JPH10195413A - Moisture-curable reactive hot melt adhesive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition comprising a polyisocyanate, a specific polyol, a specified wax, and ethylene-vinyl acetate copolymer, exhibiting a strong adhering power and a cohesive power from just after adhered, good in thermal stability, when thermally melted, and exhibiting sufficient heat resistance. SOLUTION: This adhesive composition consists essentially of (A) a polyisocyanate (preferably diphenylmethane diisocyanate), (B) a component selected from a rosin skeleton-containing polyester polyol, a rosin skeleton- containing polyether polyol and a terpene phenol copolymer resin, (C) a wax having functional groups capable of reacting with the isocyanate groups (NCO) (preferably a hydroxyl group-containing wax) and (D) ethylene-vinyl acetate copolymer having a vinyl acetate content of 25-60wt.%, preferably 30-50wt.%. The component D is contained in an amount of 20-40wt.% based on the total amount of the components B, C and D. The component A is preferably added so that the ratio of the NCO groups to the functional groups reacting with the NCO groups is 1.5-3.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a moisture-curable reactive hot-melt adhesive composition having both hot-melt and reactive adhesive properties.

[0002]

2. Description of the Related Art Moisture-curable reactive hot-melt adhesives have attracted attention as adhesives having both the instantaneous adhesive properties of hot-melt adhesives and the high heat resistance obtained by a reaction after bonding. Research is being done. As a urethane-based moisture-curable reactive hot-melt adhesive, a moisture-curable reactive hot-melt adhesive comprising an active isocyanate group-containing urethane prepolymer obtained by a reaction between a polyester polyol and an excess of a polyisocyanate compound is known. However, there was a problem that the initial adhesive strength was low.

[0003] Therefore, in order to improve the initial adhesion, a urethane prepolymer obtained by the reaction of a polyester polyol with an excess of a polyisocyanate compound is added to ethylene-polyurethane.
Attempts have been made to mix a vinyl acetate copolymer (hereinafter abbreviated as EVA) (Japanese Patent Application Laid-Open (JP-A) Nos. 5-214312, 5-271639 and 5-102).
780), the compatibility between the urethane prepolymer and EVA is poor, and the instantaneous adhesive property comparable to that of an EVA-based hot melt adhesive cannot be obtained.

There is also an attempt to introduce a hydroxyl group into EVA to make EVA itself reactive (Japanese Patent Publication No. Hei 6-498).
No. 59), there is a problem that the melt viscosity is high and the workability is poor.

Further, there is a report of a urethane prepolymer obtained by reacting a polyester polyol and a polyester polyol or a polyether polyol having a rosin skeleton in the molecule with an excess of a polyisocyanate compound for the purpose of improving initial adhesion. (JP-A-3-252490, JP-A-5-263059, JP-A-7-126600, JP-A-7-179)
559, JP-A-7-228855), but also has the disadvantage that instantaneous adhesiveness comparable to that of an EVA hot melt adhesive cannot be obtained.

As an attempt to obtain instant adhesiveness, there is an attempt to increase the solidification rate by reacting a urethane prepolymer with a wax having a functional group capable of reacting with an isocyanate group (Japanese Patent Application Laid-Open No. 4-226852, JP-A-6-287532), the amount of wax is limited, and a sufficient solidification rate has not been obtained.

As described above, at present, there is no moisture-curable reactive hot-melt adhesive composition which sufficiently satisfies the requirements of the market. In the market, a moisture-curing reactive hot that has a fast solidification rate, exhibits strong adhesive and cohesive strength immediately after bonding, has good thermal stability during heating and melting, and can eventually exhibit sufficient heat resistance At present, there is a strong desire for a melt adhesive composition.

[0008]

An object of the present invention is to solve the above-mentioned problems, and an object of the present invention is to provide an adhesive composition which has a high solidification rate and exhibits strong adhesive strength and cohesive strength immediately after bonding. Another object of the present invention is to provide a moisture-curable reactive hot-melt adhesive composition which has good thermal stability at the time of heating and melting and which can finally exhibit sufficient heat resistance.

[0009]

The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have found that when synthesizing a urethane prepolymer which is a main component of a moisture-curable reactive hot melt adhesive composition. When one or more of (A) a polyester polyol having a rosin skeleton in the molecule, a polyether polyol having a rosin skeleton in the molecule, and a terpene phenol copolymer resin are used instead of the polyester polyol and the polyether polyol used in the above. ,
The compatibility with (B) EVA having a vinyl acetate content of 25 to 60% and (C) a wax having a functional group capable of reacting with an isocyanate group in the molecule becomes very good, and these (A) + (B) + It has been found that all the above problems can be solved by the combination of (C) or (A) + (C). That is, the first invention of the present invention is as follows. A first component comprising a polyisocyanate;
Polyester polyol having a rosin skeleton in the molecule,
Polyether polyol having a rosin skeleton in the molecule,
A second component composed of at least one of terpene phenol copolymer resins, a third component composed of a wax having a functional group capable of reacting with an isocyanate group in the molecule, and a vinyl acetate content of 25 to 60% by weight. It is a moisture-curable reactive hot melt adhesive composition comprising four components, a fourth component consisting of a certain EVA, as essential components. The second invention of the present invention is as follows. Indispensable are a first component composed of a polyisocyanate, a second component composed of a polyether polyol having a rosin skeleton in the molecule, and a third component composed of a wax having a functional group capable of reacting with an isocyanate group in the molecule. It is a moisture-curable reactive hot melt adhesive composition formulated as a component.

As the polyisocyanate compound used in the present invention, various known aromatic, aliphatic or alicyclic polyisocyanates can be used. For example, diphenylmethane diisocyanate (MD
I), tolylene diisocyanate (TDI), naphthylene diisocyanate, xylylene diisocyanate, polymethylene polyphenyl polyisocyanate (polymeric MDI), hexamethylene diisocyanate (HD)
I), isophorone diisocyanate (IPDI), hydrogenated diphenylmethane diisocyanate (HMDI), hydrogenated tolylene diisocyanate, and the like. From the viewpoint of safety, MDI is preferably used.

The polyester polyol or polyether polyol having a rosin skeleton in the molecule (hereinafter, referred to as a polyol having a rosin skeleton in the molecule) used in the present invention is mainly composed of tackiness (tack) and sufficient tackiness after moisture curing. A polymerized rosin is used as an acid component of the polyester, and is obtained by reacting with glycol (Japanese Patent Application Laid-Open No. 3-252490) or by reacting a compound having a glycidyl group in the molecule with rosin. (Japanese Unexamined Patent Publication (KOKAI) Hei 5-155972, Japanese Patent Laid-Open Publication No. H5-263059)
JP-A-7-179559). The polyol having a rosin skeleton in the molecule is already commercially available. For example, trade names KE-601, KE-615-3, KE-622, and KE manufactured by Arakawa Chemical Industries, Ltd.
-624, KE-624.

The terpene phenol copolymer resin used in the present invention mainly provides tackiness (tack) and sufficient heat resistance after moisture curing similarly to the above-mentioned polyol having a rosin skeleton in the molecule. It can also be used. Preferred examples of terpenes include monoterpenes having 10 carbon atoms, such as α-pinene, β-pinene, limonene, and diterpenes having 20 carbon atoms. The number of phenolic hydroxyl groups in the molecule is not particularly limited.
Or two are preferred. In the case of three or more, gelation is easily caused by crosslinking. The terpene phenol copolymer resin is already commercially available. For example, YP-90 and YP-90 (trade names, manufactured by Yashara Chemical Co., Ltd.)
L, Mighty Ace.

The wax having a functional group capable of reacting with an isocyanate group used in the present invention has the effects of increasing the solidification rate, lowering the melt viscosity, and increasing the heat resistance by a moisture curing reaction. Examples of the functional group capable of reacting with the isocyanate group include a hydroxyl group, a carboxyl group, an amino group, a mercapto group, an amide group and the like. Among them, a hydroxyl group is preferred in view of reactivity with the isocyanate group, availability, and odor. preferable. The number of functional groups in the molecule is not particularly limited, but is preferably one or two. In the case of three or more, gelation is easily caused by crosslinking.
The above wax having a hydroxyl group may be any solid wax. For example, a product name N manufactured by Nippon Seiro
There are PS-9210, OX-1949 and Unilin 425 manufactured by Toyo Petrolite Co., Ltd.

[0014] EV used in claim 1 of the present invention
A contributes to imparting rubber elasticity to the obtained urethane prepolymer, and has a vinyl acetate content of 25 to 60% by weight, preferably 30 to 50% by weight. If the vinyl acetate content is less than 25%, the compatibility with the urethane prepolymer becomes poor, and if the vinyl acetate content exceeds 60%, the rubber-like properties unique to EVA become insufficient. E
If the mixing ratio of VA is too large, the heat resistance after moisture curing is reduced, and if it is too small, sufficient rubber elasticity cannot be obtained.
1.0 to the total of a polyol having a rosin skeleton in the molecule, a terpene phenol copolymer resin, a wax having a functional group capable of reacting with an isocyanate group, and EVA.
It is preferable to mix in a range of 50 to 50% by weight, more preferably 20 to 40% by weight. EVA used in the present invention is within a range that does not inhibit the effects of the present invention.
It may have a functional group capable of reacting with an isocyanate group.

A second aspect of the present invention relates to a polyether polyol having a rosin skeleton in the molecule, wherein the urethane prepolymer obtained by reacting the polyether polyol having a rosin skeleton in the molecule with a polyisocyanate after moisture curing. By using a material having a particularly low glass transition point (hereinafter abbreviated as Tg), a strong adhesive force and a cohesive force can be obtained immediately after bonding without using EVA, and a suitable rubber elasticity can be obtained even after moisture curing. become. [NCO] / [OH] = 2.0 (molar ratio) by mixing the polyether polyol having a rosin skeleton in the molecule with the polyisocyanate
In the case of urethane prepolymer obtained by reacting at a ratio of, after moisture curing (after curing at 60 ° C., 50% RH for 7 days)
Has a Tg of -70 ° C to 0 ° C. The Tg of the urethane prepolymer of claim 2 after moisture curing is preferably -70 ° C to -10 ° C, and more preferably -70 ° C.
~ -20 ° C. As such a polyether polyol having a rosin skeleton having a low Tg after moisture curing of the urethane prepolymer, Arakawa Chemical Industry Co., Ltd., trade name KE-
624, KE-624, and the Tg of these urethane prepolymers after moisture curing is -32 ° C.

In the present invention, the ratio of the isocyanate group to the functional group capable of reacting with the isocyanate group (hereinafter referred to as isocyanate ratio) is 1.0 to 5.0, preferably 1.5 to 5.0. 3.0
So that When the isocyanate ratio is less than 1.0, the terminal becomes a urethane resin having a hydroxyl group, and a moisture-curable reactive hot melt adhesive composition cannot be obtained. When the isocyanate ratio exceeds 5.0, the residual excess remaining in the composition is obtained. The isocyanate monomer causes problems such as a decrease in cohesive force, a decrease in solidification rate, and foaming during moisture curing.

The moisture-curable reactive hot melt adhesive composition of the present invention comprises the above-mentioned polyol having a rosin skeleton in its molecule, a terpene phenol copolymer resin, a wax having a functional group capable of reacting with an isocyanate group, and EV.
A can be obtained by mixing A, but a filler such as calcium carbonate, titanium oxide, barium sulfate, talc, clay, or carbon black, a tertiary amine, an organometallic compound, or the like is used as long as the effect of the present invention is not impaired. , An antioxidant such as hindered phenols, an antioxidant, an ultraviolet absorber, a flame retardant, a colorant, a plasticizer, or an oil. These additives are not particularly limited, and conventionally known additives usually used for a reactive hot melt adhesive composition are used.

In order to produce the moisture-curable reactive hot melt adhesive composition of the present invention, the above-mentioned polyisocyanate is reacted with a polyol having a rosin skeleton in the molecule, a terpene phenol copolymer resin, and an isocyanate group. Or a wax having a functional group capable of reacting with an isocyanate group, and a polyol having a rosin skeleton in the molecule, and an EVA may be mixed first. After melting, it may be reacted with the polyisocyanate.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail with reference to production examples and examples, but the present invention is not limited to these examples. Hereinafter, parts and% are by weight unless otherwise specified.

Example 1 A rosin skeleton-containing polyol (KE-6 manufactured by Arakawa Chemical Industries, Ltd.)
22 (hydroxyl value 94.1, acid value 4.4)) 20.00
Part, alcohol-type wax (NPS-92, manufactured by Nippon Seiro)
10 (hydroxyl value 80, acid value 10)) 20.00 parts, EV
A (EV45X manufactured by DuPont-Mitsui Polychemicals, Inc. (vinyl acetate content 46%, melt flow rate 95)) 2
After mixing and melting 0.00 parts and 0.0394 parts of a moisture curing acceleration catalyst (dibutyltin dilaurate (DBTDL) manufactured by Wako Pure Chemical Industries, Ltd.) at 130 ° C. and defoaming for 45 minutes,
Under a nitrogen stream, diphenylmethane diisocyanate (Millionate MT (MDI) manufactured by Nippon Polyurethane Industry Co., Ltd.) 1
8.69 parts were added and reacted at 130 ° C. for 45 minutes to obtain a moisture-curable reactive hot melt adhesive composition. The results are shown in Table 1.

Example 2 Polyether polyol having a rosin skeleton (KE-624, modified by Arakawa Chemical Industries, hydroxyl value 33.9, acid value 0.1)
30.00 parts, alcohol-type wax (Nippon Seiwa Co., Ltd. N
PS-9210) and 30.00 parts of a moisture curing accelerating catalyst (dibutyltin dilaurate (DBTD manufactured by Wako Pure Chemical Industries, Ltd.)
L)) 0.0393 parts were mixed and melted at 130 ° C.
After vacuum degassing for 1 minute, 18.55 parts of diphenylmethane diisocyanate (Millionate MT (MDI) manufactured by Nippon Polyurethane Industry Co., Ltd.) was added under a nitrogen stream, and the mixture was added at 130 ° C. for 4 minutes.
The reaction was carried out for 5 minutes to obtain a moisture-curable reactive hot melt adhesive composition. The results are shown in Table 1.

Example 3 A rosin skeleton-containing polyol (KE-6 manufactured by Arakawa Chemical Industries, Ltd.)
22) 20.00 parts, alcohol-type wax (NPS-9210 manufactured by Nippon Seiro) 20.00 parts, EVA (Mitsui
ELVAX140W manufactured by DuPont Polychemicals (vinyl acetate content 33%, melt flow rate 400)) 2
After mixing and melting 0.00 parts and 0.0394 parts of a moisture curing acceleration catalyst (dibutyltin dilaurate (DBTDL) manufactured by Wako Pure Chemical Industries, Ltd.) at 130 ° C. and defoaming for 45 minutes,
Under a nitrogen stream, diphenylmethane diisocyanate (Millionate MT (MDI) manufactured by Nippon Polyurethane Industry Co., Ltd.) 1
8.69 parts were added and reacted at 130 ° C. for 45 minutes to obtain a moisture-curable reactive hot melt adhesive composition. The results are shown in Table 1.

Example 4 A rosin skeleton-containing polyol (KE-6 manufactured by Arakawa Chemical Industries, Ltd.)
22) 20.00 parts, alcohol-type wax (NPS-9210 manufactured by Nippon Seiro) 20.00 parts, EVA (Mitsui
ELVAX4310 manufactured by DuPont Polychemicals (acid value 5.6, methacrylic acid content 1%, vinyl acetate content 2
5%, melt flow rate 500)) 20.00 parts and moisture curing accelerating catalyst (dibutyltin dilaurate (DBTDL) 0.0396 parts, manufactured by Wako Pure Chemical Industries, Ltd.) were mixed and melted at 130 ° C., and vacuum degassing was performed for 45 minutes. Thereafter, 19.24 parts of diphenylmethane diisocyanate (Millionate MT (MDI) manufactured by Nippon Polyurethane Industry Co., Ltd.) was added under a nitrogen stream, and the mixture was reacted at 130 ° C. for 45 minutes to obtain a moisture-curable reactive hot melt adhesive composition. The results are shown in Table 2.

Example 5 Rosin skeleton-containing polyether polyol (KE-624, manufactured by Arakawa Chemical Industry Co., Ltd. (hydroxyl value 38.6, acid value 2.1))
30.00 parts, 7.50 parts of terpene phenol copolymer resin (YP-90L (hydroxyl value 291.3, acid value 48.2) manufactured by Yashara Chemical Co., Ltd.), alcohol type wax (NPS-9210 manufactured by Nippon Seirosu Co., Ltd.) 22 .50 parts and 0.0348 parts of a moisture hardening promoting catalyst (dibutyltin dilaurate (DBTDL) manufactured by Wako Pure Chemical Industries, Ltd.) were mixed and melted at 130 ° C., vacuum degassed for 45 minutes, and then diphenylmethane diisocyanate (Japan) under a nitrogen stream. 16.77 parts of Millionate MT (MDI) manufactured by Polyurethane Industry Co., Ltd.
The reaction was carried out at 30 ° C. for 45 minutes to obtain a moisture-curable reactive hot melt adhesive composition. The results are shown in Table 2.

Example 6 A rosin skeleton-containing polyol (KE-6 manufactured by Arakawa Chemical Industries, Ltd.)
01 (hydroxyl value 113.5, acid value 0.1)) 10.00
Part, rosin skeleton-containing polyol (KE from Arakawa Chemical Co., Ltd.)
-624) 15.00 parts, alcohol-type wax (NPS-9210 manufactured by Nippon Seiro) 20.00 parts, EVA
(EV45X manufactured by DuPont-Mitsui Polychemicals) 20.
00 parts and 0.0411 parts of a moisture curing acceleration catalyst (dibutyltin dilaurate (DBTDL) manufactured by Wako Pure Chemical Industries, Ltd.)
After mixing and melting at 30 ° C. and vacuum degassing for 45 minutes, diphenylmethane diisocyanate (Millionate MT (MDI) manufactured by Nippon Polyurethane Industry Co., Ltd.) under a nitrogen stream.
11 parts were added and reacted at 130 ° C. for 45 minutes to obtain a moisture-curable reactive hot melt adhesive composition. Table 2 shows the results
Shown in

Example 7 Rosin skeleton-containing polyol (KE-6 manufactured by Arakawa Chemical Industries, Ltd.)
22) 20.00 parts, alcohol-type wax (NPS-9210 manufactured by Nippon Seiro) 20.00 parts, EVA (Mitsui
ELVAX140W manufactured by DuPont Polychemicals) 30.
00 parts and 0.0444 parts of a moisture curing acceleration catalyst (dibutyltin dilaurate (DBTDL) manufactured by Wako Pure Chemical Industries, Ltd.)
After mixing and melting at 30 ° C. and degassing in vacuo for 45 minutes, diphenylmethane diisocyanate (Millionate MT (MDI) manufactured by Nippon Polyurethane Industry Co., Ltd.) under a nitrogen stream.
69 parts were added and reacted at 130 ° C. for 45 minutes to obtain a moisture-curable reactive hot melt adhesive composition. Table 3 shows the results
Shown in

Comparative Example 1 Polyhexamethylene adipate (N-136, Nippon Polyurethane Industry Co., Ltd. (hydroxyl value 42.4, acid value 0.2)) 6
0.00 parts and 0.0363 parts of a moisture curing acceleration catalyst (dibutyltin dilaurate (DBTDL) manufactured by Wako Pure Chemical Industries, Ltd.)
After mixing and melting at 30 ° C. and degassing in vacuo for 45 minutes, diphenylmethane diisocyanate (Millionate MT (MDI) manufactured by Nippon Polyurethane Industry Co., Ltd.) under a nitrogen stream 12.
53 parts were added and reacted at 130 ° C. for 45 minutes to obtain a moisture-curable reactive hot melt adhesive composition. The resulting moisture-curable reactive hot melt adhesive composition had insufficient initial adhesive strength and peeled off at the interface with the substrate. The results are shown in Table 3.

Comparative Example 2 40.00 parts of polyhexamethylene adipate (N-136, manufactured by Nippon Polyurethane Industry Co., Ltd.), 20.00 parts of EVA (EV45X, manufactured by DuPont-Mitsui Polychemicals) and a catalyst for accelerating moisture curing (Wako Pure Chemical Industries, Ltd.) 0.0342 parts of dibutyltin dilaurate (DBTDL)) was mixed and melted at 130 ° C., degassed in vacuum for 45 minutes, and then diphenylmethane diisocyanate (Millionate MT (MDI) manufactured by Nippon Polyurethane Industry Co., Ltd.) 8.36 under a nitrogen stream. Add one part
The reaction was carried out at 30 ° C., but the compatibility was poor and could not be used. The results are shown in Table 3.

Comparative Example 3 40.00 parts of polyhexamethylene adipate (N-136, manufactured by Nippon Polyurethane Industry Co., Ltd.), 20.00 parts of alcohol-type wax (NPS-9210, manufactured by Nippon Seiwa Co., Ltd.) and a catalyst for accelerating moisture hardening (Wako Pure Chemical Industries, Ltd.) 0.0387 parts of dibutyltin dilaurate (DBTDL) manufactured by Yakuhin Co., Ltd. were mixed and melted at 130 ° C., degassed under vacuum for 45 minutes, and then diphenylmethane diisocyanate (Millionate MT (MDI) manufactured by Nippon Polyurethane Industry Co., Ltd.) 17 under a nitrogen stream. After adding 39 parts, the mixture was reacted at 130 ° C. for 45 minutes to obtain a moisture-curable reactive hot melt adhesive composition. The results are shown in Table 4.

Comparative Example 4 40.00 parts of polyhexamethylene adipate (N-136 manufactured by Nippon Polyurethane Industry Co., Ltd.) and a rosin skeleton-containing polyol (KE-622 manufactured by Arakawa Chemical Industry Co., Ltd.
3, acid value 3.7)) 20.00 parts and a moisture-curing acceleration catalyst (dibutyltin dilaurate (DBTD manufactured by Wako Pure Chemical Industries, Ltd.)
L)) 0.0392 parts were mixed and melted at 130 ° C.
After vacuum degassing for 1 minute, 18.27 parts of diphenylmethane diisocyanate (Millionate MT (MDI) manufactured by Nippon Polyurethane Industry Co., Ltd.) was added under a nitrogen stream, and the mixture was added at 130 ° C. for 4 minutes.
The reaction was carried out for 5 minutes to obtain a moisture-curable reactive hot melt adhesive composition. The results are shown in Table 4.

Comparative Example 5 Alcohol-type wax (NPS-921 manufactured by Nippon Seiro Co., Ltd.)
0) 20.00 parts, EVA (EV45X manufactured by DuPont-Mitsui Polychemicals Co., Ltd.) 20.00 parts and a moisture-curing acceleration catalyst (dibutyltin dilaurate (DBTD manufactured by Wako Pure Chemical Industries, Ltd.)
L)) 0.0245 parts were mixed and melted at 130 ° C.
After defoaming in vacuo for one minute, 9.03 parts of diphenylmethane diisocyanate (Millionate MT (MDI) manufactured by Nippon Polyurethane Industry Co., Ltd.) was added under a nitrogen stream,
The reaction was carried out for 1 minute to obtain a moisture-curable reactive hot melt adhesive composition. The obtained moisture-curable reactive hot-melt adhesive composition was liable to peel off at the interface with the substrate, and the heat resistance after curing was also reduced. The results are shown in Table 4.

Comparative Example 6 A rosin skeleton-containing polyol (KE-6 manufactured by Arakawa Chemical Industries, Ltd.)
22) 20.00 parts, EVA (EV45X manufactured by DuPont-Mitsui Polychemicals Co., Ltd.) 20.00 parts and a moisture hardening accelerating catalyst (dibutyltin dilaurate (DBT manufactured by Wako Pure Chemical Industries, Ltd.)
DL)) 0.0250 parts were mixed and melted at 130 ° C.
After vacuum degassing for 5 minutes, 9.91 parts of diphenylmethane diisocyanate (Millionate MT (MDI) manufactured by Nippon Polyurethane Industry Co., Ltd.) was added under a nitrogen stream, and the reaction was carried out at 130 ° C., but the melt viscosity was high and could be used. Did not.
The results are shown in Table 5.

Comparative Example 7 Rosin skeleton-containing polyol (KE-6 manufactured by Arakawa Chemical Industries, Ltd.)
22) 20.00 parts, alcohol-type wax (Nippon Seiro Co., Ltd. NPS-9210) 20.00 parts and moisture curing accelerating catalyst (Wako Pure Chemical Industries dibutyltin dilaurate (DB)
TDL)) mixing and melting 0.0295 parts at 130 ° C.
After vacuum degassing for 45 minutes, 18.94 parts of diphenylmethane diisocyanate (Millionate MT (MDI) manufactured by Nippon Polyurethane Industry Co., Ltd.) was added under a nitrogen stream, and 130 ° C.
For 45 minutes to obtain a moisture-curable reactive hot melt adhesive composition. The resulting moisture-curable reactive hot melt adhesive composition was brittle after curing and had reduced heat resistance. The results are shown in Table 5.

Comparative Example 8 Rosin skeleton-containing polyol (KE-6 manufactured by Arakawa Chemical Industries, Ltd.)
24) 30.00 parts and moisture curing acceleration catalyst (dibutyltin dilaurate (DBTDL) manufactured by Wako Pure Chemical Industries, Ltd.) 0.01
After mixing and melting 75 parts at 130 ° C. and degassing in vacuo for 45 minutes, diphenylmethane diisocyanate (Millionate MT (MD manufactured by Nippon Polyurethane Industry Co., Ltd.)
I)) 5.00 parts was added and reacted at 130 ° C. for 45 minutes to obtain a moisture-curable reactive hot melt adhesive composition.
The results are shown in Table 5.

The moisture-curable reactive hot melt adhesive composition was evaluated by the following method. The results are shown in Tables 1 to 5. B) Compatibility Compatibility was visually confirmed (○: transparent, ○ to Δ: cloudy (transparency), Δ: cloudy (no transparency), Δ
-X: cloudy, x: phase separation). B) Setting time The moisture-curable reactive hot melt adhesive composition is applied to a 25 mm wide K liner paper with a hand gun at 2 mmφ on one side, then bonded 2 seconds later, and pressed with a 1 kg load for a predetermined time.
Remove immediately afterwards. The pressing time at which the material destruction rate at this time was 80% or more was defined as the setting time. C) Shear adhesive strength, elevated temperature Shear breaking temperature The moisture-curable reactive hot melt adhesive composition was applied to a 25 mm-wide base material with a hand gun at 2 mmφ on one side, and after 2 seconds, bonded together and pressed at 1 kg load for 2 seconds. , Then 2
Cured at 3 ° C./45-60% RH for a predetermined time, shear adhesive strength (plywood / plywood, pulling speed 100 mm / min)
And the heating shear fracture temperature (K liner paper / K liner paper, load 1 kg, heating rate 0.4 ° C / min)
The temperature was raised to 26 ° C., and the measurement was performed (A: interfacial peeling, C: cohesive failure, S: material fracture).

[0036]

[Table 1]

[0037]

[Table 2]

[0038]

[Table 3]

[0039]

[Table 4]

[0040]

[Table 5]

[0041]

EFFECT OF THE INVENTION The moisture-curable reactive hot melt adhesive composition of the present invention has a very high solidification rate as compared with the conventionally known moisture-curable reactive hot melt adhesive composition, Since it exhibits strong adhesive and cohesive strength, the working process can be significantly reduced. Furthermore, the polyol having a rosin skeleton in the molecule, the terpene phenol copolymer resin, the wax having a functional group capable of reacting with an isocyanate group in the molecule, and the EVA having a vinyl acetate content of 25 to 60% used in the present invention are mutually compatible. Due to its excellent compatibility, a wide range of performance grades can be selected and used for many different applications and use conditions, and can be adapted to fine adjustment of physical properties.

In the present invention, a terpene phenol copolymer resin, a wax having a functional group capable of reacting with an isocyanate group and EVA are polyesters which are the main raw materials of the conventional moisture-curable reactive hot melt adhesive composition. It is inexpensive as compared with polyols and contributes not only to the effect of the present invention but also to cost reduction.

Claims (2)

[Claims] 1. A first component comprising a polyisocyanate, at least one of a polyester polyol having a rosin skeleton in a molecule, a polyether polyol having a rosin skeleton in a molecule, and a terpene phenol copolymer resin
A second component comprising a seed, a third component comprising a wax having a functional group capable of reacting with an isocyanate group in the molecule,
Ethylene having a vinyl acetate content of 25 to 60% by weight
A moisture-curable reactive hot melt adhesive composition comprising, as essential components, four components, a fourth component comprising a vinyl acetate copolymer. 2. A first component comprising a polyisocyanate, a second component comprising a polyether polyol having a rosin skeleton in the molecule, and a third component comprising a wax having a functional group capable of reacting with an isocyanate group in the molecule. 3
A moisture-curable reactive hot melt adhesive composition comprising the components as essential components.