KR102113097B1 - Moisture-curable urethane hot melt resin composition, and laminate - Google Patents

Abstract

The present invention includes polyethylene glycol and / or polyoxyethylene polyoxypropylene glycol (a1), aromatic polyester polyol (a2) based on phthalic acid, and crystalline aliphatic polyester polyol (a3), and oxyethylene It is to provide a moisture-curable urethane hot-melt resin composition comprising a urethane prepolymer having an isocyanate group that is a reactant of polyol (A) and polyisocyanate (B) having a structure content of 5 to 18 mol / kg. Moreover, this invention provides the laminated body which has the hardened | cured material (i) of the said moisture hardening type urethane hot-melt resin composition, and a bubble (ii). The problem to be solved by the present invention is to provide an adhesive that provides excellent lamination with both excellent moisture permeability and peel strength, and provides excellent wind bonding.

Description

Moisture-curable urethane hot melt resin composition, and laminate

The present invention relates to a moisture-curable urethane hot-melt resin composition that can be particularly suitably used as an adhesive for producing a moisture-permeable waterproof fabric or synthetic leather that requires moisture permeability.

In general, in mountaineering clothes and sportswear, in addition to mobility and lightness when worn, excellent moisture permeability and waterproofness are required. Among them, moisture permeability is an important property for suppressing the discomfort caused by sweating caused by water accumulating in the body due to sweating and the like.

As the moisture-permeable waterproof fabric having the moisture-permeable property, a material in which a base material and a moisture-permeable material are bonded together using an adhesive is generally used (for example, refer to Patent Documents 1 and 2). While excellent moisture permeability is also required as the adhesive, it has been disclosed that a urethane adhesive using a polyol having an oxyethylene group having excellent hydrophilicity as a raw material has excellent moisture permeability (for example, see Patent Document 3).

However, when a large number of oxyethylene groups having high hydrophilicity are included, there is a problem in that the peel strength is low and the washing resistance is poor.

Japanese Patent Publication No. 2009-12309 Japanese Patent Publication No. 63-291968 Japanese Patent Publication No. 2007-77191

The problem to be solved by the present invention is to provide an adhesive that provides excellent lamination with both excellent moisture permeability and peel strength, and provides excellent wind bonding.

The present invention includes polyethylene glycol and / or polyoxyethylene polyoxypropylene glycol (a1), aromatic polyester polyol (a2) based on phthalic acid, and crystalline aliphatic polyester polyol (a3), and oxyethylene It is to provide a moisture-curable urethane hot-melt resin composition comprising a urethane prepolymer having an isocyanate group that is a reactant of polyol (A) and polyisocyanate (B) having a structure content of 5 to 18 mol / kg.

Moreover, this invention provides the laminated body which has a bubble (i) and hardened | cured material (ii) of the said moisture hardening type urethane hot melt resin composition.

The moisture-curable urethane hot-melt resin composition of the present invention is compatible with excellent moisture permeability and peel strength, and the resulting laminate is excellent in air-conditioning. Therefore, the moisture-curable urethane hot melt of the present invention can be particularly preferably used as an adhesive for producing a moisture-permeable waterproof fabric or synthetic leather that requires moisture permeability.

The moisture-curable urethane hot-melt resin composition of the present invention includes polyethylene glycol and / or polyoxyethylene polyoxypropylene glycol (a1), aromatic polyester polyol (a2) based on phthalic acid, and crystalline aliphatic polyester polyol (a3). ), And a urethane prepolymer having an isocyanate group which is a reactant of polyol (A) and polyisocyanate (B) having an oxyethylene structure content of 5 to 18 mol / kg.

Since the polyethylene glycol and / or polyoxyethylene polyoxypropylene glycol (a1) has an oxyethylene group excellent in hydrophilicity, it is an essential component for obtaining excellent moisture permeability.

As a number average molecular weight of the said polyethylene glycol and polyoxyethylene polyoxypropylene glycol, it is preferable that it is the range of 900-20,000, and it is more preferable that it is the range of 1,000-5,000 from the point which the outstanding moisture permeability is obtained. Moreover, the number average molecular weight of the said polyethylene glycol and polyoxyethylene polyoxypropylene glycol shows the value measured by the gel permeation chromatography (GPC) method on the following conditions.

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

Column: The following columns manufactured by Tosoh Corporation were used in series.

 `` TSKgel G5000 '' (7.8 mmI.D. x 30 cm) x 1

 `` TSKgel G4000 '' (7.8 mmI.D. x 30 cm) x 1

 `` TSKgel G3000 '' (7.8 mmI.D. x 30 cm) x 1

 `` TSKgel G2000 '' (7.8 mmI.D. x 30 cm) x 1

Detector: RI (differential refractometer)

Column temperature: 40 ℃

Eluent: Tetrahydrofuran (THF)

Flow rate: 1.0 mL / min

Injection volume: 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

The amount of polyethylene glycol and polyoxyethylene polyoxypropylene glycol (a1) used (total amount) is preferably in the range of 20 to 80% by mass in polyol (A), from the viewpoint of obtaining a more excellent moisture permeability, and 40 to 70 It is more preferable that it is the range of mass%, and it is more preferable that it is the range of 50-60 mass%.

In the present invention, it is essential that the content of the oxyethylene structure is in the range of 5 to 18 mol / kg in the polyol (A), preferably in the range of 8 to 16 mol / kg, more preferably 10 to 14 mol / kg Range. When the content of the oxyethylene structure is less than 5 mol / kg, the desired moisture permeability is not obtained, and when it exceeds 18 mol / kg, the desired peel strength or wind resistance is not obtained. Moreover, since the said oxyethylene structure is supplied from the said (a1) component, content of the said oxyethylene structure can be appropriately determined by preparing the said (a1) component.

The aromatic polyester polyol (a2), in order to obtain excellent compatibility, it is essential to use phthalic acid as a raw material. By using phthalic acid as a raw material, since a polyester polyol having a high viscosity and starch syrup can be obtained, it can be considered that a laminate having excellent fusion is obtained by using this.

As the aromatic polyester polyol (a2), for example, a reactant of a polybasic acid containing phthalic acid and a compound having two or more hydroxyl groups can be used.

As said phthalic acid, orthophthalic acid, isophthalic acid, terephthalic acid, phthalic anhydride can be used. These phthalic acids may be used alone or in combination of two or more. Among these, it is preferable to use orthophthalic acid and / or phthalic anhydride from the viewpoint that even better mixing is obtained.

Other polybasic acids can be used in combination with the phthalic acid if necessary. As content of the said phthalic acid in that case, it is preferable that it is 60 mass% or more in all polybasic acids, and it is more preferable that it is 80 mass% or more.

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

As the compound having two or more hydroxyl groups, for example, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, dodecane Diol, trimethylolpropane, trimethylolethane, glycerin, neopentyl glycol, 3-methyl-1,5-pentanediol, 2,2-dimethyl-1,3-propylene glycol, 2,4-diethyl-1,5 -Pentanediol, 2-methyl-1,8-octanediol, 2-ethyl-2-butyl-1,3-propanediol, and the like can be used. These compounds may be used alone or in combination of two or more. Among these, it is preferable to use neopentyl glycol and diethylene glycol from the viewpoint that the amorphous property can be further enhanced.

As a number average molecular weight of the said aromatic polyester polyol (a2), it is preferable that it is the range of 900-5,000, and it is more preferable that it is the range of 1,000-3,000 from the point which further excellent mixing is obtained. In addition, the number average molecular weight of the said aromatic polyester polyol (a2) shows the value measured like the number average molecular weight of the said polyethylene glycol and polyoxyethylene polyoxypropylene glycol.

As the usage-amount of the said aromatic polyester polyol (a2), it is preferable that it is the range of 10-40 mass% in polyol (A), and it is more preferable that it is the range of 15-30 mass% from the point which further excellent mixing is obtained. , It is more preferably in the range of 18 to 25% by mass.

The content of the aromatic ring in the polyol (A) is preferably 0.3 to 1.2 mol / kg, more preferably 0.5 to 1 mol / kg, and more preferably 0.55 to 0.55 to 1 mol / kg, from the viewpoint of further excellent mixing. It is more preferable to be in the range of 0.8 mol / kg. Moreover, content of the aromatic ring in the said polyol (A) shows content of the aromatic ring in the said raw material with respect to the total mass of each raw material which comprises the said polyol (A). In addition, in the above calculation, it is assumed that the molecular weight of the benzene ring or the naphthalene ring excluding the organic group is used as the molecular weight of the aromatic ring.

The crystalline aliphatic polyester polyol (a3) is an essential component for obtaining excellent peel strength and moisture permeability. When the crystalline aliphatic polyester polyol (a3) having excellent peel strength is not used, not only good peel strength is not obtained, but also the urethane prepolymer rich in the aromatic polyester polyol (a2) is obtained, so that air bubbles are present. Too impregnated, causing clogging, and the desired moisture permeability is not obtained. In addition, in this invention, "crystallinity" means that the peak of the heat of crystallization or heat of fusion can be confirmed in DSC (differential scanning calorimeter) measurement based on JISK7121-1987.

Examples of the crystalline aliphatic polyester polyol (a3) include polybasic acids such as oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid and 1,12-dodecanedicarboxylic acid, and the aromatic polyester polyol A reactant with a compound having two or more of the above hydroxyl groups which can be used as a raw material for (a2) can be used. Among them, at least one compound selected from the group consisting of ethylene glycol, butanediol, hexanediol, and dodecanediol, adipic acid, sebacic acid, and the like, from the viewpoint of improving crystallinity and obtaining a superior peel strength. It is preferable to use a reactant with at least one polybasic acid selected from the group consisting of 1,12-dodecanedicarboxylic acid.

As a number average molecular weight of the said crystalline aliphatic polyester polyol (a3), it is preferable that it is the range of 900-10,000, and it is more preferable that it is the range of 1,000-6,000 from the point which further excellent peel strength and moisture permeability are obtained. Moreover, the number average molecular weight of the said crystalline aliphatic polyester polyol (a3) shows the value measured similarly to the number average molecular weight of the said polyethylene glycol and polyoxyethylene polyoxypropylene glycol.

As a usage-amount of the said crystalline aliphatic polyester polyol (a3), it is preferable that it is the range of 10-40 mass% in polyol (A), and it is more preferable that it is the range of 15-30 mass% from the point which further excellent mixing is obtained. It is preferable, and it is more preferable that it is 18-25 mass% of range.

The said polyol (A) contains the said (a1)-(a3) as an essential component, but can contain other polyol as needed.

As said other polyol, polyoxypropylene glycol, polyoxytetramethylene glycol, polyacrylic polyol, polycarbonate polyol, polybutadiene polyol, etc. can be used, for example. These polyols may be used alone or in combination of two or more.

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

As the usage-amount of the said polyisocyanate (B), it is preferable that it is the range of 5-40 mass% of the total mass of the raw material which comprises a urethane prepolymer, and it is more preferable that it is the range of 10-30 mass%.

The urethane prepolymer is a reactant of the polyol (A) and the polyisocyanate (B), but from the viewpoint of forming a crosslinked structure and further improving the balance between peel strength and moisture permeability, it has three additional hydroxyl groups. It is preferable to use compound (C) as a raw material.

Examples of the compound (C) include glycerin and trimethylolpropane; Polyoxypropylene triols, polymers of glycerin and propylene oxide, and compounds having oxyalkylene groups, such as polymers of polyoxypropylene triol and ethylene oxide, can be used. These compounds may be used alone or in combination of two or more. Among these, it is preferable to use the compound having the oxyalkylene group from the viewpoint of good compatibility with the polyol (A), and further excellent moisture permeability and peel strength, and polyoxypropylene triol is used. It is more preferable to use.

As a number average molecular weight of the compound which has the said oxyalkylene group, it is preferable that it is 300-800 range from the point which compatibility with the said polyol (A) is favorable, and further excellent moisture permeability and peel strength are obtained. . Moreover, the number average molecular weight of the compound which has the said oxyalkylene group shows the value measured similarly to the number average molecular weight of the said polyethylene glycol and polyoxyethylene polyoxypropylene glycol.

As a usage-amount in the case of using the said compound (C), since it has good compatibility with the said polyol (A), and further excellent moisture permeability and peel strength are obtained, about 100 mass parts of polyol (A), It is preferably in the range of 0.01 to 10 parts by mass, more preferably in the range of 0.1 to 7 parts by mass, and more preferably in the range of 0.5 to 5 parts by mass.

The urethane prepolymer is obtained by reacting the polyol (A) with the polyisocyanate (B), preferably the compound (C), and reacting with moisture present in the air or a substrate to which the urethane prepolymer is applied to form a crosslinked structure. It has an isocyanate group that can be formed.

As a method for producing the urethane prepolymer, for example, the polyol (A) and preferably the compound (C) are mixed in a reaction vessel containing the polyisocyanate (B), heated after mixing, and the polyisocyanate (B ) Can be produced by reacting the isocyanate group of the polyol (A) with an excess of the hydroxyl group.

When preparing the urethane prepolymer, as the equivalent ratio (isocyanate group / hydroxyl group) of the isocyanate group of the polyisocyanate (B) and the hydroxyl group of the polyol (A) and the compound (C), further excellent peel strength From the obtained point, it is preferable to be in the range of 1.1 to 5, and more preferably 1.5 to 3.

As the isocyanate group content rate (hereinafter abbreviated as "NCO%") of the urethane prepolymer obtained by the above method, it is preferable that it is in the range of 1.7 to 5, and in the range of 1.8 to 3, from the viewpoint of obtaining more excellent peel strength. It is more preferable. Moreover, NCO% of the said urethane prepolymer shows the value measured by the potentiometric titration method based on JISK1603-1: 2007.

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

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

As described above, the moisture-curable urethane hot-melt resin composition of the present invention is compatible with excellent moisture permeability and peel strength, and the obtained laminate is excellent in air-conditioning. Therefore, the moisture-curable urethane hot melt of the present invention can be particularly preferably used as an adhesive for producing a moisture-permeable waterproof fabric or synthetic leather that requires moisture permeability.

As a method for producing the moisture-permeable waterproof fabric and synthetic leather in the case where the moisture-curable urethane hot-melt resin composition of the present invention is used as an adhesive when producing the moisture-permeable waterproof fabric and synthetic leather, for example, known moisture-permeable A cured product of a moisture-permeable film and a moisture-curable urethane hot-melt resin composition by applying a moisture-curable urethane hot-melt resin composition of the present invention melted at, for example, 50 to 130 ° C on a film, and then bonding bubbles (i). and ii) and a method of forming a laminate having bubbles (i).

When the moisture-curable urethane hot-melt resin composition of the present invention is applied on the moisture-permeable film, it is preferable to apply the moisture-curable urethane hot-melt resin composition intermittently in a dot or network shape, and more preferably in a dot shape.

As a method of intermittently applying the moisture-curable urethane hot melt resin composition, for example, a gravure transfer coat, a screen coat method, a T-die coat method, a die coater method having a gear pump, a fiber coat method, etc. And a method of use.

As said bubble (i), For example, Chemical fiber, such as polyester fiber, nylon fiber, acrylic fiber, polyurethane fiber, acetate fiber, rayon fiber, polylactic acid fiber; What is obtained from cotton, hemp, silk, wool, these blend fibers, etc. can be used.

After the bubbles (i) are bonded, the moisture-curable urethane hot melt resin composition may be dried and cured by a known method.

The thickness of the cured product (ii) of the moisture-curable urethane hot melt resin composition is, for example, in the range of 0.001 to 0.5 cm.

(Example)

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

[Example 1]

To a four-necked flask equipped with a thermometer, stirrer, inert gas inlet and reflux cooler, 47 parts by mass of polyoxyethylene glycol (number average molecular weight: 3,000, abbreviated as "PEG3000"), aromatic polyester polyol (neopentyl) Glycol, diethylene glycol, and phthalic anhydride reacted, and the number average molecular weight: 1,000, or less, abbreviated as "aromatic PEs-1", 17.5 parts by mass, crystalline aliphatic polyester polyol (hexane diol and sebacic acid are reacted) Number average molecular weight: 3,500, hereinafter abbreviated as "crystalline PEs-1" 17.5 parts by weight, polyoxypropylene triol (Mitsui Chemical Co., Ltd. "T-700", number average molecular weight: 700 , Hereinafter abbreviated as "T-700") was added 1 part by mass, mixed, and dehydrated until the moisture in the flask became 0.05% by mass or less by heating under reduced pressure at 100 ° C.

Next, the inside of the flask was cooled to 90 ° C, and 22 parts by mass of 4,4'-diphenylmethane diisocyanate (hereinafter abbreviated as "MDI") melted at 70 ° C was added, and the isocyanate group content was constant under a nitrogen atmosphere. A urethane prepolymer was obtained by reacting at 110 ° C. for about 3 hours until done.

[Examples 2 to 3 and Comparative Examples 1 to 6]

As shown in Table 1, a urethane prepolymer was obtained in the same manner as in Example 1 except that the type and amount of the polyol and the amount of the polyisocyanate were changed.

[Production Method of Laminate]

The urethane prepolymer obtained in Examples and Comparative Examples was melted at 120 ° C. for 1 hour, and then, using a 40-line / inch lattice gravure roll heated to 120 ° C., a moisture-permeable urethane film (solvent system manufactured by DCC) Using a urethane resin composition "Crisbon S-525", it was applied intermittently in a dot form at 20 g / m2 on a urethane film produced with a film thickness of 12 mu m. Next, a 40 denier nylon taffeta was bonded as a bubble to the coated surface, and a laminate was obtained by leaving it under the conditions of a temperature of 23 ° C and a relative humidity of 65% for 3 hours.

[Method of evaluating moisture permeability]

The moisture permeability of the obtained laminate was measured in accordance with the A-1 method (potassium chloride method) and the B-1 method (potassium acetate method) of JISL1099: 2012. The moisture permeability was evaluated to have excellent moisture permeability in the case of 4,000 (g / m 2 / 24h) or more in the A-1 method and 30,000 (g / m 2 / 24h) or more in the B-1 method.

[Method for measuring peel strength]

(State peel strength)

For the obtained laminate, the peel strength (N / cm) was measured under a condition of crosshead speed: 200 mm / min using Tensiron (Tensiron Universal Testing Machine "RTC-1210A" manufactured by Orientec Co., Ltd.). It was made into peeling strength in the state.

(Wet peel strength)

The obtained laminate was immersed in water at a temperature of 23 ° C. for 24 hours. Then, peeling strength (N / cm) was measured similarly, and it was set as the wet peeling strength.

When the said state peeling strength was 5 (N / cm) or more, and the wet peeling strength was 4 (N / cm) or more, it evaluated that it had excellent peeling strength.

[Method of evaluating compatibility]

The wind of the obtained laminate was evaluated as follows according to the feel.

「A」: Very flexible

「B」: Good flexibility

「C」: Hardness

[Table 1]

The abbreviation in Table 1 is demonstrated.

"PEG2000": polyoxyethylene glycol (number average molecular weight: 2,000)

"PEG3000": Polyoxyethylene glycol (number average molecular weight: 3,000)

"PTMG3000": polyoxytetramethine glycol (number average molecular weight: 3,000)

"D-3000": Polyoxypropylene glycol (Mitsui Chemicals "Actocol D-3000", number average molecular weight: 3,000)

It was found that the laminate obtained by using the moisture-curable urethane hot-melt resin composition of the present invention has excellent moisture permeability, peel strength, and wind affinity.

On the other hand, Comparative Example 1 is an aspect in which the content of the oxyethylene structure in the polyol (A) exceeds the range specified in the present invention, but the peel strength and the mixing are insufficient.

In Comparative Example 2, although the content of the oxyethylene structure in the polyol (A) was below the range specified in the present invention, moisture permeability was insufficient.

In Comparative Examples 3 and 4, instead of (a1), polyoxytetramethylene glycol or polyoxypropylene glycol was used, but both had poor moisture permeability.

Comparative Example 5 is an embodiment in which the crystalline aliphatic polyester polyol (a3) was not used, but the moisture permeability and peel strength in the A-1 method were insufficient.

Comparative Example 6 is an aspect in which an aromatic polyester polyol (a2) was not used, but the mixing was poor.

Claims (5)

Polyethylene glycol and / or polyoxyethylene polyoxypropylene glycol (a1),
Aromatic polyester polyol (a2) based on phthalic acid and
Crystalline aliphatic polyester polyol (a3),
Polyol (A) having a content of oxyethylene structure in the range of 5 to 18 mol / kg, polyisocyanate (B), isocyanate as a reactant of a compound (C) having three hydroxyl groups and having a number average molecular weight in the range of 300 to 800 A moisture-curable urethane hot melt resin composition comprising a urethane prepolymer having a group. According to claim 1,
The moisture-curable urethane hot melt resin composition in which the content of the aromatic ring in the polyol (A) is in the range of 0.3 to 1.2 mol / kg. delete According to claim 1,
Moisture-curable urethane hot-melt resin composition in which the compound (C) has an oxyalkylene group. A laminate comprising a base material (i) and a cured product (ii) of the moisture-curable urethane hot melt resin composition according to claim 1 or 2.