JP6459500B2 - Moisture curable polyurethane hot melt resin composition, adhesive, and laminate - Google Patents

Description

  The present invention relates to a moisture-curable polyurethane hot melt resin composition having excellent adhesion to a metal substrate such as aluminum.

  Moisture curable polyurethane hot melt resin compositions are widely used mainly in the field of building materials and fibers, and are widely used for bonding wood, cloth, sheets, paper, and the like as adherends. Not only this but in recent years, attention is also attracting attention also in the field of an automobile, an electrical machinery field, etc. from a good production efficiency of a moisture hardening type polyurethane hot melt resin composition which is a solvent-free (for example, refer to patent documents 1). .

  However, with the spread of the fields and applications used in this way, excellent adhesion to various adherends is required, and in particular, adhesion to metal substrates such as aluminum is the conventional moisture-curing type It was difficult with a polyurethane hot melt resin composition.

JP, 2014-122299, A

  The problem to be solved by the present invention is to provide a moisture curable polyurethane hot melt resin composition having excellent adhesion to a metal substrate such as aluminum.

  The present invention contains a urethane prepolymer obtained by reacting a polymer (A-1) having two or more thiol groups, a polyol (A-2), and a polyisocyanate (B). A moisture-curable polyurethane hot melt resin composition is provided.

  The present invention also provides an adhesive obtained by moisture-curing the moisture-curable polyurethane hot melt resin composition.

  Furthermore, this invention provides the laminated body characterized by having an adhesive layer which consists of a metal base material and the said adhesive agent.

  The moisture-curable polyurethane hot melt resin composition of the present invention is excellent in adhesiveness (initial creep property (initial adhesive strength) and final adhesive strength) to a metal substrate such as aluminum. However, it can be suitably used for the manufacture of members used in the field of automobiles, electrical machinery and the like.

  The moisture curable polyurethane hot melt resin composition of the present invention is a urethane obtained by reacting a polymer (A-1) having two or more thiol groups, a polyol (A-2), and a polyisocyanate (B). It contains a prepolymer.

  The polymer (A-1) having two or more thiol groups is an essential component for obtaining excellent adhesion to a metal substrate such as aluminum.

  As said polymer (A-1), what has an ether bond, a thioether bond, a polysulfide bond, a urethane bond, an ester bond, etc. in a principal chain other than two or more thiol groups contributing to a urethanation reaction, for example. Can be used. These polymers may be used alone or in combination of two or more. As said polymer (A-1), it is preferable to use what has a polysulfide bond from the point which can improve the adhesiveness with respect to metal base materials, such as aluminum, and it is preferable to use what has a polysulfide bond and an ether bond. More preferred.

  Specifically, the polymer (A-1) is preferably a polymer represented by the following general formula (1).

（式（１）中、Ｒ^１は、Ｃ_２Ｈ_４ＯＣＨ_２ＯＣ_２Ｈ_４又は炭素原子数１〜１２のアルキレン基を示し、ｘは１〜５の整数を示し、ｎは１〜１００の繰り返し単位の平均値を示す。）

(In the formula (1), ^{R 1} _{is, C 2 H 4 OCH 2 OC} 2 H 4 or an alkylene group having 1 to 12 carbon atoms, x is an integer of 1 to 5, n is from 1 to 100 Indicates the average value of repeating units.)

Among the polymers represented by the general formula (1), R ¹ is preferably C ₂ H ₄ OCH ₂ OC ₂ H ₄ from the viewpoint that the adhesion to a metal substrate such as aluminum can be further improved. Is preferably in the range of 1 to 3, n is preferably in the range of 3 to 50, and more preferably in the range of 5 to 30.

  The number average molecular weight of the polymer (A-1) is preferably in the range of 300 to 100,000, more preferably in the range of 500 to 30,000, from the viewpoint of adhesion to a metal substrate such as aluminum. The range of 600 to 10,000 is more preferable. In addition, the number average molecular weight of the said polymer (A-1) shows the value measured on condition of the following by gel permeation chromatography (GPC) method.

Measuring device: High-speed GPC device (“HLC-8220GPC” manufactured by Tosoh Corporation)
Column: The following columns manufactured by Tosoh Corporation were connected in series.
"TSKgel G5000" (7.8 mm ID x 30 cm) x 1 "TSKgel G4000" (7.8 mm ID x 30 cm) x 1 "TSKgel G3000" (7.8 mm ID x 30 cm) x 1 “TSKgel G2000” (7.8 mm ID × 30 cm) × 1 detector: RI (differential refractometer)
Column temperature: 40 ° C
Eluent: Tetrahydrofuran (THF)
Flow rate: 1.0 mL / min Injection amount: 100 μL (tetrahydrofuran solution with a sample concentration of 0.4 mass%)
Standard sample: A calibration curve was prepared using the following standard polystyrene.

(Standard polystyrene)
"TSKgel standard polystyrene A-500" manufactured by Tosoh Corporation
"TSKgel standard polystyrene A-1000" manufactured by Tosoh Corporation
"TSKgel standard polystyrene A-2500" manufactured by Tosoh Corporation
"TSKgel standard polystyrene A-5000" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-1" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-2" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-4" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-10" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-20" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-40" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-80" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-128" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-288" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-550" manufactured by Tosoh Corporation

  As the polymer (A-1), for example, “thiocol LP” manufactured by Toray Fine Chemical Co., Ltd., “THIOPLAST polymer” manufactured by AKZO NOBEL, etc. can be obtained as commercial products.

  As the usage-amount of the said polymer (A-1), the polymer (A-1), a polyol (A-2), and a polyisocyanate (B) from the point which can further improve the adhesiveness with respect to metal base materials, such as aluminum. ) Is preferably in the range of 0.1 to 20% by mass, more preferably in the range of 1 to 15% by mass.

  Examples of the polyol (A-2) include polyester polyol, polyether polyol, polycarbonate polyol, acrylic polyol, polybutadiene polyol, polyisoprene polyol, and dimer diol. These polyols may be used alone or in combination of two or more. As the polyol (A-2), polyester polyol and / or polyether polyol from the point that adhesion to various substrates as well as metal substrates, flexibility, and initial creep property can be further improved. It is preferable to contain. The total amount of the polyester polyol and the polyether polyol in the polyol (A-2) is preferably 50% by mass or more, and more preferably 80% by mass or more.

  As said polyester polyol, crystalline polyester polyol, amorphous polyester polyol, etc. can be used, for example. These polyester polyols may be used alone or in combination of two or more.

  As the crystalline polyester polyol, for example, a reaction product of a compound having a hydroxyl group and a polybasic acid can be used. In the present invention, “crystallinity” means that the peak of crystallization heat or heat of fusion can be confirmed in DSC (Differential Scanning Calorimetry) measurement based on JISK7121: 2012. Indicates that the peak cannot be confirmed.

  Examples of the compound having a hydroxyl group include ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, trimethylolpropane, trimethylolethane, and glycerin. Can do. These compounds may be used alone or in combination of two or more.

  Examples of the polybasic acid include oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, 1,12-dodecanedicarboxylic acid, and the like. These polybasic acids may be used alone or in combination of two or more.

  The number average molecular weight of the crystalline polyester polyol is preferably in the range of 500 to 6,000, more preferably in the range of 1,000 to 5,000, from the viewpoint of adhesion to various substrates. preferable. In addition, the number average molecular weight of the said crystalline polyester polyol shows the value obtained by measuring similarly to the number average molecular weight of the said polymer (A-1).

  As the amorphous polyester polyol, for example, a reaction product of a compound having a hydroxyl group and a polybasic acid can be used.

  Examples of the compound having a hydroxyl group include ethylene glycol, propylene glycol, 1,4-butanediol, pentanediol, 2,4-diethyl-1,5-pentanediol, 3-methyl-1,5-pentanediol, Hexanediol, neopentyl glycol, hexamethylene glycol, glycerin, trimethylolpropane, bisphenol A, bisphenol F, and alkylene oxide adducts thereof can be used. These compounds may be used alone or in combination of two or more.

  Examples of the polybasic acid include adipic acid, glutaric acid, pimelic acid, suberic acid, dimer acid, sebacic acid, undecanedicarboxylic acid, hexahydroterephthalic acid, phthalic acid, phthalic anhydride, orthophthalic acid, isophthalic acid, terephthalic acid. An acid or the like can be used. These polybasic acids may be used alone or in combination of two or more.

  The number average molecular weight of the amorphous polyester polyol is preferably in the range of 500 to 7,000, more preferably in the range of 1,000 to 6,000, from the viewpoint that the adhesion to various base materials can be further improved. Is more preferable. In addition, the number average molecular weight of the said amorphous polyester polyol shows the value obtained by measuring similarly to the number average molecular weight of the said polymer (A-1).

  Examples of the polyether polyol include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyoxyethylene polyoxypropylene glycol, polyoxyethylene polyoxytetramethylene glycol, and polyoxypropylene polyoxytetramethylene glycol. it can. These polyether polyols may be used alone or in combination of two or more.

  The number average molecular weight of the polyether polyol is preferably in the range of 500 to 5,000, more preferably in the range of 1,000 to 4,000, from the viewpoint that the flexibility and initial creep property can be further improved. . In addition, the number average molecular weight of the said amorphous polyether polyol shows the value obtained by measuring similarly to the number average molecular weight of the said polymer (A-1).

  Examples of the polyisocyanate (B) include aromatic polyisocyanates such as polymethylene polyphenyl polyisocyanate, diphenylmethane diisocyanate, polymeric diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, phenylene diisocyanate, tolylene diisocyanate, and naphthalene diisocyanate; Aliphatic or alicyclic polyisocyanates such as lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate, and tetramethylxylylene diisocyanate can be used. These polyisocyanates may be used alone or in combination of two or more. Among these, it is preferable to use diphenylmethane diisocyanate and / or polymeric diphenylmethane diisocyanate from the viewpoint of reactivity, mechanical strength, and adhesive strength.

  The urethane prepolymer has an isocyanate group capable of forming a crosslinked structure by reacting with moisture present in the air, a casing to which the urethane prepolymer is applied, an adherend, a mold, a mold, or the like. Have.

  As a method for producing the urethane prepolymer, for example, a mixture of the polymer (A-1) and the polyol (A-2) is added dropwise to a reaction vessel containing the polyisocyanate (B), and then heated. It can be produced by reacting the isocyanate group of the isocyanate (B) with an excess of the hydroxyl group of the polyol (A).

  The equivalent ratio of the isocyanate group that the polyisocyanate (B) has to the total of the hydroxyl group that the polyol (A-2) has and the thiol group that the polymer (A-1) has when producing the urethane prepolymer ( [NCO / SH + OH]) is preferably in the range of 1.1 to 5, more preferably in the range of 1.5 to 3, from the viewpoint of further improving the adhesion and mechanical strength to a metal substrate such as aluminum. Is more preferable.

  As the isocyanate group content of the urethane prepolymer obtained by the above method (hereinafter abbreviated as “NCO%”), it is possible to further improve the adhesion and mechanical strength to a metal substrate such as aluminum, The range of 1.1 to 10% is preferable, and the range of 1.5 to 5% is more preferable. In addition, the isocyanate group content rate of the said urethane prepolymer shows the value measured by the potentiometric titration method based on JISK1603-1: 2007.

  As the viscosity of the urethane prepolymer, the melt viscosity at 120 ° C. is preferably in the range of 1,000 to 50,000 mPa · s from the viewpoint of further improving the coatability and mechanical strength, and 2,000 More preferably, it is in the range of 10,000 mPa · s. In addition, the melt viscosity at 120 ° C. of the urethane prepolymer indicates a value measured with a cone plate viscometer (ICP, 20P cone).

  The moisture curable polyurethane hot melt resin composition of the present invention contains the urethane prepolymer as an essential component, but may contain other additives as necessary.

  Examples of the other additives include a curing agent, an antioxidant, a tackifier, a plasticizer, a stabilizer, a filler, a dye, a pigment, a fluorescent brightener, a silane coupling agent, and a wax. it can. These additives may be used alone or in combination of two or more.

  Examples of a method for obtaining an adhesive using the moisture curable polyurethane hot melt resin composition of the present invention include a method in which a substrate and a sheet or film are bonded together and moisture-cured.

  Examples of the base material include wood base materials such as plywood, MDF (medium density fiber board), and particle board; metal base materials such as aluminum, iron, steel, and plating. Further, the base material may have a complicated shape such as a groove, an R portion, and an inverted R portion.

  As the sheet or film, for example, a sheet or film obtained using a resin such as polyester, polyamide, polystyrene, polycarbonate, vinyl chloride, ethylene-vinyl acetate copolymer, polyvinyl alcohol, polyethylene, polypropylene, polyethylene terephthalate, or the like. Or paper, metal foil, a veneer, etc. can be used.

  As a method of bonding the substrate and the sheet or the like using the moisture curable polyurethane hot melt resin composition of the present invention, for example, the moisture curable polyurethane hot melt resin composition is in the range of 60 to 150 ° C. It is melted by heating and applied onto a substrate using a roll coater, spray coater, T-die coater, knife coater, etc., and the sheet or the like is bonded to the coated surface, or the roll coater is used. Coating on the sheet or the like, pasting the base material on the coated surface, and using a method such as roll press, flat press, belt press, etc., and appropriately pressing according to the shape of the base material. Can do. After the crimping, it may be cured for 1 to 7 days as necessary.

  The thickness of the cured product layer of the moisture curable polyurethane hot melt resin composition is appropriately determined depending on the application, and is, for example, in the range of 10 to 200 μm.

  As described above, the moisture-curable polyurethane hot melt resin composition of the present invention is excellent in adhesiveness (initial creep properties (initial adhesive strength) and final adhesive strength) to a metal substrate such as aluminum. An adhesive layer obtained by moisture-curing the moisture curable polyurethane hot melt resin composition and a laminate in which a metal substrate is laminated. Therefore, the moisture curable polyurethane hot melt resin composition of the present invention can be suitably used for the manufacture of members used not only in the field of building materials and fibers, but also in the fields of automobiles, electrical machinery and the like.

  Hereinafter, the present invention will be described in more detail with reference to examples.

[Example 1]
A four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet and a reflux condenser, PEs-1 (crystalline polyester polyol obtained by reacting adipic acid and 1,6-hexanediol, number average Molecular weight: 3,500) 28 parts by mass, PEs-2 (crystalline polyester polyol obtained by reacting dodecanedioic acid and 1,6-hexanediol, number average molecular weight; 3,500) 26 parts by mass, PEs-3 (ethylene Amorphous polyester polyol obtained by reacting glycol, neopentyl glycol, 1,6-hexanediol and adipic acid, number average molecular weight: 5,000) 25 parts by mass, “Thiocol LP-” manufactured by Toray Fine Chemical Co., Ltd. 33 "(wherein R ¹ is C ₂ H ₄ OCH ₂ OC ₂ H ₄ , x is 2 and n is about 7) Polymer, number average molecular weight: 1,000, hereinafter abbreviated as “LP-33”.) 5 parts by mass was charged and dehydrated under reduced pressure until the water content became 0.05% by mass or less.
Next, after cooling to 70 ° C. in the container, 16 parts by mass of 4,4′-diphenylmethane diisocyanate (hereinafter abbreviated as “MDI”) is added, the temperature is raised to 100 ° C., and the isocyanate group content is constant. It was made to react for about 3 hours until it became, and the moisture hardening type polyurethane hot-melt resin composition containing NCO%; 3 urethane prepolymer was obtained.

[Examples 2-7, Comparative Examples 1-3]
Except having changed the quantity of the polymer (A-1) to be used, the kind and / or quantity of a polyol (A-2), and the quantity of polyisocyanate as shown in Tables 1-2, it carried out similarly to Example 1, and changed. A moisture curable polyurethane hot melt resin composition was obtained.

[Evaluation method of initial creep property]
The moisture curable polyurethane hot melt resin compositions obtained in Examples and Comparative Examples were heated and melted to 120 ° C., and applied to a 100 μm thick PET (polyethylene terephthalate) film at a thickness of 50 μm. An aluminum plate having a thickness of 1 mm was placed and bonded. Three minutes after this bonding, under an atmosphere of 35 ° C., a load of 75 g with respect to a width of 25 mm was applied in the 90 ° direction, and the peel length of the aluminum plate 15 minutes after the load was applied was measured. It was evaluated as follows.
“T”; peeling length is less than 5 mm.
“F”; peeling length is 5 mm or more.

[Evaluation method of adhesive strength]
The moisture curable polyurethane hot melt resin compositions obtained in Examples and Comparative Examples were heated and melted to 120 ° C., and applied to a 100 μm thick PET (polyethylene terephthalate) film at a thickness of 80 μm. An aluminum plate having a thickness of 1 mm was placed and bonded. After bonding, after curing for 5 days under the conditions of 23 ° C. and 50% humidity, peeling was performed at a rate of 200 mm / min in the direction of 180 ° with respect to the width of 25 mm, and the peel strength at that time was measured. Evaluated.
“T”: Peel strength is 20 N / 25 mm or more.
“F”; peel strength is less than 20 N / 25 mm.

Abbreviations in Tables 1 and 2 will be described.
“PEs-4”; amorphous polyester polyol obtained by reacting diethylene glycol, neopentyl glycol, 1,6-hexanediol and adipic acid, number average molecular weight; 2,000
“PEs-5”; amorphous polyester polyol obtained by reacting ethylene glycol, adipic acid, orthophthalic acid and terephthalic acid, number average molecular weight; 3,500
“PEt-1”; polypropylene glycol, number average molecular weight; 2,000

  It turned out that Examples 1-7 which are the moisture hardening type polyurethane hot-melt resin composition of this invention have the initial stage creep property and adhesive strength outstanding with respect to the aluminum plate.

  On the other hand, although Comparative Examples 1-3 is an aspect which does not use a polymer (A-1), all had insufficient adhesive strength with respect to an aluminum plate.

Claims (5)

It possesses two or more thiol groups, and the polymer number average molecular weight in the range of 300 to 100,000 having a polysulfide bond (A-1), polyol (A-2), and polyisocyanate (B) is the reaction a moisture vapor-curable polyurethane hot-melt resin composition you containing urethane prepolymer obtained by,
The usage-amount of the said polymer (A-1) is in the range of 0.1-20 mass% in the sum total of the said polymer (A-1), the said polyol (A-2), and the said polyisocyanate (B). A moisture-curable polyurethane hot melt resin composition characterized by being. The moisture-curable polyurethane hot melt resin composition according to claim 1, wherein the polymer (A-1) is represented by the following general formula (1).

(In the formula (1), ^{R 1} _{is, C 2 H 4 OCH 2 OC} 2 H 4 or an alkylene group having 1 to 12 carbon atoms, x is an integer of 1 to 5, n is from 1 to 100 Indicates the average value of repeating units.) The moisture-curable polyurethane hot melt resin composition according to claim 1, wherein the polyol (A-2) contains a polyester polyol and / or a polyether polyol. An adhesive obtained by moisture-curing the moisture-curable polyurethane hot melt resin composition according to any one of claims 1 to 3 . A laminate comprising a metal substrate and the adhesive layer according to claim 4 .