR00021## where: each of three R.sup.4s is independently a linear or cyclic alkylene group which may be substituted with an alkyl group, an alkoxysilyl group, an acyl group, an alkoxycarbonyl group or a carboxyl group; or an organic group having a phenylene group which may be substituted with an alkyl group, an alkoxysilyl group, an acyl group, an alkoxycarbonyl group or a carboxyl group; an adduct-type polyfunctional isocyanate being an adduct of a diisocyanate to a poly-hydric alcohol, wherein the polyisocyanate is represented by the following chemical formula 6: ##STR00022## where: each of three R.sup.5s is independently a linear or cyclic alkylene group which may be substituted with an alkyl group, an alkoxysilyl group, an acyl group, an alkoxycarbonyl group or a carboxyl group; or an organic group having a phenylene group which may be substituted by any of an alkyl group, an alkoxysilyl group, an acyl group, an alkoxycarbonyl group or a carboxyl group, and X is a trivalent hydrocarbon group having 1 to 3 carbon atoms; and an allophanate-type polyfunctional isocyanate being an adduct of a diisocyanate to a urethane group formed of a diisocyanate and an alcohol, wherein the polyisocyanate is represented by the following chemical formula 7: ##STR00023## where: each of two R.sup.6s is independently a linear or cyclic alkylene group which may be substituted with an alkyl group, an alkoxysilyl group, an acyl group, an alkoxycarbonyl group or a carboxyl group; or an organic group having a phenylene group which may be substituted by any of an alkyl group, an alkoxysilyl group, an acyl group, an alkoxycarbonyl group or a carboxyl group, and Y is an alkyl group having 1 to 3 carbon atoms; and (C1) a first curing catalyst, and a curing product comprising (D) a hydrophobic polyol and a polyoxyalkylene polyol, and (C2) a second curing catalyst.

2. The two-liquid type urethane-based adhesive according to claim 1, wherein (A) the urethane prepolymer having an isocyanate group at the end thereof is a prepolymer formed by a reaction through a polyol and an isocyanate.

3. The two-liquid type urethane-based adhesive according to claim 2, wherein at least a part of the polyol is one or more polyol selected from a group consisted of a hydrogenated polyisoprene polyol, a rosin-modified polyol and a polybutadiene polyol.

4. The two-liquid type urethane-based adhesive according to claim 1, wherein the polyfunctional isocyanate compound having an alkoxysilyl group is a bissilylamine group-bonded polyfunctional isocyanate compound represented by the following chemical formula 10: ##STR00024##

5. The two-liquid type urethane-based adhesive according to claim 1, wherein the (D) hydrophobic polyol is selected from a group consisted of a hydrogenated polyisoprene polyol, a rosin-modified polyol, and a polybutadiene polyol.

6. The two-liquid type urethane-based adhesive according to claim 1 further comprising a filler or a plasticizer.

7. The two-liquid type urethane-based adhesive according to claim 1, wherein (C1) the first curing catalyst and (C2) the second curing catalyst are respectively selected from the group consisting of an organotin compound; 2,2-dimorpholinodiethyl ether, di(2,6-dimethylmorpholinoethyl)ether; bismuth carboxylate; carboxylic acid; triethylenediamine and a salt thereof; N,N-dimethylaminoethylmorpholine; bis(2-dimethylaminoethyl) ether; 1,8-diazabicyclo(5,4,0)undecene-7 and a salt thereof; imidazole-based compound.

8. The two-liquid type urethane-based adhesive according to claim 1, wherein the polyoxyalkylene polyol has a weight-average molecular weight of 100 to 10,000.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is a schematic cross-sectional view of a sample for shear adhesion strength testing.

(2) The urethane-based adhesive of the present invention comprises at least: (A) a urethane prepolymer having an isocyanate group at the end thereof; (B) an alkoxysilyl group-containing polyfunctional isocyanate compound which is obtained through a reaction of a silane compound having two or more alkoxysilyl groups in one molecule and a polyisocyanate having an isocyanate group at the end thereof; and (C) a curing catalyst.

(3) The urethane-based adhesive of the present invention may be a one-liquid type moisture-curing adhesive composition.

(4) The urethane-based adhesive of the present invention may further comprise (D) a polyol to make a two-liquid type adhesive composition which comprises; a main agent comprising (A) a urethane prepolymer having an isocyanate group at the end thereof; (B) an alkoxysilyl group-containing polyfunctional isocyanate compound which is obtained through a reaction of a silane compound having two or more alkoxysilyl groups in one molecule and a polyisocyanate having an isocyanate group at the end thereof; and (C1) a first curing catalyst; and a curing product comprising (D) a polyol; and (C2) a second curing catalyst.

(5) The urethane prepolymer (A) used as a main component in the adhesive composition in the present invention is a urethane prepolymer having an isocyanate group at the end thereof (hereinafter referred to as NCO-terminated prepolymer). The NCO-terminated prepolymer may be produced by reacting an excess amount of a polyisocyanate compound (in general, OH/NCO=1/1.5-1/4.0) with respect to various polyols in the usual manner. The polyols include, for example, polyether polyol such as polyoxyalkylene polyol, polyether polyol-modified product and polytetramethylene ether glycol; polyester polyol such as condensation-based polyester polyol, lactone-based polyester polyol, and polycarbonate diol; a polyol whose main chain consists of CC bonds, such as acrylic polyol, polybutadiene-based polyol, polyolefin-based polyol, saponified ethylene-vinyl acetate copolymer; and others such as flame-retardant polyols, phosphorus-containing polyols, and halogen-containing polyol. The polyisocyanate compounds include, for example, tolylene diisocyanate (TDI), 4,4-diphenylmethane diisocyanate (MDI), xylene diisocyanate (XDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), lysine diisocyanate, isopropylidenebis(4-cyclohexylisocyanate), pentamethylene diisocyanate (PDI), hydrogenated XDI etc.

(6) The alkoxysilyl group-containing polyfunctional isocyanate compound (B) used as an adherence agent in the present invention may be obtained through a reaction of a silane compound having two or more alkoxysilyl groups in one molecule and a polyisocyanate having an isocyanate group at the end thereof.

(7) The silane compound having two or more alkoxysilyl groups in one molecule in order to obtain the adherence agent used in the present invention include, but not limited to, for example, a bissilylamine compound represented by the following chemical formula 1:

(8) ##STR00001##
where: each of six R.sup.1s is independently an alkyl group having 1 to 3 carbon atoms; and each of two Res is independently an alkylene group having 1 to 10 carbon atoms. More specifically, it is a bis[3-(trimethoxy)silylpropyl]amine represented by the following chemical formula 2:

(9) ##STR00002##
or a N-Phenyl-N-[3-(trimethoxysilyl)propyl]-2-hydroxy-3-(trimethoxysilyl)propoxypropylamine represented by the following chemical formula 3:

(10) ##STR00003##

(11) The diisocyanates which constitutes the polyisocyanate having an isocyanate group at the end thereof in order to obtain the adherence agent in the present invention includes, but not limited to, for example, an aromatic isocyanates such as tolylene diisocyanate (TDI), 4,4-diphenylmethane diisocyanate (MDI), xylene diisocyanate (XDI); and an aliphatic isocyanate such as hexamethylene diisocyanate (HDI), pentamethylene diisocyanate (PDI), lysine diisocyanate, isophorone diisocyanate (IPDI), isopropylidenebis(4-cyclohexylisocyanate) and hydrogenated XDI.

(12) The polyisocyanate includes, but not limited to, more specially, an isocyanurate-type polyfunctional isocyanate being a cyclic trimer of a diisocyanate represented by the following chemical formula 4:

(13) ##STR00004##
where: each of three R.sup.3s is independently a linear or cyclic alkylene group which may be substituted with an alkyl group, an alkoxysilyl group, an acyl group, an alkoxycarbonyl group or a carboxyl group; or an organic group having a phenylene group which may be substituted with an alkyl group, an alkoxysilyl group, an acyl group, an akoxycarbonyl group or a carboxyl group; a biuret-type polyfunctional isocyanate being an adduct of a diisocyanate to a urea group formed of a diisocyanate and an amine, wherein the polyisocyanate is represented by the following chemical formula 5:

(14) ##STR00005##
where: each of three R.sup.4s is independently a linear or cyclic alkylene group which may be substituted with an alkyl group, an alkoxysilyl group, an acyl group, an alkoxycarbonyl group or a carboxyl group; or an organic group having a phenylene group which may be substituted with an alkyl group, an alkoxysilyl group, an acyl group, an alkoxycarbonyl group or a carboxyl group; an adduct-type polyfunctional isocyanate being an adduct of a diisocyanate to a poly-hydric alcohol, wherein the polyisocyanate is represented by the following chemical formula 6:

(15) ##STR00006##
where: each of three R.sup.5s is independently a linear or cyclic alkylene group which may be substituted with an alkyl group, an alkoxysilyl group, an acyl group, an alkoxycarbonyl group or a carboxyl group; or an organic group having a phenylene group which may be substituted with an alkyl group, an alkoxysilyl group, an acyl group, an alkoxycarbonyl group or a carboxyl group, and X is a trivalent hydrocarbon group having 1 to 3 carbon atoms; and an allophanate-type polyfunctional isocyanate being an adduct of a diisocyanate to a urethane group formed of a diisocyanurate and an alcohol, wherein the polyisocyanate is represented by the following chemical formula 7:

(16) ##STR00007##
where: each of two R.sup.6s is independently a linear or cyclic alkylene group which may be substituted with an alkyl group, an alkoxysilyl group, an acyl group, an alkoxycarbonyl group or a carboxyl group; or an organic group having a phenylene group which may be substituted by any of an alkyl group, an alkoxysilyl group, an acyl group, an alkoxycarbonyl group or a carboxyl group, and Y is an alkyl group having 1 to 3 carbon atoms.

(17) The polyisocyanate compound having an isocyanate group at the end thereof in order to obtain the adherence agent in the present invention further includes, for example, a polyurethane prepolymer represented by the following chemical formula 8:

(18) ##STR00008##
where: each of two R.sup.7s is independently a linear or cyclic alkylene group which may be substituted by any of an alkyl group, an alkoxysilyl group, an acyl group, an alkoxycarbonyl group or a carboxyl group; or an organic group having a phenylene group which may be substituted by any of an alkyl group, an alkoxysilyl group, an acyl group, an alkoxycarbonyl group or a carboxyl group, and Z is an oxyalkylene group having 1 to 40 carbon atoms, which may be substituted.

(19) The oxyalkylene group having 1 to 40 carbon atoms, which may be substituted with an alkylene group having 1 to 3 carbon atoms, being represented by Z in the above polyurethane prepolymer, includes, but not limited to, for example, the oxyalkylene groups represented by the following chemical formula 9:

(20) ##STR00009##

(21) The adherence agent used in the present invention may be obtained through a reaction of the above silane compound and the above polyisocyanate. A polyfunctional isocyanate compound having two or more alkoxysilyl groups may be obtained by bonding at least one isocyanate group of a plurality of isocyanate groups which the polyisocyanate has and a functional group of a silane compound. As such a polyfunctional isocianate compound, one example of a bissilylamine group-bonded polyfunctional isocyanate compound which may be obtained through a reaction of a hexamethylene diisocyanate (HDI) biuret and a bis[3-(trimethoxy)silylpropyl]amine is represented by the following chemical formula 10:

(22) ##STR00010##

(23) The content of the component (B) is 0.5 parts by weight or more, preferably 1.0 parts by weight or more, and more preferably 2 parts by weight or more based on 100 parts by weight of the component (A) of the present invention. The upper limit of the content of the component (B) is 20 parts by weight or less, preferably 15 parts by weight or less, and more preferably 10 parts by weight or less.

(24) The ratio of NCO group/NH group in the adherence agent of the present invention is 1.5 or more, preferably 2.0 or more, more preferably 2.7 or more. The upper of the ratio is 4.0 or less, preferably 3.7 or less, the most preferably 3.5 or less. When the ratio of NCO group/NH group is below 1.5, the amount of the NCO group in the adherence agent becomes lower and the extent of the reaction with the prepolymer is reduced, so that the adhesiveness cannot be enhanced. When the ratio of NCO group/NH group is above 4.0, the amount of the silyl group in the adherence agent becomes higher and the amount of the addition of the adherence agent is needed to increase, so that there is an adverse effect on economy and other physical properties.

(25) The curing catalyst (C) used in order to cure the adhesive composition in the present invention includes, for example, an organotin compound (dibutyltin diacetylacetonate, dibutyltin dilaurate, tin octylate, dibutyltin dimaleate); 2,2-dimorpholinodiethyl ether, di(2,6-dimethylmorpholinoethyl) ether; bismuth carboxylate (such as bismuth 2-ethylhexanoate, bismuth octylate, and bismuth neodecanoate); carboxylic acid (such as benzoic acid, phthalic acid, 2-ethylhexanoic acid, octyl acid, stearic acid, oleic acid, and linoleic acid); triethylenediamine and a salt thereof; N,N-dimethylaminoethylmorpholine; bis(2-dimethylaminoethyl) ether; 1,8-diazabicyclo(5,4,0)undecene-7 and a salt thereof (such as phenol salt, octyl acid salt, oleic acid salt, p-toluenesulfonic acid salt, and formic acid salt); imidazole-based compound (such as 2-methylimidazole, 2-undecylimidazole, 2-heptadecyl imidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 2,4-diamino-6-[2-methylimidazolyl-(1)]-ethyl-s-triazine, 2,4-diamino-6-[2-undecylimidazolyl-(1)]-ethyl-s-triazine, 2,4-diamino-6-[2-ethyl-4-methylimidazolyl-(1)]-ethyl-s-triazine, 2,4-diamino-6-[2-methylimidazolyl-(1)]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylbenzimidazole isocyanuric acid adduct, 2-methylbenzimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole 2-phenylimidazoline, and 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole). In general, an amount of the catalyst may be determined within a range of 0.005-0.5% in the entire amount of the composition.

(26) The polyol (D) contained, when the urethane-based adhesive of the present invention is the two-liquid type adhesive composition, includes, for example, polyoxyalkylene polyol; polyester polyol such as condensation-based polyester polyol, lactone-based polyester polyol and polycarbonate polyol; polyol whose main chain is consisted of the CC bound such as acrylic polyol, polybutadiene-based polyol, polyolefin-based polyol, and saponified ethylene-vinyl acetate copolymer; and other flame-retardant polyols, phosphorus-containing polyol, halogen-containing polyol etc. Among the polyols, diols and triols are preferred.

(27) The polyoxyalkylene polyol is a compound which is obtained by polymerizing ethylene oxide, propylene oxide, butylene oxide etc. using diol, triol, tetraol etc. as an initiator. The polyoxyalkylene polyol includes, for example, polyethylene glycol, polypropylene glycol (PPG), polyoxypropylene triol, ethylene oxide/propylene oxide copolymers, polytetramethylene ether glycol (PTMEG), polytetrafluoroethylene, and sorbitol-based polyols. Among them, polypropylene glycol and/or polyoxypropylene triol is preferable because it is excellent in balance of hardness and breaking elongation of the composition containing a liquid component and balance of cost.

(28) A polyol having a weight-average molecular weight of about 100 to 10,000 is preferred, and a polyol having a weight-average molecular weight of 1000 to 5000 is more preferable. When the weight-average molecular weight is within this range, physical properties (for example, hardness, breaking strength, breaking elongation) and a viscosity of the urethane prepolymer produced by the reaction with the polyisocyanate compound described later are good.

(29) The polyol (D) contained, when the urethane-based adhesive of the present invention is the two-liquid type adhesive composition, is not limited to the above polyol and at least a part of the polyol may be replaced with, for example, a hydrophobic polyol such as a hydrogenated polyisoprene polyol, a rosin-modified polyol, a polybutadiene polyol etc. represented by the following chemical formulas. Since the two-liquid type urethane adhesive of the present invention contains these hydrophobic polyols, it is possible to further improve adhesion to a hardly adhesive resin adherend such as a polyolefin resin even if surface treatment is not sufficient by partially reacting with an alkoxysilyl group-containing polyfunctional isocyanate compound. More preferably, the hydrophobic polyol is added to the curing agent.

(30) ##STR00011##
when: each of k, l, m, n independently represents an integral number.

(31) Other additives used for the urethane-based adhesive of the present invention are, for example, a filler or a plasticizer.

(32) The filler includes, for example, calcium carbonate, silica, carbon black, clay, glass balloon, silica balloon, ceramic balloon, plastic balloon, talc, titanium oxide, quicklime, kaolin, zeolite and diatomaceous earth. In general, the amount of the filler may be determined within a range of 5-50% in the entire amount of the composition.

(33) The plasticizer includes, for example, diisononyl phthalate, diisononyl cyclohexane 1,2-dicarboxylate (DINCH), dioctyl phthalate (DOP), dibutyl phthalate, dilauryl phthalate, butylbenzyl phthalate, dioctyl adipate, diisodecyl adipate, trioctyl phosphate, tris(chloroethyl) phosphate, tris (dichloropropyl) phosphate, adipic acid propylene glycol polyester, adipic acid butylene glycol polyester, epoxystearic acid alkyl, alkylbenzene, epoxidized soybean oil etc. In general, the amount of the plasticizer may be determined within a range of 5 to 50% of the entire amount of the composition.

(34) In addition, an appropriate amount of an anti-aging agent, an antioxidant, a foaming agent, an ultraviolet absorber, a flame retardant, and a pigment etc. may be added.

EXAMPLES

(35) 1. Prepolymer

(36) 350 g of a 4,4-diphenylmethane diisocyanate (MDI) was added to 3000 g of a polyoxypropylenetriol having a hydroxyl value of 25.0, and they were reacted at 80 C. for 3 hours under a nitrogen atmosphere to prepare a NCO-terminated prepolymer having a NCO % content of 1.90% and a viscosity (20 C.) of 50000 MPa.Math.s. Here, the NCO % content was measured according to JIS K 0113 by a potential difference titration method.

(37) 2. Adherence Agent

(38) (1) An Adherence Agent for Comparison

(39) For comparison, a 3-(triethoxysilyl)propyl isocyanate was prepared as an adherence agent A instead of the conventional silane compounds, which is represented by the following chemical formula 12:

(40) ##STR00012##

(41) Preparing a N-3-(trimethoxysilyl)propyl-N-phenylamine represented by the following chemical formula 13:

(42) ##STR00013##
and a 3-(trimethoxysilyl)propanethiol represented by the following chemical formula 14:

(43) ##STR00014##
and each of them was reacted with a biuret hexamethylene diisocyanate (HDI biuret) represented by the following chemical formula 15:

(44) ##STR00015##
to prepare an adherence agent B and an adherence agent C having a NCO % content of 10%.
(2) An Adherence Agent of the Present Invention

(45) A bis[3-(trimethoxy)silylpropyl] amine, as the adherence agent of the present invention, represented by the chemical formula 16:

(46) ##STR00016##
was reacted with a HDI biuret to prepare an adherence agent D having a NCO % content of 10%.

(47) Preparing a bis[3-(trimethoxy)silylpropyl]amine as the adherence agent of the present invention, it was reacted with an allophanate type hexamethylene diisocyanate (HDI allophanate) represented by the chemical formula represented by the chemical formula 17:

(48) ##STR00017##
to prepare an adherence agent E having a NCO % content of 10%.

(49) Preparing a bis[3-(trimethoxy)silylpropyl]amine as the adherence agent of the present invention, it was reacted with an isocyanurate type hexamethylene diisocyanate (HDI isocyanurate) represented by the chemical formula 18:

(50) ##STR00018##
to prepare an adherence agent F having a NCO % content of 10%.

(51) Preparing a bis[3-(trimethoxy)silylpropyl]amine as the adherence agent of the present invention, it was reacted with a urethane prepolymer (NCO-terminated prepolymer) having an isocyanate group at the end thereof to prepare an adherence agent G having a NCO % content of 1.6%.

(52) The NCO-terminated prepolymer may be the same with and different from the prepolymer used as the main component of the adherence agent. Here, 350 g of 4,4-diphenylmethane diisocyanate (MDI) was added to 3000 g of polyoxypropylenetriol having a hydroxyl value of 25.0, and they were reacted at 80 C. for 3 hours under a nitrogen atmosphere to prepare a NCO-terminated prepolymer having a NCO % content of 1.90% and a viscosity (20 C.) of 50000 mPa.Math.S.

(53) 3. Preparation of a Two-Liquid Type Adhesive Composition

(54) Main agents for the two-liquid type adhesive compositions were prepared according to the respective formulations shown in Table 1.

(55) TABLE-US-00002 TABLE 1 (weight %) Main Main Main Main Main Main Main Main main agent component agent 1 agent 2 agent 3 agent 4 agent 5 agent 6 agent 7 agent 8 urethane prepolymer 38.0 38.0 38.0 38.0 38.0 38.0 38.0 28.0 adherence A 3.0 agent B 3.0 C 3.0 D 3.0 E 3.0 F 3.0 G 13.0 carbon black Mixture of 20.0 20.0 20.0 20.0 20.0 20.0 20.0 20.0 Carbon black 1/Carbon black 2 (mass ratio = 70/30) filler calcium carbonate 21.0 21.0 21.0 21.0 21.0 21.0 21.0 21.0 plasticizer diisononyl phthalate 20.0 17.0 17.0 17.0 17.0 17.0 17.0 17.0 catalyst 2,2-dimorpholino diethyl ether 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 total 100 100 100 100 100 100 100 100 Carbon black 1: Niteron #200 produced by Shinnichika carbon Carbon black 2: Niteron #300 produced by Shinnichika carbon

(56) Curing agents for the two-liquid type adhesive compositions are prepared according to the respective formulations shown in Table 2.

(57) TABLE-US-00003 (weight %) Curing Curing Curing Curing curing agent component agent 1 agent 2 agent 3 agent 4 diol PPG diol *1 68.0 45.0 45.0 45.0 hydrogenated polyisoprene diol *2 23.0 rosin-modified diol *3 23.0 polybutadiene diol *4 23.0 filler calcium carbonate 30.0 30.0 30.0 30.0 catalyst 1,8-diazabicyclo[5,4,0]-undesen7-octylate 2.0 2.0 2.0 2.0 total 100 100 100 100 *1: Asahi Glass Co., Ltd. Exenol 2020 Diol with a number average molecular weight of 200 (OH value: 56 mgKOH/g) *2: Idemitsu Kosan Co., Ltd. Poly ip (Hydroxy group content 0.83 mol/kg, number average molecular weight 2500) *3: Arakawa Chemical Industries, Ltd. D-6011 (Hydroxyl value 120 mgKOH/g) *4: Idemitsu Kosan Co., Ltd. Poly bd R-45HT (Hydroxy group content 47 mgKOH/g, number average molecular weight 2800)
4. Adhesion Strength to Glass Fiber Reinforced Polypropylene

(58) Plasma treatment was performed on 3 mmt glass fiber reinforced polypropylene (PP-GF40, hereinafter referred to as PPGF) possessed by Sunstar Engineering Inc. to obtain PPGF plates with two types of surface treatment levels.

(59) The surface treatment level in the plasma treatment measures a wetting index (dyne) according to JIS K 6768. The wetting index is measured at 23 C. under a standard test chamber atmosphere at a relative humidity of 50%. On the test specimens, a mixed liquid for test (a liquid prepared by mixing stepwise ethylene glycol monoethyl ether, formamide, methanol, and water in a predetermined ratio) is spread over the surface of the test specimens using a cotton swab. After 2 seconds, a liquid film is visually observed at a bright place to confirm whether or not tearing occurs. When tearing occurs, a similar procedure is carried out with a mixed liquid having a low surface tension, and when tearing does not occur, a similar procedure is carried out with a mixed liquid having a high surface tension. This operation is repeated to measure the wetting index. The higher the wetting index measured in this way is, the higher the hydrophilicity is, that is, the higher the improvement of the surface treatment level is. Typically, the surface treatment level specifications required in automotive manufacturing are 42 dyne to 55 dyne. Therefore, a surface treatment level showing a wetting index of less than 42 dyne is insufficient in surface treatment, and the adhesive having the high adhesion strength even with such conditions is determined to be excellent.

(60) Then, in this experiment, plasma treatment was performed on the PPGF to prepare a surface-treated PPGF plate A showing a wetting index of 42 dyne which is a lower limit of the specifications, and a surface-treated PPGF plate B showing a 35 dyne wetting index below the lower limit.

(61) Each surface-treated PPGF plate was cut into a size of 100 mm25 mm to prepare PPGF test specimens 1. A shear adhesion strength test sample (FIG. 1) was prepared by applying each adhesive so that the thickness is 3 mmt between the PPGF test specimen 1 and the electrodeposition coated steel sheet 2 cut to a size of 100 mm25 mm, and curing them. The thickness is indicated with the value before curing, and the thickness of the adhesive does not change before and after curing. Here, by using an electrodeposition coated steel sheet for an adherend, one side of the test specimens is surely adhered to the adhesive.

(62) The shear adhesion strength test sample prepared in this way was mounted on a tensile strength tester, and the PPGF test specimens 1 and the electrodeposition coated steel sheet 2 were pulled in the reverse direction at a speed of 200 mm/min to confirm the failure state. The evaluation criteria of the failure state are as follows: A: cohesive failure of the adhesive layer B: partial interfacial failure between PPGF and the adhesive layer C: complete interfacial failure between PPGF and the adhesive layer

(63) Each adhesive was prepared by mixing the main agent shown in Table 1 and the curing agent shown in Table 2 at a ratio of 1 part by weight of the curing agent to 10 parts by weight of the main agent.

(64) The value of the shear adhesion strength measured after storing the shear adhesion strength test sample for 3 days at 20 C. and 65% RH was used as an initial characteristic, and after the storage, the value of the shear adhesion strength measured after heating the sample at 100 C. for 400 hours was evaluated as a heat resistance, and the results are shown in Table 3.

(65) TABLE-US-00004 TABLE 3 adhesive evaluation to PPGF *1 main curing initial characteristic *2 heat resistance characteristic *3 agent agent Plate A Plate B Plate A Plate B Comparative 1 1 C C C C example 1 1.2 0.8 1.0 0.9 Comparative 2 1 B B C C example 2 2.1 2.0 1.3 1.1 Comparative 3 1 A B B C example 3 3.0 2.7 2.9 1.2 Comparative 4 1 A B B C example 4 3.1 2.6 2.5 1.1 Example 1 5 1 A A A B 3.3 3.1 3.4 2.2 Example 2 6 1 A A A B 3.2 3.1 3.3 2.0 Example 3 7 1 A A A B 3.3 3.1 3.4 2.4 Example 4 8 1 A A A B 3.1 3.0 3.2 2.2 Example 5 5 2 A A A A 3.6 3.5 3.7 3.5 Example 6 5 3 A A A A 3.8 3.7 3.8 3.6 Example 7 5 4 A A A A 3.8 3.6 3.6 3.5 *1: A cohesive failure of an adhesive layer: B partial interfacial failure between PPGF and an adhesive layer; C complete interfacial failure between PPGF and an adhesive layer. *2: Shear test was carried out after storing for 3 days at 20 C. and 65% RH. *3: After the storage, shear test was carried out after the load test at 100 C. for 400 days.
5. Test Results
(1) Influence on Adhesion of Silane Compound Constituting an Adherence Agent

(66) Comparative example 1 represents a result of an adherence agent-free adhesive.

(67) For the PPGF plate A of the surface treatment level of 42 dyne at an initial stage, the adhesive layer caused interfacial rupture from PPGF at 100% area.

(68) Comparative examples 2-4 represent respectively the results of adhesives prepared by conventional adherence agents (adherence agents A-C). Although the initial characteristics were improved, especially for the PPGF plate B of the surface treatment level insufficient for 35 dyne, the heat resistance was poor.

(69) Example 1 represents the result of an adhesive prepared with the adherence agent D of the present invention using bis[3-(trimethoxy)silylpropyl]amine as a silane compound constituting the adherence agent.

(70) The initial characteristic was improved and the cohesive failure of the adhesive layer was observed with respect to the PPGF plate B having 35 dyne which was an insufficient surface treatment level, that is, the adhesion strength to PPGF was excellent. In addition, the heat resistance was improved and the adhesive layer did not completely break away from PPGF with respect to the PPGF plate B having 35 dyne which was an insufficient surface treatment level.

(71) (2) Influence on Adhesion of Polyfunctional Isocyanate Constituting an Adherence Agent

(72) Examples 2-4 represent respectively the results of an adhesive prepared by the reaction of bis[3-(trimethoxy) silylpropyl]amine and various polyfunctional isocyanates, as a silane compound constituting the adherence agent and prepared with the adherence agents E-G of the present invention

(73) As in Example 1, the initial characteristics were improved and the cohesive failure of the adhesive layer was observed with respect to the PPGF plate B having 35 dyne which was an insufficient surface treatment level, that is, the adhesion strength to PPGF was excellent. In addition, the heat resistance was improved and the adhesive layer did not completely break away from PPGF with respect to the PPGF plate B having 35 dyne which was an insufficient surface treatment level.

(74) (3) Influence on Adhesion of Polyol

(75) Examples 5-7 represent the results of an adhesive prepared by submitting a part of PPG diol with a hydrogenated polyisoprene diol, a rosin-modified diol, and a polybutadiene diol, each of which used a bis[3-(trimethoxy)silylpropyl]amine as a silane compound constituting an adherence agent in the same manner as in Example 1 as an adherence agent.

(76) When a hydrophobic polyol such as hydrogenated polyisoprene diol, rosin-modified diol and polybutadiene diol was used in at least a portion of the polyol, heat resistance was further improved with respect to the PPGF plate B having 35 dyne which was the insufficient surface treatment level, and cohesive failure of the adhesive layer was observed, that is, adhesion strength to PPGF was excellent.

INDUSTRIAL APPLICABILITY

(77) The heat-curable urethane-based adhesive of the present invention exhibits high adhesion without using a primer even if the surface treatment level of a back door (resin back door) employing a PP-based resin as a structural material is insufficient in an automotive manufacturing process.

DESCRIPTION OF REFERENCE NUMERALS

(78) 1: a glass fiber reinforced polypropylene plate 2: an electrodeposition coated steel sheet 3: an adhesive layer