TW201940639A - Moisture curing hot melt adhesive and adhesive body - Google Patents

Abstract

This moisture curing hot melt adhesive comprises a urethane prepolymer which is a reactant of a polyol which includes at least one selected from the group consisting of a polybutadiene polyol and a hydrogenated polybutadiene polyol, a hydroxyl group-containing rosin compound, and a polyisocyanate, wherein the hydroxyl group-containing rosin compound has a hydroxyl value of 20 to 100 mgKOH/g.

Description

Moisture hardening hot melt adhesive and adherend

The invention relates to a moisture-curable hot-melt adhesive and an adherend.

The hot-melt adhesive is a solvent-free adhesive, so it has less burden on the environment and the human body, and can adhere in a short time. Therefore, it is an adhesive suitable for improving productivity. Hot-melt adhesives can be roughly classified into the following two types: hot-melt adhesives containing a thermoplastic resin as a main component; and hot-melt adhesives containing a reactive resin as a main component. As a reactive resin, an urethane prepolymer having an isocyanate group at the terminal is mainly used. A reactive hot-melt adhesive containing an amine ester prepolymer as a main component can exhibit a certain degree of adhesion strength (initial adhesion) in a short time by cooling and solidifying the adhesive itself after coating. Then, by reacting the terminal isocyanate group of the amine ester prepolymer with moisture in the air or moisture on the surface of the adherend, the polymer is quantified and crosslinked, whereby the adhesive hardens and exhibits adhesiveness. Such an adhesive is called a "moisture-curable hot-melt adhesive." Moisture-curable hot-melt adhesives containing an amine ester prepolymer as a main component tend to show good adhesion strength even when heated.

In addition, in order to improve the initial adhesion of a moisture-curable hot-melt adhesive, the use of a tackifier with an amine ester prepolymer is being studied (for example, see Patent Documents 1 and 2).
[Prior technical literature]
(Patent Literature)

Patent Document 1: Japanese Patent Application Laid-Open No. 3-111475 Patent Document 2: Japanese Patent Application Laid-Open No. 2010-126615

[Problems to be solved by the invention]
In recent years, moisture-curable hot-melt adhesives have also gradually been used for materials such as clothing and diapers, such as cloth and paper. From the viewpoint of operability, it has been sought for an adhesive used in a joint portion of clothing such as sportswear and underwear to exhibit adhesiveness immediately after the cloths are pasted to each other and to exhibit excellent adhesiveness after moisture curing. In addition, such an adhesive requires, in addition to the adhesion to the cloth, a cured product having excellent flexibility in order to provide good wearing feeling.

Therefore, the main object of the present invention is to provide a moisture-curable hot-melt adhesive, which has high initial adhesion, excellent adhesion to cloth, and can form a cured product having excellent flexibility.
[Technical means to solve the problem]

One aspect of the present invention provides a moisture-curable hot-melt adhesive, which contains an amine ester prepolymer, which is a reactant of a polyol, a rosin compound containing a hydroxyl group, and a polyisocyanate. The alcohol includes at least one selected from the group consisting of a polybutadiene polyol and a hydrogenated polybutadiene polyol, and the hydroxyl value of the rosin compound containing a hydroxyl group is 20 to 100 mgKOH / g.

One aspect of the present invention provides a moisture-curable hot-melt adhesive containing an amine ester prepolymer having a polymer chain including a structural unit derived from a polyol and a polyisocyanate derived The structural unit of the polyol includes at least one selected from the group consisting of a polybutadiene polyol and a hydrogenated polybutadiene polyol; a group derived from a rosin compound containing a hydroxyl group, One of the ends; and, an isocyanate group at the other end of the polymer chain.

The polyol may comprise a hydrogenated polybutadiene polyol. The hydroxyl-containing rosin compound may be a rosin compound having one hydroxyl group.

Moisture-hardening hot-melt adhesives can be used to adhere multiple pieces of cloth to each other.

In another aspect, the present invention provides an adherend including: a plurality of pieces of cloth; and a hardened material, which is a hardened material of the moisture-curable hot-melt adhesive, and the hardened material adheres the plurality of pieces of cloth to each other.
[efficacy]

According to the present invention, it is possible to provide a moisture-curable hot-melt adhesive, which has high initial adhesion, is excellent in adhesion to a cloth, and can form a cured product having excellent flexibility. Furthermore, according to the present invention, it is possible to provide an adhesive body using such a moisture-curable hot-melt adhesive.

Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.

In the present specification, "polyol" means a compound having an average of more than one hydroxyl group in the molecule, and "polyisocyanate" means a compound having an average of more than one isocyanate group in the molecule.

In this specification, the "initial adhesion" means the adhesion before the moisture-hardening of the adhesive layer after the adherends are pressed together via the adhesive layer formed by the adhesive, and the so-called "after curing" "Adhesiveness" means the adhesiveness of the above-mentioned adhesive layer after moisture hardening.

＜ Moisture hardening hot melt adhesive ＞
A moisture-curable hot-melt adhesive according to one embodiment includes an amine ester prepolymer. The amine ester prepolymer is a reactant of a polyol, a rosin compound containing a hydroxyl group, and a polyisocyanate. The polyol contains a polymer from a polymer. At least one selected from the group consisting of butadiene polyol and hydrogenated polybutadiene polyol, wherein the hydroxyl value of the rosin compound containing a hydroxyl group is 20 to 100 mgKOH / g.

In general, moisture-curable hot-melt adhesives can exhibit high-molecular-weight properties through chemical reactions, and exhibit adhesiveness and the like. The amine ester prepolymer having an isocyanate group at the end of the polymerization chain is hardened by reacting with moisture, so the use of the amine ester prepolymer alone can produce the effect of a moisture-hardening hot-melt adhesive. The moisture-curable hot-melt adhesive may contain components other than the amine ester prepolymer.

[Amine ester prepolymer]
The amine ester prepolymer according to this embodiment can be obtained by reacting a polyol, a hydroxyl-containing rosin compound, and a polyisocyanate. The polyol includes a polybutadiene polyol and a hydrogenated polybutadiene polyol. At least one selected from the group.

The amine ester prepolymer according to this embodiment has a polymer chain including a structural unit derived from a polyhydric alcohol and a structural unit derived from a polyisocyanate. The polyol includes a polybutadiene polyol and a hydrogenated polybutadiene polyol. At least one selected from the group consisting of: a group derived from a rosin compound containing a hydroxyl group at one end of the polymer chain; and an isocyanate group at the other end of the polymer chain. Since such an amine ester prepolymer has a non-reactive group (a group derived from a rosin compound) and a reactive group (isocyanate group), it has excellent initial adhesion and can adjust the crosslinking density of the cured product. And improve flexibility and stretchability.

The moisture-curable hot-melt adhesive of this embodiment may further contain an amine ester prepolymer having groups derived from a rosin compound containing a hydroxyl group at both ends of the polymer chain. Since such an amine ester prepolymer does not have an isocyanate group, it does not contribute to the adhesiveness after aging, but since both ends have a group derived from a rosin compound, the initial adhesiveness can be improved. The moisture-curable hot-melt adhesive may further contain a compound derived from the reaction of a hydroxyl-containing rosin compound with a polyisocyanate. Since such a compound does not have a group derived from a rosin compound, it can contribute to increase the initial adhesion. The moisture-curable hot-melt adhesive may further include an amine ester prepolymer having isocyanate groups at both ends of the polymer chain. Since such an amine ester prepolymer has isocyanate groups at both ends, it is possible to increase the crosslinking density of the cured product and to improve the tackiness after curing.

(Hydroxy-containing rosin compound)
The hydroxyl value of the hydroxyl-containing rosin compound of this embodiment is 20 to 100 mgKOH / g, and from the viewpoint of initial adhesion, it may be 25 mgKOH / g or more, 30 mgKOH / g or more, or 35 mgKOH / g or more. From the viewpoint of flexibility and stretchability, it may be 80 mgKOH / g or less, 70 mgKOH / g or less, 60 mgKOH / g or less, or 50 mgKOH / g or less. The hydroxyl value can be measured in accordance with JIS K 1557-1.

From the viewpoint of the balance between adhesiveness, softness, and stretchability after hardening, the acid value of the hydroxyl-containing rosin compound may be 5 to 30 mgKOH / g, 8 to 25 mgKOH / g, 9 to 20 mgKOH / g, or 10-15 mgKOH / g. The acid value can be measured in accordance with JIS K 0070.

From the viewpoint of improving initial adhesion, the softening point of the hydroxyl-containing rosin compound may be 90 to 110 ° C, 95 to 105 ° C, or 98 to 103 ° C. The softening point can be measured by the ring and ball method in accordance with JIS K 5601-2-2.

The rosin compound containing a hydroxyl group according to this embodiment has at least one rosin skeleton derived from rosin and a hydroxyl group bonded to the rosin skeleton. The rosin skeleton may include a structure in which two or more rosins are bonded, and may also include a rosin ester structure. From the viewpoint of forming a cured product excellent in flexibility and stretchability, a rosin compound having one hydroxyl group (hereinafter referred to as "rosin monool") can be used as the hydroxyl-containing rosin compound. A rosin monool and a rosin compound having two or more hydroxyl groups (hereinafter referred to as "rosin polyol") can be used in combination as a rosin compound containing a hydroxyl group. The rosin polyol may have, for example, a first partial structure including a first hydroxyl group, a second partial structure including a second hydroxyl group, and a rosin skeleton, and the first partial structure and the second partial structure may be connected to each other by a rosin skeleton. Structure together.

The rosin compound containing a hydroxyl group can use a commercial item as it is. As a commercially available thing of the hydroxyl-containing rosin compound of this embodiment, the trade name "KE-359" by Arakawa Chemical Industry Co., Ltd. is mentioned, for example.

The content of the hydroxy-containing rosin compound may be 5 masses based on the total mass of the polyol and the hydroxy-containing rosin compound (hereinafter referred to as "the total mass of the component having a hydroxy group") from the viewpoint of initial adhesion. % Or more, 10% by mass or more, or 15% by mass or more. The content of the hydroxyl-containing rosin compound may be 50% by mass or less, 40% by mass or less based on the total mass of the component having a hydroxyl group from the viewpoint of the balance between flexibility, stretchability, and adhesion. Or less than 35% by mass. The larger the content of the hydroxyl-containing rosin compound, the easier it is to improve the initial tackiness of the moisture-curable hot-melt adhesive.

From the viewpoint of further improving the initial adhesion, the hydroxyl-containing rosin compound is preferably a compound that is compatible with the polybutadiene polyol and the hydrogenated polybutadiene polyol.

(Polyol)
A polybutadiene polyol is a compound having a polymer chain derived from butadiene and hydroxyl groups at both ends of the polymer chain, and the hydrogenated polybutadiene polyol is a hydride of the polybutadiene polyol. . The polybutadiene polyol and hydrogenated polybutadiene polyol may have an average of about 1.8 to 2.5 hydroxyl groups in the molecule. The polymer chain derived from polybutadiene and its hydride can act as an elastomer. By having such a polymer chain, it is possible to impart adhesiveness, softness, and stretchability to the amine ester prepolymer. The polymer chain of the urethane prepolymer preferably contains a structural unit derived from a hydrogenated polybutadiene polyol.

As the polybutadiene polyol and the hydrogenated polybutadiene polyol, commercially available products can be used as they are. Examples of commercially available products of hydrogenated polybutadiene polyols include GI-1000, GI-2000, and GI-3000 (all of which are trade names and manufactured by Soda Co., Ltd.). As commercially available products of polybutadiene polyols, for example: GI-1000, GI-2000, GI-3000 (all are trade names, manufactured by Soda Co., Ltd.); Poly bd R-15HT, Poly bd R -45HT (both are trade names, manufactured by Idemitsu Kosan Co., Ltd.); Krasol LBH-P3000 (trade name, manufactured by Cray Valley) and the like. These may be used alone or in combination of two or more.

From the viewpoint of the balance between viscosity and adhesion, the number average molecular weight (Mn) of the polybutadiene polyol and the hydrogenated polybutadiene polyol may be 500 to 100,000, 700 to 50,000, 900 to 10,000, or 1000 to 5000. In this specification, the number average molecular weight (Mn) is a value measured by gel permeation chromatography (GPC) and converted by standard polystyrene.

When preparing an amine ester prepolymer, a polyol other than a polybutadiene polyol and a hydrogenated polybutadiene polyol (hereinafter referred to as "other polyol") may be used in combination. Examples of other polyols include polyester polyols, polyether polyols, polyacrylate polyols, polycarbonate polyols, polysiloxane polyols, polyisoprene polyols, and polyolefin polyols. alcohol. Other polyols may be used singly or in combination of two or more kinds.

The total content of the polybutadiene polyol and the hydrogenated polybutadiene polyol may be 50% by mass or more, based on the total mass of the component having a hydroxyl group, from the viewpoint of improving flexibility and stretchability. At least 65% by mass or more. The total content of the polybutadiene polyol and the hydrogenated polybutadiene polyol can be calculated from the viewpoint of the balance between flexibility, stretchability, and adhesiveness based on the total mass of the component having hydroxyl groups. 95% by mass or less, 90% by mass or less, or 85% by mass or less.

The content of the other polyhydric alcohol may be 0 to 45% by mass, 0 to 30% by mass, or 0 to 20% by mass based on the total mass of the component having a hydroxyl group.

(Polyisocyanate)
The polyisocyanate can be used without particular limitation as long as it has two or more isocyanato groups. From the viewpoint of handleability during the reaction, a diisocyanate is preferred. Examples of such diisocyanates include aromatic polyisocyanates such as diphenylmethane diisocyanate, dimethyldiphenylmethane diisocyanate, toluene diisocyanate, xylene diisocyanate, and terephthalic acid diisocyanate; hexamethylene Aliphatic polyisocyanates such as diisocyanate; and alicyclic polyisocyanates such as dicyclohexylmethane diisocyanate and isophorone diisocyanate. The polyisocyanates may be used singly or in combination of two or more kinds. Among these, the polyisocyanate preferably contains diphenylmethane diisocyanate.

The polymer chain of the amine ester prepolymer according to this embodiment has an isocyanate group at one end thereof, and the polymer chain includes a structural unit derived from a polyol and a structural unit derived from a polyisocyanate. When synthesizing such an amine ester prepolymer, the mixing ratio of the polyisocyanate, the polyol, and the hydroxyl-containing rosin compound is preferably an isocyanate group (NCO) equivalent of the polyisocyanate / hydroxyl of the polyol and the hydroxyl-containing rosin compound (OH) equivalent, that is, NCO equivalent / OH equivalent is adjusted to 1.1 or more. The NCO equivalent / OH equivalent may be 1.1 to 2.2 or 1.1 to 2.1. When the NCO equivalent / OH equivalent is 1.1 or more, the viscosity of the obtained amine ester prepolymer tends to be suppressed, and the workability tends to be improved. When the NCO equivalent / OH equivalent is 2.2 or less, there is a tendency that the amine ester prepolymer does not easily foam when the moisture curing reaction proceeds, and tends to suppress a decrease in adhesion.

The weight average molecular weight (Mw) of the amine ester prepolymer may be 10,000 to 1,000,000, 50,000 to 500,000, or 100,000 to 300,000. Generally, the Mw of the amine ester prepolymer tends to increase as the NCO equivalent / OH equivalent approaches 1. In addition, the higher the Mw of the amine ester prepolymer, the higher the viscosity tends to be.

The moisture-curable hot-melt adhesive may further contain a catalyst. Examples of the catalyst include dibutyltin dilaurate, dibutyltin octoate, dimethylcyclohexylamine, dimethylbenzylamine, trioctylamine, and bis (N-morpholinyl) diethyl Based ether. Based on the total amount of the moisture-curable hot-melt adhesive, the content of the catalyst may be 0.001 to 0.5% by mass.

From the viewpoint of improving rubber elasticity and imparting stronger adhesion, the moisture-curable hot-melt adhesive may further contain a thermoplastic polymer. Examples of the thermoplastic polymer include polyurethane, ethylene-based copolymer, propylene-based copolymer, vinyl chloride-based copolymer, acrylic copolymer, and styrene-conjugated diene copolymer. Based on the total amount of the moisture-curable hot-melt adhesive, the content of the thermoplastic polymer may be 10 to 50% by mass.

From the viewpoint of imparting stronger adhesion, the moisture-curable hot-melt adhesive may further contain a tackifier. Examples of the tackifier include: rosin resin, rosin ester resin, hydrogenated rosin ester resin, terpene resin, terpene phenol resin, hydrogenated terpene resin, petroleum resin, hydrogenated petroleum resin, coumarone resin, ketone resin, Styrene resin, modified styrene resin, xylene resin, and epoxy resin. Based on the total amount of the moisture-curable hot-melt adhesive, the content of the tackifier may be 10 to 50% by mass. In addition, based on the total amount of the moisture-curable hot-melt adhesive, the total content of the thermoplastic polymer and the tackifier may be 10 to 50% by mass.

The moisture-curable hot-melt adhesive may further contain other components as required. Other components include, for example, antioxidants, pigments, ultraviolet absorbers, surfactants, flame retardants, fillers, photochromic agents, thermal colorant preventive agents, perfumes, developers, and thermal crosslinking agents. Based on the total amount of the moisture-curable hot-melt adhesive, the content of other components may be 0.001 to 10% by mass.

Moisture-curable hot-melt adhesive (moisture-curable hot-melt adhesive before curing), its viscosity at 120 ° C can be 0.01 Pa · s or more, 0.05 Pa · s or more, 0.1 Pa · s or more, 1 Pa · s or more, or 2 Pa · s or more, may be 35 Pa · s or less, 30 Pa · s or less, 25 Pa · s or less, or 20 Pa · s or less. When the viscosity at 120 ° C is within the above range, the handleability (handling property) when applying a moisture-curable hot-melt adhesive to an adherend using a dispenser or the like is good.

The moisture-curable hot-melt adhesive can react with moisture in the air or moisture on the surface of the adherend because the terminal isocyanate group of the amine ester prepolymer contained in the adhesive can be reacted, for example, by To harden: Place in a thermostatic bath at 23 ° C. and 50% RH for 1 day.

From the viewpoint of flexibility, the tensile elastic modulus of the moisture-curable hot-melt adhesive after curing may be 0.01 MPa or more, 0.05 MPa or more, 0.1 MPa or more, or 0.5 MPa or more, or 5 MPa or less. 4.5 MPa or less, 4 MPa or less, or 3.5 MPa or less. When it is used for clothing, the tensile elastic modulus is within the above-mentioned range, whereby the elasticity is excellent, and the strange feeling during wearing can be further reduced. In addition, in this specification, the tensile elasticity modulus after hardening means the value measured by the method as described in an Example.

After using a moisture-hardening hot-melt adhesive to adhere the adherend, the adhesive strength (initial adhesive strength) measured before the adhesive hardens can be 0.275 N / mm (2.2 N / 8 mm) or more and 0.300 N / mm (2.4 N / 8 mm) or more, or 0.325 N / mm (2.6 N / 8 mm) or more. The upper limit of the initial adhesive strength is not particularly limited, and may be 1.25 N / mm (10 N / 8 mm) or less. In addition, in this specification, the initial adhesive strength means the value measured by the method as described in an Example.

Using a moisture-curable hot-melt adhesive to adhere the adherend, the adhesive strength (adhesive strength after curing) measured after the adhesive is cured can be 0.95 N / mm (7.6 N / 8 mm) or more and 1.00 N / mm (8 N / 8 mm) or more, or 1.10 N / mm (8.8 N / 8 mm) or more. The upper limit of the adhesive strength after curing is not particularly limited, and may be 2.5 N / mm (20 N / 8 mm) or less. In addition, in this specification, the initial adhesive strength means the value measured by the method as described in an Example.

The moisture-curable hot-melt adhesive can be used, for example, by applying it to an adherend after melting at 60 to 130 ° C. The coating method is not particularly limited, and examples thereof include a method using a coating device such as a die coater, a roll coater, and a sprayer. When applied to small parts such as small parts, a dispenser is suitable.

The adherend is not particularly limited, and may be, for example, cloth or paper. The moisture-curable hot-melt adhesive of this embodiment can be suitably used to adhere a plurality of cloths or papers to each other. Here, the adhered object (adhered body) may be cloth and cloth, paper and paper, or cloth and paper.

The moisture-curable hot-melt adhesive can be used in the form of a thin film. The moisture-curable hot-melt adhesive film can be formed, for example, by applying the moisture-curable hot-melt adhesive to a supporting film such as a polyethylene terephthalate (PET) film. The thickness of the moisture-curable hot-melt adhesive film may be 10 μm or more, 20 μm or more, 30 μm or more, or 50 μm or more, and may be 300 μm or less, 250 μm or less, 200 μm or less, or 150 μm or less. When the moisture-curable hot-melt adhesive film is thick, the adhesiveness tends to be ensured, and when the moisture-curable hot-melt adhesive film is thin, the flexibility and stretchability tend to be more easily secured.

The moisture-curable hot-melt adhesive is produced by, for example, a method including a step of obtaining a amine ester prepolymer by reacting a polyol, a rosin compound containing a hydroxyl group, and a polyisocyanate. Including at least one selected from the group consisting of a polybutadiene polyol and a hydrogenated polybutadiene polyol; and a step of mixing an amine ester polymer with other optional ingredients as necessary.

The moisture-curable hot-melt adhesive of this embodiment can bond cloth, paper, leather, resin substrate, and the like. The attached objects can be the same material (such as cloth and cloth) or different materials (such as cloth and paper). Such an adhesive can be suitably used for clothing products such as clothes, protective gear, backpacks, wallets, interior decoration products, various covers, containers, wearable devices, and the like.

＜ Adhesive body ＞
An adherend according to an embodiment includes a plurality of pieces of cloth; and a hardened material, which is a hardened material of the moisture-curable hot-melt adhesive, and the hardened materials adhere the plurality of pieces of cloth to each other. The adherend of this embodiment can be used, for example, as a seamless garment.

From the viewpoint of adhesiveness, the thickness of the cured product may be 10 μm or more, 20 μm or more, 30 μm or more, or 50 μm or more. From the viewpoint of flexibility, the thickness of the cured product may be 300 μm or less, 250 μm or less, 200 μm or less, or 150 μm or less.

The adhesive body can be produced by, for example, a method including applying the moisture-curable hot-melt adhesive to a cloth to form an adhesive layer, and further disposing the cloth on the adhesive layer. A step of obtaining a precursor of an adherend by pressing and bonding a circuit board or the like; and placing the obtained precursor of the adherent in the air (for example, at 23 ° C for 1 day) to make the adhesive layer (moisture-hardened Hot melt adhesive) hardening step. In the step of obtaining the adherend precursor, for example, a pressure roller can be used.

The first is a schematic diagram showing an example of a procedure for producing an adherend according to this embodiment. The manufacturing process of the adhesive body using a stretchable cloth as a cloth is demonstrated with reference to FIG.

First, the stretchable fabric 1 is installed along the jig 10 (refer to FIG. 1 (a)). Then, the moisture-curable hot-melt adhesive of this embodiment is applied to a predetermined portion of the stretchable fabric 1 to form an adhesive layer as the adhesive portion 4 (see FIG. 1 (b)). The material and shape of the jig 10 are not particularly limited, and can be appropriately selected according to the purpose. The application of the adhesive can be performed using, for example, a dispenser. Then, the stretchable fabric 2 is placed on the adhesive portion 4 and the pressure is applied from the stretchable fabric 2 by a roller or the like, and the stretchable fabric 1 and the stretchable fabric 2 are bonded together with the adhesive portion 4 interposed therebetween. Then, the precursor of the adherend is obtained (refer to FIG. 1 (c) and (d)). Then, the adhesive precursor is cured, and the adhesive portion 4 is hardened with moisture to complete the adhesive of the stretchable cloth.

In FIG.1 (b), the adhesive layer 4 previously formed on the mold release base material can be transferred to the stretchable fabric 1, and the adhesive part 4 can be formed. The adhesive portion 4 may be provided on the stretchable fabric 2 and bonded to the stretchable fabric 1. Furthermore, by changing the stretchable fabric 2 to a stretchable wiring board, an adhesive body of the stretchable fabric and the wiring board can be produced.

The adhesive body of this embodiment maintains a stretchable shape even after being removed from the jig 10, and can be restored to its original shape after the adhesive body is stretched.
[Example]

The following examples are given to explain the present invention more specifically. However, the present invention is not limited by these examples.

[Preparation of amine ester prepolymer (moisture hardening hot melt adhesive)]
(Examples 1 to 5)
Polyols, rosin monohydric alcohols, polyisocyanates, and catalysts of the types and parts by mass shown in Table 1 were used. A polyol, a rosin monohydric alcohol, a diphenylmethane diisocyanate as a polyisocyanate, and a bis (N-morpholinyl) diethyl ether as a catalyst were added and mixed using a vacuum dryer in advance, and mixed. Until it becomes uniform. Then, the obtained mixture was reacted at 110 ° C for 1 hour, and further degassed under reduced pressure at 110 ° C for 1 hour to prepare an amine ester prepolymer. As shown in Table 1, the mol ratio of the isocyanate group of the polyisocyanate to the hydroxyl group (OH) of the polyol, that is, the NCO equivalent / OH equivalent is greater than 1, and it is speculated that the obtained amine ester prepolymer contains an amine ester prepolymer. Substance having a polymer chain comprising a structural unit derived from a polyol and a structural unit derived from a polyisocyanate, the polyol comprising a group consisting of a polybutadiene polyol and a hydrogenated polybutadiene polyol At least one selected from the group consisting of a hydroxy-containing rosin compound at one end of the polymer chain; and an isocyanate group at the other end of the polymer chain. The obtained amine ester prepolymer was directly used as a moisture-hardening hot-melt adhesive.

(Comparative Examples 1 to 3)
An amine ester prepolymer was prepared in the same manner as in the example, except that the polyols, polyisocyanates, and catalysts of the types and parts by mass shown in Table 2 were used.

(Comparative Example 4)
Except having used the kind and mass part of polyol, polyisocyanate, catalyst, and tackifier shown in Table 2, it carried out similarly to Example, and prepared the urethane prepolymer.

The details of each component shown in Tables 1 and 2 are as follows.

Hydrogenated polybutadiene polyol a1: made by Japan Soda Co., Ltd., trade name "GI-3000" (number of hydroxyl groups: 2, number average molecular weight: 3000)
Hydrogenated polybutadiene polyol a2: manufactured by Soda Co., Ltd. under the trade name "GI-1000" (number of hydroxyl groups: 2, number average molecular weight: 1400)
Rosin compound with one hydroxyl group: manufactured by Arakawa Chemical Industry Co., Ltd. under the trade name "KE-359" (hydroxyl value: 44 mgKOH / g, acid value 11 mgKOH / g, softening point: 100 ° C)
Rosin diol: manufactured by Arakawa Chemical Industry Co., Ltd., trade name "D-6011" (hydroxyl value: 117 mgKOH / g, acid value 0.1 mgKOH / g, softening point: 95 ° C)
Crystalline polyester polyol b1: A crystalline polyester polyol obtained by reacting adipic acid with 1,6-hexanediol (number of hydroxyl groups: 2, number average molecular weight: 5000)
Crystalline polyester polyol b2: A crystalline polyester polyol obtained by reacting adipic acid with ethylene glycol (number of hydroxyl groups: 2, number average molecular weight: 2000)
Amorphous polyester polyol c1: An amorphous polyester polyol obtained by reacting isophthalic acid with neopentyl glycol (number of hydroxyl groups: 2, number average molecular weight: 2000)
Amorphous polyester polyol c2: An amorphous polyester polyol obtained by reacting azelaic acid with ethylene glycol (number of hydroxyl groups: 2, number average molecular weight: 8000)
Polyether polyol: polypropylene glycol (number of hydroxyl groups: 2, number average molecular weight: 2000)
Diphenylmethane diisocyanate: manufactured by Tosoh Corporation under the trade name "Millionate MT"
Rosin compound without hydroxyl group: manufactured by Arakawa Chemical Industries, Ltd., trade name "KE-311"

The moisture-curable hot-melt adhesive was evaluated under the following conditions. The results are shown in Tables 1 and 2.

(Viscosity of moisture hardening hot melt adhesive)
Using a rheometer (manufactured by AntonPaar, trade name "MCR-301"), the viscosity of the moisture-hardening hot-melt adhesive was measured at a frequency of 1 Hz, a strain swing angle of 2%, a gap of 0.2 mm, and 120 ° C. .

(Tensile elastic modulus)
The moisture-curable hot-melt adhesive was melted at 120 ° C. and applied to a PET film, and then coated with a bar coater to a thickness of 80 μm to form an adhesive layer. The formed adhesive layer was left to stand in a constant temperature bath at 23 ° C. and 50% RH for 1 day to harden, thereby obtaining a cured product of the adhesive layer. The hardened | cured material of the obtained adhesive layer was die-cut to the size of 5 mm x 50 mm, and the PET film was peeled, and it was set as the measurement sample. The tensile elastic modulus was measured using a tensile tester (manufactured by Shimadzu Corporation, trade name: EZ-Test EZ-SX) at a measurement temperature of 25 ° C, a tensile speed of 100 mm / min, and a distance between the chucks of 30 mm The measurement was carried out under the conditions of 5%, and the elastic modulus was obtained from the slope of the stress-strain curve in the initial stage of stretching.

(Adhesive strength)
The moisture-curable hot-melt adhesive was melted at 120 ° C. and applied to a PET film, and then coated with a bar coater to a thickness of 80 μm to form an adhesive layer. The formed adhesive layer was cut into 8 mm width, and it was sandwiched with 8 mm wide stretchable cloth (Spandex, TORAY OPELONTEX Co., Ltd., LYCRA (registered trademark)), and then the temperature was 120 ° C. It is pressed between the cloths to obtain a pressed body. A dynamometer (manufactured by IMADA Corporation, trade name: DS250N) was used to measure the adhesive strength of the compact after 5 minutes had elapsed from the time after compaction, and the initial adhesiveness was evaluated.
Then, the laminated body was left to stand in a thermostatic bath at 23 ° C. and 50% RH for 1 day to harden moisture to obtain an adherend. Using a tensile tester (EZ-Test EZ-SX, manufactured by Shimadzu Corporation) under the conditions of a measurement temperature of 25 ° C and a tensile speed of 100 mm / min, the obtained T-peel strength test was used to measure the obtained Adhesive strength of the adherend and evaluation of the adhesiveness after curing.

[Table 1]

[Table 2]

From the above results, it can be confirmed that the moisture-curable hot-melt adhesive of the present invention has high initial adhesiveness to cloth and adhesiveness after aging, and can form a cured product having excellent flexibility.

1, 2‧‧‧ stretch fabric

4‧‧‧ Adhesive

10‧‧‧ Jig

FIG. 1 is a schematic diagram showing an example of a procedure for producing an adherend according to this embodiment.

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no

Claims (6)

A moisture-hardening hot-melt adhesive containing an amine ester prepolymer, the amine ester prepolymer being a reactant of a polyol, a rosin compound containing a hydroxyl group, and a polyisocyanate. At least one selected from the group consisting of olefin polyols and hydrogenated polybutadiene polyols, The hydroxyl value of the hydroxyl-containing rosin compound is 20 to 100 mgKOH / g. A moisture-hardening hot-melt adhesive containing an amine ester prepolymer, the amine ester prepolymer having: A polymer chain comprising a structural unit derived from a polyol and a structural unit derived from a polyisocyanate, the polyol comprising at least 1 selected from the group consisting of a polybutadiene polyol and a hydrogenated polybutadiene polyol Species A group derived from a hydroxy-containing rosin compound at one of the ends of the aforementioned polymer chain; and, An isocyanate group at the other end of the aforementioned polymer chain. The moisture-curable hot-melt adhesive according to claim 1 or 2, wherein the polyol includes a hydrogenated polybutadiene polyol. The moisture-curable hot-melt adhesive according to any one of claims 1 to 3, wherein the hydroxyl-containing rosin compound is a rosin compound having one hydroxyl group. The moisture-curable hot-melt adhesive according to any one of claims 1 to 4, which is used to adhere a plurality of pieces of cloth to each other. An adhesive body having: Plural pieces of cloth; and, The hardened | cured material is a hardened | cured material of the moisture hardening type | mold hot-melt-adhesive agent as described in any one of Claims 1-4, This hardened | cured material adhered the said several sheets of cloth mutually.