KR102220758B1 - Moisture-curable polyurethane hot melt resin composition, and laminate - Google Patents

Abstract

The present invention is a moisture curable polyurethane hot melt resin composition characterized in that the melt viscosity at 120°C is in the range of 160 to 800 mPa·s, and the melt viscosity at 80°C is in the range of 850 to 10,000 mPa·s. Is to provide. In addition, the present invention provides a layered product in which a cured product layer of the moisture-curable polyurethane hot-melt resin composition and a resin film or a fiber substrate are sequentially laminated. The moisture-curable polyurethane hot melt resin composition is a reaction product of a polyol (a) and a polyisocyanate (b), and preferably contains a urethane prepolymer (i) having an isocyanate group, and a specific polyol (a) is used. It is desirable to do.

Description

Moisture-curable polyurethane hot melt resin composition, and laminate

The present invention relates to a moisture-curable polyurethane hot-melt resin composition, and a laminate having a cured product layer thereof.

In general, mountaineering clothes, sportswear, etc., in addition to ease of movement and lightness when worn, excellent moisture permeability and waterproofness are required. Among them, moisture permeability is an important characteristic in suppressing the discomfort caused by sweating caused by moisture generated from the body due to sweating and the like staying in the clothes.

As the moisture-permeable material having moisture permeability, for example, a polyol containing polyoxyethylene glycol as a main component, a chain extender, and a moisture-permeable polyurethane made from polyisocyanate as raw materials are disclosed (for example, Patent Documents See 1).

The moisture permeable polyurethane has a problem in that it has excellent moisture permeability, but has a low peel strength, since it contains polyoxyglycol having high hydrophilicity as a raw material. In addition, in recent years, not only a fiber substrate, but also a film made of a resin as a raw material has been used as a base material of a moisture-permeable material. There has been a demand for development of a material having excellent adhesive strength even when these various substrates are used.

Japanese Unexamined Patent Publication No. 2003-246832

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

The present invention is a moisture curable polyurethane hot melt resin composition characterized in that the melt viscosity at 120°C is in the range of 160 to 800 mPa·s, and the melt viscosity at 80°C is in the range of 850 to 10,000 mPa·s. Is to provide. In addition, the present invention is to provide a laminate, characterized in that the cured product 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 hot melt resin composition of the present invention has excellent adhesive strength.

The moisture-curable polyurethane hot melt resin composition of the present invention has a melt viscosity at 120°C of 160 to 800 mPa·s, and a melt viscosity at 80°C of 850 to 10,000 mPa·s. When the melt viscosity is within such a range, good wettability to the substrate is expressed, and excellent adhesive strength can be obtained. In addition, the melt viscosity at 120° C. and 80° C. of the moisture-curable polyurethane hot melt resin composition represents a value measured by a cone plate viscometer, and the measurement method is described in Examples described later.

The melt viscosity at 120°C is more preferably in the range of 200 to 700 mPa·s, and still more preferably in the range of 300 to 600 mPa·s, from the viewpoint of obtaining even more excellent adhesive strength with moderate wettability.

The melt viscosity at 80°C is more preferably in the range of 1,500 to 8,000 mPa·s, more preferably in the range of 2,000 to 6,000 mPa·s, and 2,200 from the viewpoint of obtaining even more excellent adhesive strength with moderate wettability. The range of -5,500 mPa·s is particularly preferred.

Further, as the moisture-curable polyurethane hot-melt resin composition, the ratio of the melt viscosity at 80°C and the melt viscosity at 120°C [at 80°C] from the viewpoint of obtaining even more excellent adhesive strength with moderate wettability. The melt viscosity/melt viscosity at 120°C] is preferably in the range of 6 to 13, more preferably in the range of 6.5 to 10, and still more in the range of 7 to 9.5.

Specific examples of the moisture-curable polyurethane hot melt resin composition include those containing a urethane prepolymer (i) having an isocyanate group, which is a reaction product of a polyol (a) and a polyisocyanate (b).

As the polyol (a), for example, polyether polyol, polyester polyol, polycarbonate polyol, polycaprolactone polyol, polybutadiene polyol, dimerdiol, and 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, and more preferably in the range of 350 to 5,000. In addition, the number average molecular weight of the polyol (a) represents a value measured under the following conditions by a 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 and used.

「TSKgel G5000」(7.8㎜I.D.×30cm)×1ea

「TSKgel G4000」(7.8㎜I.D.×30cm)×1ea

「TSKgel G3000」(7.8㎜I.D.×30cm)×1

「TSKgel G2000」(7.8㎜I.D.×30cm)×1ea

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% by 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 polyol (a), among the above, a polyol (a-1) having a number average molecular weight of less than 1,000 alone, or a number average molecular weight, from the viewpoint of having a low viscosity and obtaining even more excellent adhesive strength with moderate wettability. The combined use of the polyol (a-1) of less than 1,000 and the polyol (a-2) of 1,000 or more is preferable, and the number average molecular weight is the polyol alone in the range of 500 to 800, or the number average molecular weight is in the range of 300 to 600 The combination of a polyol and a polyol in the range of 1,000 to 5,000 is more preferable. Moreover, as said polyol (a-1) and (a-2), it is preferable that it is a polyether polyol and/or a liquid polyester polyol at 23 degreeC, respectively. In addition, the "liquid" refers to a polyester polyol exhibiting fluidity at 23°C.

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

As the polyether polyol, for example, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyoxyethylene polyoxypropylene glycol, polyoxyethylene polyoxytetramethylene glycol, polyoxypropylene polyoxytetramethylene glycol, and the like can be used. I can. These polyether polyols may be used alone or in combination of two or more. Among these, polypropylene glycol is preferable from the viewpoint of obtaining even more favorable wettability and even more excellent adhesive strength.

The liquid polyester polyol at 23°C indicates that the viscosity at 23°C is 3,000 mPa·s or less. For example, a reaction product of a compound having two or more hydroxyl groups and a polybasic acid can be used.

Examples of the compound having two or more hydroxyl groups include ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, trimethylolpropane, trimethylolethane, glycerin, etc. You can use 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, azelaic acid, and 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 preferable to contain 50% by mass or more of the polyether polyol in the polyol (a), more preferably 60% by mass or more, from the viewpoint of obtaining even more excellent adhesive strength with moderate wettability. Do.

Examples of the polyisocyanate (B) include polymethylene polyphenyl polyisocyanate, diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate isocyanate, xylylene diisocyanate, phenylene diisocyanate, tolylene diisocyanate, naphthalene diisocyanate, and the like. Aromatic polyisocyanate; Aliphatic or alicyclic polyisocyanates such as hexamethylene diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and tetramethylxylylene diisocyanate can be used. These polyisocyanates may be used alone or in combination of two or more. Among these, since excellent reactivity and adhesive strength are obtained, it is preferable to use an aromatic polyisocyanate, and diphenylmethane diisocyanate is more preferable.

The amount of the polyisocyanate (B) used is preferably 5 to 60 parts by mass, more preferably 35 to 49 parts by mass, based on 100 parts by mass of the total of the polyol (a) and the polyisocyanate (b), 37 to 45 parts by mass is more preferable.

The hot-melt urethane prepolymer (i) is obtained by reacting the polyol (a) and the polyisocyanate (b), and reacts with moisture present in the substrate to which the moisture-curable polyurethane hot-melt resin composition is applied to form a crosslinked structure. It has an isocyanate group which can be formed.

As a method for producing the hot-melt urethane prepolymer (i), for example, the polyol (a) is put in a reaction vessel containing the polyisocyanate (b), and the isocyanate group of the polyisocyanate (b) is selected from the polyol ( It can be produced by reacting under conditions in which a) has an excess of hydroxyl groups.

When preparing the hot-melt urethane prepolymer (i), as the equivalent ratio (isocyanate group/hydroxyl group) of the isocyanate group of the polyisocyanate (b) and the hydroxyl group of the polyol (a), a more excellent peel strength is obtained. Here, it is preferable that it is a range of 1.1-5, and it is more preferable that it is a range of 1.3-3.

The isocyanate group content (hereinafter abbreviated as "NCO%") of the hot-melt urethane prepolymer (i) obtained by the above method is preferably in the range of 1.5 to 10 from the viewpoint of obtaining a more excellent peel strength, and 3 to The range of 8 is more preferable. In addition, the NCO% of the hot-melt urethane prepolymer represents a value measured by a potential difference titration method in accordance with JISK1603-1:2007.

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

As the other additives, for example, curing catalysts, antioxidants, tackifiers, plasticizers, stabilizers, fillers, dyes, pigments, optical brighteners, silane coupling agents, waxes, thermoplastic resins, and the like can be used. These additives may be used alone or in combination of two or more.

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

The laminate is one in which a cured product layer of the moisture-curable polyurethane hot-melt resin composition and a resin film or a fiber substrate are sequentially laminated. Moreover, in the said laminated body, a resin film and a fiber base material may be bonded together by a moisture-curable polyurethane hot-melt resin composition.

As the resin film, polyester such as polyethylene terephthalate, polyethylene naphthalate, and polybutylene terephthalate, olefin resin, polyacrylate, polyvinyl chloride, polyethylene, polypropylene ethylene vinyl alcohol, polyurethane resin, polyamide resin, What made a polyimide resin, a fluororesin, etc. a raw material can be used. Among these, even when a urethane resin film such as a thermoplastic urethane resin (TPU), which has recently been increasingly used for moisture permeability, a fluororesin film, an olefin resin film, etc., is used, by using the moisture-curable polyurethane hot melt resin composition of the present invention , Excellent adhesive strength can be obtained.

As the fiber base material, for example, polyester fiber, polyethylene fiber, nylon fiber, acrylic fiber, polyurethane fiber, acetate fiber, rayon fiber, polylactic acid fiber, cotton, hemp, silk, wool, glass fiber, carbon fiber, Non-woven fabrics, woven fabrics, and knitted fabrics made of these blended fibers or the like can be used. Further, in the present invention, even when a fiber substrate made of a raw material is water-repelled according to a known method, excellent adhesive strength can be obtained.

As a method of forming a cured product layer of the moisture-curable polyurethane hot melt resin composition on the resin film or fiber substrate, for example, melting at 50 to 130°C on the resin film or fiber substrate. A method of coating the moisture-curable polyurethane hot melt resin composition; A method of coating the moisture-curable polyurethane hot-melt resin composition melted at, for example, 50 to 130°C on a release paper, and then bonding the cured product layer to the resin film or fiber substrate, etc. Can be mentioned.

In any of the above methods, as a method of coating the moisture-curable polyurethane hot melt resin composition, for example, a method of using a roll coater, a knife coater, a spray coater, a gravure coater, a comma coater, a T-die coater, an applicator, etc. Can be lifted.

After coating the moisture-curable polyurethane hot melt resin composition, it can be dried and cured according to a known method.

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

[Example]

Hereinafter, the present invention will be described in more detail using examples.

[Example 1]

100 parts by mass of polypropylene glycol (number average molecular weight; 700, hereinafter abbreviated as "PPG700") was added to a four-necked flask equipped with a thermometer, stirrer, inert gas inlet and reflux condenser, mixed, and heated under reduced pressure at 70°C. By doing this, it dehydrated until the moisture in a flask became 0.05 mass% or less.

Then, the flask was cooled to 90°C, and 65.2 parts by mass of 4,4′-diphenylmethane diisocyanate (hereinafter abbreviated as “MDI”) melted at 70°C was added, and the isocyanate group content was NCO% by reacting at 110° C. for about 3 hours until it becomes constant; A 5.9 mass% hot melt urethane prepolymer was obtained.

Next, after melting the obtained urethane prepolymer at 80°C for 1 hour, using a gravure coater (speed: 8 m/min) on a thermoplastic urethane resin film (hereinafter abbreviated as “TPU”), the applied amount is 15 g/m 2 Applied. Then, the polyester fiber base material was bonded and left to stand for 3 hours under conditions of a temperature of 23°C and a relative humidity of 65% to obtain a laminate (1).

In addition, instead of the polyester fiber base material, a nylon fiber base material was used to similarly produce the laminate (2).

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

A moisture-curable polyurethane hot-melt resin composition and a laminate were obtained in the same manner as in Example 1, except that the types and blending amounts of the raw materials used in the production of the urethane prepolymer (i) were changed as shown in Tables 1-2. .

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

After melting the moisture-curable polyurethane hot-melt resin composition obtained in Examples and Comparative Examples at 80°C or 120°C for 1 hour, 1 ml was sampled and a cone plate viscometer (M·S·T Engineering Co., Ltd. digital viscometer “ CV-1S RT type”, 40P cone, rotor rotation: 50 rpm), and (40P cone, rotor rotation: 50 rpm), the melt viscosity (80°C or 120°C melt viscosity) was measured.

[Adhesion Strength Evaluation Method]

About the obtained laminated body, the crosshead measurement was carried out using Tenshiro (Tenshiro universal testing machine "RTC-1210A" manufactured by Orientech Co., Ltd.); The peel strength was measured under the conditions of 200 mm/min, and it was set as the adhesive strength.

"○"; 10N／inch or more

"X"; Less than 10N／inch

[Table 1]

[Table 2]

Abbreviations in Tables 1 to 2 are as follows.

"PPG400"; Polypropylene glycol (number average molecular weight; 400)

"PEs1"; What made diethylene glycol, neopentyl glycol, hexanediol, and adipic acid react, and the number average molecular weight; 2000, liquid at room temperature

"PPG1000"; Polypropylene glycol (number average molecular weight; 1,000)

"PPG2000"; Polypropylene glycol (number average molecular weight; 2,000)

It was found that the moisture-curable polyurethane hot-melt resin composition of the present invention has excellent adhesive strength.

On the other hand, in Comparative Examples 1 and 2, both of the melt viscosity at 120°C and 80°C were used, which were less than the range specified in the present invention, but the adhesive strength was insufficient.

In Comparative Examples 3 and 4, both of the melt viscosity at 120°C and 80°C were used which exceeded the range specified in the present invention, but the adhesive strength was insufficient.

Claims (12)

The melt viscosity at 120°C is in the range of 160 to 600 mPa·s, and the melt viscosity at 80°C is in the range of 850 to 6,000 mPa·s, and the melt viscosity at 80°C is in the range of 120°C. The moisture-curable polyurethane hot-melt resin composition characterized in that the ratio [melt viscosity at 80°C/melt viscosity at 120°C] is in the range of 7 to 9.5. delete The method of claim 1,
A moisture-curable polyurethane hot-melt resin composition comprising a urethane prepolymer (i) which is a reaction product of a polyol (a) and a polyisocyanate (b) and has an isocyanate group. The method of claim 3,
Moisture wherein the polyol (a) is a polyol (a-1) having a number average molecular weight of less than 1,000, or a combination of a polyol (a-1) having a number average molecular weight of less than 1,000 and a polyol (a-2) having a number average molecular weight of 1,000 or more Curable polyurethane hot melt resin composition. The method of claim 3,
The moisture curable polyurethane hot melt resin composition, wherein the polyol (a) contains 50% by mass or more of a polyether polyol. The method of claim 5,
The polyether polyol is a moisture-curable polyurethane hot melt resin composition in which polypropylene glycol. The method of claim 3,
Moisture-curable polyurethane hot-melt resin composition in which the amount of polyisocyanate (b) as a raw material for the urethane prepolymer (i) 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 method of claim 3,
The polyisocyanate (b) is a moisture-curable polyurethane hot melt resin composition, wherein the polyisocyanate (b) is diphenylmethane diisocyanate. A laminate comprising: a cured product layer of the moisture-curable polyurethane hot-melt resin composition according to claim 1, and a resin film or a fibrous substrate are sequentially laminated. The method of claim 9,
A laminate in which the fibrous substrate has been subjected to a water repellent treatment. The method of claim 9,
A laminate in which the resin film is formed of a fluororesin, a urethane resin, or an olefin resin. The method of claim 9,
The laminated body wherein the resin film is a thermoplastic urethane resin.