TW201841962A - Moisture-curable hot-melt polyurethane resin composition and laminate - Google Patents

Abstract

The present invention provides a moisture-curable hot-melt polyurethane resin composition which is characterized in that the melt viscosity at 120 DEG C is within the range of 160-800 mPa·s and the melt viscosity at 80 DEG C is within the range of 850-10,000 mPa·s. The present invention also provides a laminate which is characterized in that a cured layer of the moisture-curable hot-melt polyurethane resin composition and a resin film or a fiber base material are laminated in this order. The moisture-curable hot-melt polyurethane resin composition preferably contains an isocyanate group-containing urethane prepolymer (i) which is a reaction product of a polyol (a) and polyisocyanate (b). Preferably, a specific one is used as the polyol (a).

Description

 Moisture-curing polyurethane hot melt resin composition and laminate  

The present invention relates to a moisture-curing polyurethane thermal melt resin composition and a laminate having the cured layer thereof.

For mountaineering wear and sportswear, etc., in addition to the ease of movement and lightness during normal wear, good moisture permeability and water repellency are required. Among them, the moisture permeability is an important characteristic in suppressing the uncomfortable feeling caused by the vapor caused by the moisture generated in the body due to sweating and the like.

As the moisture permeable material having the above moisture permeability, for example, a polyol having a polyoxyethylene glycol as a main component, a chain extender, and a moisture permeable polyurethane having a polyisocyanate as a raw material are disclosed ( For example, refer to Patent Document 1).

The moisture-permeable polyurethane has a high moisture permeability due to the main component of the highly hydrophilic polyoxyethylene glycol, but has a problem that the peel strength is low. In addition, in recent years, the base of the moisture permeable material has not only a fibrous base material, but also a water-repellent processor and a resin-based film are used, and it is necessary to have various substrates. Development of materials with good adhesion strength.

Advanced technical literature Patent literature

Patent Document 1 Japanese Patent Laid-Open Publication No. 2003-246832

The problem to be solved by the present invention is to provide a moisture-curable polyurethane thermal melt resin composition having good strength.

The present invention provides a moisture-curing polyurethane thermal melt resin composition characterized by a melt viscosity of 160 to 800 mPa at 120 ° C. The range of s, and the melt viscosity at 80 ° C is 850 ~ 10,000 mPa. The scope of s. Moreover, the present invention provides a laminate in which a cured layer of the moisture-curable polyurethane hot-melt resin composition and a resin film or a fiber substrate are sequentially laminated.

The moisture-curing polyurethane thermal melt resin composition of the present invention has good adhesion strength.

Form of implementing the invention

The composition of the moisture-hardening polyurethane thermal melt resin of the invention has a melt viscosity of 160-800 mPa at 120 ° C. The range of s, and the melt viscosity at 80 ° C is 850 ~ 10,000 mPa. The scope of s. By setting the melt viscosity to such a range, it is possible to exhibit good wettability to the substrate and obtain good adhesion strength. Further, the melt viscosity of the moisture-curable polyurethane foam composition at 120 ° C and 80 ° C is a value measured by a cone-and-plate viscometer. This measurement method is described in the examples described later.

The melt viscosity at 120 ° C is more preferably from 200 to 700 mPa from the viewpoint of obtaining a better bond strength by appropriate wettability. The range of s is further preferably 300 to 600 mPa. The scope of s.

The melt viscosity at 80 ° C is more preferably from 1,500 to 8,000 mPa from the viewpoint of obtaining a better bond strength by appropriate wettability. The range of s is further preferably 2,000 to 6,000 mPa. The range of s is particularly good at 2,200~5,500mPa. The scope of s.

Further, as the moisture-curable polyurethane thermal-melt resin composition, the melt viscosity at 80 ° C and the above-mentioned melt strength can be obtained from the viewpoint of obtaining better adhesion strength by appropriate wettability. The ratio of the melt viscosity at 120 ° C [melt viscosity at 80 ° C / melt viscosity at 120 ° C], preferably in the range of 6 to 13, more preferably in the range of 6.5 to 10, further preferably in the range of 7 to 9.5. .

Specific examples of the moisture-curable polyurethane thermal-melt resin composition include a reactant of a polyol (a) and a polyisocyanate (b), and an amine having an isocyanate group. Carbamate prepolymer (i).

As the polyol (a), for example, a polyether polyol, a polyester polyol, a polycarbonate polyol, a polycaprolactone polyol, a polybutadiene polyol, a dimer diol, or the like can be used. These polyols may be used alone or in combination of two or more.

The number average molecular weight of the polyol (a) is preferably in the range of 300 to 10,000, more preferably in the range of 350 to 5,000. In addition, the number average molecular weight of the aforementioned polyol (a) is shown by a gel. penetration. The value measured by the chromatographic (GPC) method under the following conditions.

Measuring device: High-speed GPC device ("HLC-8220GPC" manufactured by Tosoh Corporation)

Pipe string: The following pipe string manufactured by Tosoh Corporation is used in series connection.

"TSKgel G5000" (7.8mmI.D.×30cm) × 1

"TSKgel G4000" (7.8mmI.D.×30cm) × 1

"TSKgel G3000" (7.8mmI.D.×30cm) × 1

"TSKgel G2000" (7.8mmI.D.×30cm) × 1

Detector: RI (differential refractometer)

Column temperature: 40 ° C

Lysate: tetrahydrofuran (THF)

Flow rate: 1.0 mL/min

Injection amount: 100 μL (0.4 mass% sample concentration in tetrahydrofuran solution)

Standard sample: A calibration curve was prepared using the standard polystyrene described below.

 (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

In the above-mentioned polyol (a), from the viewpoint of having low viscosity and being able to obtain better adhesion strength by appropriate wettability, it is preferred that the number average molecular weight alone is less than 1,000. Polyol (a-1), or a combination of a polyol (a-1) having a number average molecular weight of less than 1,000 and a polyol (a-2) of 1,000 or more, more preferably a number average molecular weight of 500 to 800. The polyol, or a combination of a polyol having a number average molecular weight of 300 to 600 and a polyol having a range of 1,000 to 5,000. Further, the polyols (a-1) and (a-2) are preferably a polyether polyol and/or a polyester polyol which is liquid at 23 ° C. In addition, the above-mentioned "liquid state" means a polyester polyol which exhibits fluidity at 23 °C.

When the polyol (a-1) having a number average molecular weight of less than 1,000 and the polyol (a-2) of 1,000 or more are used in combination as the polyol (a), the amount of the polyol (a-1) used is The total mass of the polyol (a-1) and the polyol (a-2) is preferably 10% by mass or more, more preferably 20% by mass or more, and still more preferably 30% by mass or more.

As the polyether polyol, for example, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyoxyethylene glycol polyoxypropylene glycol, polyoxyethylene glycol polyoxytetramethylene glycol, or the like can be used. Polyoxypropylene polyoxytetramethylene glycol and the like. These polyether polyols may be used alone or in combination of two or more. Among these, from the viewpoint of obtaining a better bonding strength by better wettability, polypropylene glycol is preferred.

As the polyester polyol which is liquid at 23 ° C, the viscosity which can be used at 23 ° C is 3,000 mPa. The following are, for example, a reaction product of a compound having two or more hydroxyl groups and a polybasic acid.

As the compound having two or more hydroxyl groups, for example, ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, decanediol, decanediol, trihydroxyl can be used. Methylpropane, trimethylolethane, glycerol, and the like. These compounds may be used alone or in combination of two or more.

As the polybasic acid, for example, oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, sebacic acid, or dodecanedioic acid can be used. These polybasic acids may be used alone or in combination of two or more.

In addition, as the polyol (a), it is preferred that the polyol (a) contains 50% by mass or more of a polyether polyol from the viewpoint of obtaining a better adhesive strength by appropriate wettability. The content is preferably 60% by mass or more.

As the polyisocyanate (B), polymethylene polyphenyl polyisocyanate, diphenylmethane diisocyanate, carbodiimide modified diphenylmethane diisocyanate isocyanate, benzodimethyl diisocyanate, or extensible can be used. An aromatic polyisocyanate such as phenyl diisocyanate, toluene diisocyanate or naphthalene diisocyanate; hexamethylene diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, tetramethylbenzene An aliphatic or alicyclic polyisocyanate such as dimethyl diisocyanate. These polyisocyanates may be used alone or in combination of two or more. Among these, from the viewpoint of obtaining good reactivity and adhesion strength, it is preferred to use an aromatic polyisocyanate, more preferably diphenylmethane diisocyanate.

The amount of the polyisocyanate (B) to be used is preferably from 5 to 60 parts by mass, more preferably from 35 to 49 parts by mass, per 100 parts by mass of the total of the polyol (a) and the polyisocyanate (b). The range is further preferably from 37 to 45 parts by mass.

The hot-melt urethane prepolymer (i) is obtained by reacting the aforementioned polyol (a) with the aforementioned polyisocyanate (b), and is present in the air and coated with a moisture-curing type. The moisture in the substrate of the polyurethane hot-melt resin composition reacts to form an isocyanate group of a crosslinked structure.

As a method for producing the hot-melt urethane prepolymer (i), for example, the polyol (a) can be placed in a reaction container in which the polyisocyanate (b) has been placed, The isocyanate group which the isocyanate (b) has is produced by reacting with respect to the hydroxyl group which the said polyol (a) has excess conditions.

The equivalent ratio (isocyanate group/hydroxy group) of the isocyanate group of the polyisocyanate (b) and the hydroxyl group of the polyol (a) when the hot-melt urethane prepolymer (i) is produced, From the viewpoint of obtaining further excellent peel strength, it is preferably in the range of 1.1 to 5, more preferably in the range of 1.3 to 3.

The isocyanate group content (hereinafter, abbreviated as "NCO%") of the hot-melt urethane prepolymer (i) obtained by the above method is obtained from the viewpoint of obtaining further excellent peel strength. Look, preferably in the range of 1.5 to 10, more preferably in the range of 3 to 8. Further, the NCO% of the hot-melt urethane prepolymer is a value measured by a potentiometric titration method in accordance with JIS K1603-1:2007.

The moisture-curable polyurethane thermal melt resin composition of the present invention contains the hot-melt urethane prepolymer (i) as a main component, but may contain other additives as needed.

As the other additives, for example, a curing catalyst, an antioxidant, a tackifier, a plasticizer, a stabilizer, a filler, a dye, a pigment, a fluorescent whitening agent, a decane coupling agent, a wax, a thermoplastic resin, or the like can be used. These additives may be used alone or in combination of two or more.

Subsequently, the laminate of the present invention will be described.

The layered system is sequentially laminated with a cured layer of the moisture-curable polyurethane hot-melt resin composition, and a resin film or a fiber substrate. Further, the laminate may be bonded to the resin film and the fiber substrate by a moisture-curing polyurethane hot-melt resin composition.

As the resin film, polyester such as polyethylene terephthalate, polyethylene naphthalate or polybutylene terephthalate, olefin resin, polyacrylate, polyvinyl chloride, or poly can be used. Ethylene, polypropylene ethylene vinyl alcohol, polyurethane resin, polyamide resin, polyimide resin, fluororesin, etc. are used as raw materials. Among these, even when a urethane resin film, a fluororesin film, an olefin resin film, or the like which is used in a moisture permeable use in recent years, such as a thermoplastic urethane resin (TPU), is used, Good adhesion strength can also be obtained by using the moisture-curing polyurethane hot-melt resin composition of the present invention.

As the fiber base material, for example, polyester fiber, polyethylene fiber, nylon fiber, acrylic fiber, polyurethane fiber, acetate fiber, ray fiber, polylactic acid fiber, cotton, hemp, silk, Non-woven fabrics, woven fabrics, knitted fabrics, etc. of wool, glass fiber, carbon fiber, and such blended fibers. Further, in the present invention, even when the water-repellent fiber material is produced from a raw material by a well-known method, good adhesion strength can be obtained.

The method of forming the cured layer of the moisture-curable polyurethane thermal-melt resin composition on the resin film or the fiber substrate may be, for example, on the resin film or the fiber substrate. a method of coating a composition of the above-described moisture-curable polyurethane hot melt resin which has been melted at 50 to 130 ° C; for example, coating the moisture-cured type which has been melted at 50 to 130 ° C on a release paper. A method of laminating a polyurethane hot-melt resin composition, and then bonding the cured layer to the resin film or the fiber substrate.

In any of the above methods, as a method of applying the composition of the moisture-curable polyurethane hot-melt resin, for example, a roll coater, a knife coater, a spray coater, a gravure coater, and a notch can be used. A method such as a comma coater, a T-die coater, an applicator, or the like.

After the coating of the moisture-curing polyurethane hot-melt resin composition, the drying can be carried out by a well-known method. Cured.

The thickness of the cured layer of the moisture-curable urethane hot-melt resin composition is, for example, in the range of 5 to 200 μm.

 [Examples]  

Hereinafter, the present invention will be described in more detail by way of examples.

 [Example 1]  

In a four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser, 100 parts by mass of polypropylene glycol (number average molecular weight: 700, hereinafter abbreviated as "PPG700") was placed and mixed, and decompressed at 70 ° C. After heating, the water in the flask was dehydrated to 0.05% by mass or less.

Next, the inside of the flask was cooled to 90 ° C, and 65.2 parts by mass of 4,4'-diphenylmethane diisocyanate (hereinafter abbreviated as "MDI") which had been melted at 70 ° C was added, at 110 ° C under a nitrogen atmosphere. The reaction was carried out for about 3 hours until the content of the isocyanate group became fixed, and a hot-melt urethane prepolymer having an NCO%: 5.9% by mass was obtained.

Subsequently, the obtained urethane prepolymer was melted at 80 ° C for 1 hour, and then a film of a thermoplastic urethane resin (hereinafter referred to as "TPU") was used using a gravure coater (speed: 8 m/min). The coating was carried out so that the coating amount was 15 g/m ² . Next, the laminate (1) was obtained by laminating a polyester fiber base material under the conditions of a temperature of 23 ° C and a relative humidity of 65% for 3 hours.

Further, a polyester fiber base material was used instead of the polyester fiber base material, and a layered product (2) was produced in the same manner.

 [Examples 2 to 5, Comparative Examples 1 to 4]  

A moisture-curable polyamine group was obtained in the same manner as in Example 1 except that the kind and blending amount of the raw material used for the production of the urethane prepolymer (i) were changed as shown in Tables 1 to 2. a formate hot melt resin composition and a laminate.

 [Method for Measuring Melt Viscosity of Moisture Curing Polyurethane Hot Melt Resin Composition]  

The moisture-curable polyurethane hot-melt resin composition obtained in the examples and the comparative examples was melted at 80 ° C or 120 ° C for 1 hour, and then 1 ml was sampled to obtain a cone-plate viscometer (M.S.T project) Co., Ltd. digital viscometer "CV-1S RT type", 40P cone, rotor speed: 50 rpm) The melt viscosity (80 ° C or 120 ° C melt viscosity) was measured.

 [Following the strength evaluation method]  

To the obtained laminate, Tensilon (Tensilon Universal Testing Machine "RTC-1210A" manufactured by Orientech Co., Ltd.) was used, and the peel strength was measured under the condition of a crosshead measurement of 200 mm/min to obtain the adhesion strength.

"○": 10N/inch or more

"X": less than 10N/inch

The abbreviations in Tables 1 to 2 are as follows.

"PPG400": polypropylene glycol (quantitative molecular weight: 400)

"PEs1": those with a reaction of diethylene glycol, neopentyl glycol, hexanediol and adipic acid, the average molecular weight: 2000, liquid at room temperature

"PPG1000": polypropylene glycol (quantitative molecular weight: 1,000)

"PPG2000": Polypropylene glycol (quantitative molecular weight: 2,000)

The moisture-curing polyurethane heat-fusible resin composition of the present invention is known to have good adhesion strength.

Further, in Comparative Examples 1 and 2, the melt viscosity at 120 ° C and 80 ° C was less than the range specified in the present specification, but the strength was insufficient.

Although Comparative Examples 3 and 4 have a state in which the melt viscosity at 120 ° C and 80 ° C is larger than the range specified in the present invention, the strength is insufficient.

Claims (12)

 The invention relates to a moisture-hardening polyurethane thermal melting resin composition characterized in that the melt viscosity at 120 ° C is 160-800 mPa. The range of s, and the melt viscosity at 80 ° C is 850 ~ 10,000 mPa. The scope of s.    The moisture-curing polyurethane hot-melt resin composition of claim 1, wherein the ratio of the melt viscosity at 80 ° C to the melt viscosity at 120 ° C [melt viscosity at 80 ° C / at 120 ° C) The melt viscosity] is in the range of 6 to 13.    A moisture-curing polyurethane thermal melt resin composition according to claim 1 or 2 which is a reactant of a polyol (a) and a polyisocyanate (b), which is an amino group having an isocyanate group Acid ester prepolymer (i).    The moisture-curing polyurethane hot-melt resin composition of claim 3, wherein the polyol (a) is a polyol (a-1) having a number average molecular weight of less than 1,000, or a combined use of a number average molecular weight. Less than 1,000 polyols (a-1) and 1,000 or more polyols (a-2).    The moisture-curable polyurethane thermal melt resin composition according to claim 3 or 4, wherein the polyol (a) is a polyether polyol containing 50% by mass or more.    The moisture-curing polyurethane thermal melt resin composition of claim 5, wherein the polyether polyol is polypropylene glycol.    The moisture-curing polyurethane thermal melt resin composition according to any one of claims 3 to 6, wherein the use of the polyisocyanate (b) of the raw material of the urethane prepolymer (i) The amount is in the range of 35 to 49 parts by mass based on 100 parts by mass of the total of the polyol (a) and the polyisocyanate (b).    The moisture-curing polyurethane thermal melt resin composition according to any one of claims 3 to 7, wherein the polyisocyanate (b) is diphenylmethane diisocyanate.    A laminate comprising a cured layer of a moisture-curing polyurethane hot-melt resin composition according to any one of claims 1 to 8, and a resin film or a fibrous substrate.    The laminate of claim 9, wherein the fibrous substrate is a water repellent.    The laminate according to claim 9, wherein the resin film is formed of a fluororesin, a urethane resin, or an olefin resin.    The laminate according to claim 9, wherein the resin film is a thermoplastic urethane resin.