JPH02272013A - Reactive hot melt type composition - Google Patents

Abstract

PURPOSE:To obtain a reactive hot melt type composition providing a cured material having excellent initial adhesiveness, instant coating film forming properties, heat resistance, weather resistance, elasticity, etc., comprising specific two kinds of urethane prepolymers and a thermoplastic rubber component. CONSTITUTION:(A) A urethane prepolymer obtained by reacting a hydrocarbon- based polyol of both end group hydroxyl groups-containing saturated type with a diisocyanate compound is reacted with (B) a urethane prepolymer prepared by reacting one or more of polycarbonate polyol, adduct of glycerin with propylene oxide and/or ethylene oxide and adduct of bisphenol type diol with propylene oxide and/or ethylene oxide with a diisocyanate compound and (C) a thermoplastic rubber component in the ratios of preferably the component A/B:(90/10)-(50/50) (weight ratio) and 20-80wt.% components A+B to give a reactive type hot melt composition.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to hot melt compositions.

The present invention has particularly excellent heat resistance and weather resistance, and by performing initial adhesion and coating film formation with a true melt, and then performing a urethanization reaction (curing reaction), adhesion and coating film formation are possible. The present invention also relates to a reactive hot-melt composition characterized in that the obtained cured product has high elasticity.

[Prior Art] Hot-melt type and reactive type have been known mainly in the field of adhesive and coating compositions.

Hot-melt adhesive/coating compositions can be applied by heating and melting with a hot-melt applicator, and then cooled and solidified to obtain instant adhesive strength and instant coating film forming properties, as well as workability and instant adhesive properties. However, on the other hand, the adhesive strength and coating film rigidity at high temperatures are extremely low, and the adhesive strength is particularly poor in environments of -80°C or higher.幀性・′v! There is a limit to film hardness.

Examples of hot melt adhesive compositions include JP-A-49-25033, JP-A-51-90342, JP-A-58-17514, JP-A-58-67772,
JP-A-58-147473, JP-A-59-68385
No., JP-A-57-158276, JP-A-60-284
No. 76 etc. have been proposed, and generally ethylene-vinyl acetate type,
Compositions based on polyolefins (represented by low-density polyethylene and aggressive polypropylene), block polymers (51S, SBS, 5EBS, etc.), butyl rubber, polyester, and polyamide are known. .

Currently, hot-melt adhesive compositions are widely used in industries such as bookbinding, packaging, textiles, furniture, woodworking, light electrical appliances, and transportation, but due to the limitations of their heat-resistant adhesive strength, Each application has a limited range of use and is industry recognized as a non-structural adhesive.

Particularly in the field of product assembly, there is a demand for adhesive compositions with high heat resistance that take advantage of the initial adhesive strength of hot melts. It is currently unusable due to deterioration.

In addition, in the painting and coating field, concerns about environmental pollution are extremely high, and hotmelt coatings are being adopted in a form that takes advantage of favorable characteristics such as quick drying of the paint film. However, its heat resistance and stain resistance are still extremely poor, making it unusable for high-temperature applications.

On the other hand, reactive compositions can be expected to have high rigidity and adhesive strength at high temperatures, and are used as structural moldings, paints, and adhesives.

However, numerically (known reactive compositions such as epoxy, urethane, and acrylic have extremely poor initial adhesion and initial coating hardness, and it is essential to increase adhesive strength and coating hardness through a curing reaction. Therefore, the problem is that the curing time is long.

Because of these things, the initial adhesion of hot melt type is instant!
It! Various reactive hot-melt compositions have been studied that have properties such as film-forming properties and reactive heat-resistant adhesive strength and heat-resistant coating hardness.

The reactive hot-melt adhesive compositions described in Japanese Patent Publication No. 47-518, Japanese Patent Application Publication No. 49-98445, and Japanese Patent Application Publication No. 5i-30898 contain one type of urethane specified as ethylene-vinyl acetate resin. A product comprising a prepolymer and a tackifier (hereinafter referred to as tackifier) is disclosed.

Also, JP-A-52-37936, JP-A-52-123
436 and JP-A No. 56-45954, the reactive hot-melt adhesive composition described in JP-A No. 56-45954 is made of a specific resin such as polyethylene, polyester, ethylene-vinyl acetate, or ethylene-ethyl acrylate. done1
Reactive real-melt compositions such as Yuko, which is disclosed as being composed of various types of urethane prepolymers and tackifiers, exhibit initial adhesive strength in the thermoplastic resin that is the base polymer, and Although it has been disclosed that high-temperature rigidity is exhibited by the urethanization reaction, the compositions generally lack elasticity and have the drawbacks of lacking low-temperature properties, weather resistance, and heat aging resistance.

In addition, the reactive group 7 described in JP-A No. 63-120785
) A technology is disclosed in which a melt-type adhesive composition consists of a thermoplastic resin component based on a styrenic block copolymer and a specified urethane polyol.

In this case, the initial adhesion is achieved using a thermoplastic resin component based on a styrene block copolymer, the toughness effect of the styrene block copolymer, and an unsaturated hydrocarbon polyol such as polybutadiene polyol and polyisoprene polyol. Although it is disclosed that a cured product of a urethane prepolymer made of a mixture of polyoxybutylene glycol exhibits heat-resistant adhesion and elasticity, the disadvantage is that the heat aging resistance and weather resistance are extremely low.

In this way, there is still no moisture-curing reactive true melt composition that fully satisfies the market's demands, and has excellent elasticity and heat-resistant rigidity, as well as sufficiently high resistance to heat aging and weathering. At present, there is a strong desire for reactive hot-melt compositions.

[Problems to be Solved by the Invention] An object of the present invention is to solve the above-mentioned drawbacks of reactive hot-melt compositions. After application and pressure bonding, the hot melt cures in moisture without losing its characteristic initial adhesive strength, and can be used as an adhesive for heavy structures or as a thermosetting paint, and has particularly good heat resistance and weather resistance. An object of the present invention is to provide a novel reactive hot-melt composition with excellent properties.

[! l! ! Means for Solving the Problem] The present invention provides a urethane prepolymer (A) obtained by reacting a saturated hydrocarbon polyol containing a terminal hydroxyl group and a diisocyanate compound, a polycarbonate polyol, propylene oxide of glycerin, and Urethane prepolymer (B) obtained by reacting a diisocyanate compound with a single or mixed polyol selected from ethylene oxide adducts, propylene oxide and/or ethylene oxide adducts of bisphenol diols, and By using a reactive hot-melt composition containing a plastic rubber component (C) as a main component, the above-mentioned problems can be solved and the objects of the present invention can be achieved for the first time.

Here, the urethane prepolymer (A) has an average molecular weight of 5.000 or less and contains hydroxyl groups at both ends.
It is a reaction product of a propylene copolymerized polyol and a diisocyanate compound, and has an equivalent ratio of hydroxyl groups to isocyanate groups (NCO/OH) of 1. 9-2.
5, the total content of the urethane prepolymer (B) is 20 to 80% by weight, and the weight ratio of the urethane prepolymer (A) and urethane prepolymer CB) is 10010. ~50150 is good.

Furthermore, the urethane prepolymer (B) is a prepolymer obtained by reacting a polycarbonate polyol having a weight average molecular weight of 2.000 or less with a diisocyanate compound, and the equivalent ratio of hydroxyl groups to incyanato groups (NGO/OH ) is 1.8 to 3.0, and
The content is preferably within 40% by weight.

More preferably, the urethane prepolymer (B) is
A prepolymer obtained by reacting bisphenol A and/or bisphenol F type diol with a polyol having a weight average molecular weight of 2.000 or less modified with propylene oxide and/or ethylene oxide and a diisocyanate compound, and N COlo H equivalent ratio is 1.8
~3.0, and the content is preferably within 40% by weight, and more preferably, the urethane prepolymer (B) is an adduct of glycerin with propylene oxide and/or ethylene oxide. A prepolymer formed by reacting a polyol with a weight average molecular weight of 2,000 or less and a diisocyanate compound, and
010)! The equivalent ratio is 1.8 to 2, O, and
The content is preferably within 40% by weight.

The present invention also provides the above-mentioned urethane prepolymer (A),
Either one or both of (B) is a diisocyanate compound such as (hydrogenated) tolylene diisocyanate, (hydrogenated) diphenylmethane diisocyanate, isophorone diisocyanate, tetramethylene diisocyanate, (
It is preferable to use one or a mixture of two or more of (hydrogenated) α, αα, α-tetramethylxylylene diisocyanate, and (hydrogenated) metaxylylene diisocyanate.

In addition, the present invention provides 30% by weight of the mixture of the urethane prepolymer (B) as well as the urethane prepolymer (A) whose NC010H equivalent ratio is adjusted in the range of 1.9 to 2.5.
~80% by weight, butyl rubber as a thermoplastic rubber component,
Styrene-isoprene-styrene block copolymer, styrene-butidiene-styrene block copolymer, styrene-ethylene-butylene-styrene Procki copolymer, ethylene-ethylacrylate copolymer, ethylene-
It is highly preferable to contain a mixture of one or more polymers selected from vinyl acetate copolymer and ethylene-propyl-1-non copolymer and tackifier in a range of 70% to 20% by weight. .

In addition, the present invention includes addition of 0.01 to 5% by weight of dibutyltin dilaurate as a reaction curing accelerator, and 0.01 to 5% by weight of a tertiary amine compound as a reaction curing accelerator.
01 to 5i is added in an amount of 1%, and even more preferably, 1 to 5i is added as a tertiary amine compound as a reaction curing accelerator.
．． 0.01-5% by weight of 3-dimethylimidazolidinone
It is better to mix it with additives.

Further, the present invention provides a filler formed by drying one or more types selected from zinc oxide powder, magnesium oxide, metal powder, silica powder, calcium carbonate powder, talc powder, alumina powder, carbon black powder, etc. It is also good to use within 30% by weight.

That is, the present invention provides (11) a urethane prepolymer (A) formed by reacting a saturated hydrocarbon polyol containing hydroxyl groups at both terminals and a diisocyanate compound, and (2) a polycarbonate polyol, propylene oxide of glycerin, and /
or a urethane prepolymer (B ); and 3) a thermoplastic rubber component (C).

(2) The urethane prepolymer (A) has an average molecular weight of 5.
A reaction product of an ethylene-propylene copolymer polyol containing hydroxyl groups at both terminals of 000 or less and a diisocyanate compound, and the equivalent ratio of hydroxyl groups to isocyanate groups (NGOlo) 3) is 1.9 to 2.5. The reactive hot-melt composition according to (1), wherein the total content of the urethane prepolymer (B) is 20 to 801i% by weight.

(3) The reactive hot melt composition according to (2), wherein the weight ratio of the urethane prepolymer (A) and the urethane prepolymer (B) is 90/lo to 50/50.

(4) The urethane prepolymer (B) has an average molecular weight of 2,
It is a prepolymer obtained by reacting a polycarbonate polyol of OOO or less with a diisocyanate-1 compound, and has an N COlo H equivalent ratio of 1.8 to 3. 0
The reactive hot-melt composition according to (1) to (3), wherein the content thereof is within 40% by weight.

(5) Urethane prepolymer (B) is produced by reacting a polyol with an average molecular weight of 2,000 or less, which is a propylene oxide and/or ethylene oxide adduct of bisphenol A and/or bisphenol F type diol, with a diisocyanate compound. The obtained prepolymer is
and the N G Olo H equivalent ratio is 1.8 to 3.0, and the content is within 40% by weight (1)
-(3) The reactive true-melt composition described in (3).

(6) Urethane prepolymer (B) is a prepolymer obtained by reacting a glycol component with a weight average molecular weight of 2,000 or less, which is an adduct of glycerin with propylene oxide and/or ethylene oxide, and a diisocyanate compound. Yes, and the N COlo H equivalent ratio is 1
．． 8 to 3.0, and the content is 40% by weight
The reactive hot-melt composition according to (1) to (3), which is within the range below.

(7) Urethane prepolymer (A) and/or (B) contains (hydrogenated) tolylene diisocyanate, (hydrogenated) diphenylmethane diisocyanate, isophorone diisocyanate, tetramethylene diisocyanate as a diisocyanate compound. , (hydrogenated) α, α, α , α -tetramethylxylylene diisocyanate, (hydrogenated) metaxylylene diisocyanate or a mixture of two or more thereof (1) to (6) The reactive hot melt composition described.

(8) The mixture of urethane prepolymer (A) and urethane prepolymer (B) is 30! ! % to 80% by weight, and thermoplastic rubber components include butyl rubber and styrene.
Isoprene-styrene block copolymer, styrene-butidiene-styrene block copolymer L-styrene-ethylene-butylene-styrene Block copolymer, ethylene-ethyl acrylate copolymer, ethylene-vinyl acetate copolymer , (1) to (1) containing a mixture of one or more polymers selected from ethylene-propylene copolymers and a tackifier in a range of 70% to 20% by weight.
7) The reactive hot-melt composition according to any one of 7).

(9) Dibutyltin dilaurate as a reaction curing accelerator, 0. (1) to (1) containing 1 to 5% by weight of O
8) The reactive hot-melt composition described above.

OI tertiary amine compound as a reaction curing accelerator, 0,
The reactive hot-melt composition according to (1) to (9), further comprising 1 to 5% by weight of O.

(II) The reactive hot-melt composition according to (9), wherein the tertiary amine compound is 1,3-dimethylimidazolidinone.

021 One or more types selected from zinc oxide powder, magnesium oxide, metal powder, silica powder, calcium carbonate powder, talc powder, alumina powder, carbon black powder, etc.
Consisting of up to 30% by weight of dry-scanned filler (
8) to the reactive hot-melt composition described in qO.

The configuration of the present invention will be explained in detail below.

The thermoplastic rubber component of the present invention is one selected from thermoplastic rubber, tackifier, wax, plasticizer, antioxidant (antiaging agent), ultraviolet absorber (ultraviolet stabilizer), filler, etc. Or it means a composition consisting of two or more components.

Thermoplastic rubbers include ethylene-vinyl acetate copolymer resin (hereinafter abbreviated as EVA), ethylene-ethyl acrylate copolymer resin (hereinafter abbreviated as EEA), and ethylene-methyl acrylate copolymer resin (hereinafter abbreviated as HMA). ), styrene-isoprene-styrene block copolymer resin (hereinafter referred to as SIs), styrene-butadiene-styrene block copolymer resin (hereinafter referred to as SBS), styrene-ethylene-butylene-styrene block copolymer resin (hereinafter referred to as 5RBS) ), styrene-ethylene-propylene-styrene block copolymer resin (hereinafter abbreviated as 5EPS), ethylene-propylene copolymer resin (hereinafter abbreviated as EPR), butyl rubber, isoprene rubber, isobutylene rubber, acrylic rubber, urethane rubber It is a thermoplastic resin consisting of one or more types represented by , nitrile rubber, among others, butyl rubber,
SIS, SBS, 5EBS, 5EPS, EEA.

A polymer consisting of one or more selected from EVA and EPR is preferable.

In particular, EEA, EVA, SIS, and SBS are i! ! It is especially preferable to use it because of its high humidity.

As a tackifier, (hydrogenated) rosin, (hydrogenated)
Rosin ester, (hydrogenated) rosin ester derivative, terpene resin, terpene-phenol resin, petroleum resin (fatty acid-based, aromatic-based, copolymerized, alicyclic acid-based and hydrogenated petroleum resin), coumaron-indene resin, - Typical examples include xylene resin and ketone resin, and these may be used alone or as a blend.

Further, as the tackifier, the following are preferred examples in consideration of affinity with the urethane prepolymer, reactivity, and hue, and it is preferable to use them alone or in a blend.

That is, rosin or rosin esters include polymerized hydrogenated rosin, (hydrogenated) rosin glycerin ester, (hydrogenated) rosin pentaerythritol ester, and terpene-
Phenolic resins include resins with a softening point of 130°C, and petroleum resins (fatty acid-based, aromatic-based, copolymerized, alicyclic acid-based, and hydrogenated petroleum resins) include C5 fractions. , C9 fraction, C-5-C9 fraction copolymerization, and the like, and hydrogenated petroleum resins having a softening point of less than 125'C are preferred.

The amount of tackifier added is preferably 30 to 800 parts by weight, preferably 50 to 300 parts by weight, based on 100 parts by weight of the thermoplastic rubber component.

This is because if it is less than 30 parts by weight, the effects of the reactive hot-melt composition, such as wetting properties to the adherend, adhesion, and lowering of viscosity when melted, are poor, while if it is more than 800 parts by weight, This is because a lack of rubber elasticity results in brittleness.

Waxes include, for example, paraffin wax, microcrystalline wax, Fischer Trobia mulberry, camphor wax, polymerized wax, low molecular weight polyethylene wax, low molecular weight polypropylene wax, natural wax (beeswax, spermaceti wax, carnauba wax, wood wax, montan wax). ,
Typical examples include ozokerai day, modified wax, etc.

The amount of wax added is 100% of the thermoplastic rubber component.
Less than 500 parts by weight, preferably 10-1 parts by weight
It is preferable to use it in a range of 0.00 parts by weight. This is because if the amount exceeds 500 parts by weight, the rubber elasticity will be insufficient.

Examples of the plasticizer include liquid polyisobutylene, liquid polybutene, liquid (hydrogenated) polyisoprene, liquid (hydrogenated) polybutadiene, paraffinic oil, naphthenic oil,
Typical examples include epoxy plasticizers, phosphoric acid esters, phthalic acid esters, fatty dibasic acid esters, glycol esters, etc., which may be used alone or in combination.
Particularly preferred are hydrocarbon plasticizers such as liquid polyisobutylene, liquid polybutene, liquid (hydrogenated) polyisoprene, liquid (hydrogenated) polybutadiene, paraffin oil, and naphthenic oil in terms of affinity.

The amount of plasticizer added is less than 500 parts by weight, preferably 10 to 10 parts by weight, based on 100 parts by weight of the thermoplastic rubber component.
It is preferable to use it in a range of 0 parts by weight, but if it is more than 500 parts by weight, there will be problems with the initial adhesive strength and the cohesive strength of the melt.

As the antioxidant (antiaging agent), hindered phenols are preferably used, and it is used in an amount of less than 5 parts by weight, preferably in the range of 0.2 to 1 part by weight, based on 100 parts by weight of the thermoplastic rubber component. preferable.

As the ultraviolet absorber (ultraviolet stabilizer), hindered amines are preferred, and it is preferably used in an amount of less than 5 parts by weight, preferably in the range of 0.2 to 1 part by weight, based on 100 parts by weight of the thermoplastic rubber component.

As the filler, an inorganic or organic filler having the function and effect as a known filling reinforcing agent may be used, such as calcium carbonate, barium sulfate, talc, clay, titanium oxide, silica, colloidal silica, carbon blank, glass powder. Alternatively, there are glass fibers, urea-melamine resin powders, acrylic resin powders, phenol resin powders, etc., which may be used alone or in a blend of a plurality of them.

One of the features of the present invention is the use of a urethane prepolymer (A) formed by reacting the aforementioned saturated hydrocarbon polyol containing hydroxyl groups at both ends with a diisocyanate compound, and extensive research has been carried out. From the results, it was found that a composition that is highly compatible with the thermoplastic rubber component and has excellent weather resistance such as toughness and no yellowing is provided.

Examples of saturated hydrocarbon polyols containing hydroxyl groups at both ends include ethylene-propylene copolymer polyols containing hydroxyl groups at both ends and ethylene-butylene copolymer polyols containing hydroxyl groups at both ends with a weight average molecular weight of 15.000 or less. Typical examples are polyisobutylene type polyols containing hydroxyl groups at both ends, and ethylene-propylene copolymer polyols containing hydroxyl groups at both ends with a weight average molecular weight of 115,000 or less. Being able to provide melt-type compositions. In addition, the composition has the property of being curable without foaming. This can be cited as a preferable example.

li! This is because a saturated polyol containing hydroxyl groups at both ends with an average molecular weight of 5.000 or more has a high viscosity and lacks workability, and is significantly lacking in heat resistance imparting effect.

Further, the use or combined use of a conventionally known partially hydrogenated polyol which is an unsaturated polyol containing hydroxyl groups at both terminals is also covered by this patent.

Conventionally, saturated hydrocarbon polyols containing hydroxyl groups at both ends (only recently have it become possible to do so manually)
is not well known, and therefore the following unsaturated hydrocarbon polyols containing hydroxyl groups at both ends have been used in this field.

In other words, polybutadiene polyols and polyisoprene polyols have been widely known and used, but these products have unsaturated bonds in their molecules, resulting in problems such as poor weather resistance and high heat aging properties. Being there was a drawback.

As the diisocyanate compound for obtaining the urethane prepolymer (A) of the present invention, already known diisocyanate compounds may be used (for example, 2,4-)lylene diisocyanate, 2,6- Tolylene diisocyanate, diphenylmethane diisocyanate, α, α, α,
Typical examples include α-tetramethylxylylene diisocyanate, metaxylylene diisocyanate, and hydrogenated compounds thereof, as well as isophorone diisocyanate and tetramethylene diisocyanate. A diisocyanate compound containing up to 20% by weight of tolylene diisocyanate-based polyisocyanate may also be employed.

There is no problem in using one type or a mixture of two or more of these.

Furthermore, when providing a reactive hot melt that particularly requires long-term weather resistance, hydrogenated diphenylmethane diisocyanate, isophorone diisocyanate, and the like are preferred.

In the present invention, the reaction ratio (NCO/OH) of the hydroxyl group equivalent of the saturated hydrocarbon type polyol of the urethane prepolymer (A) and the isocyanate group equivalent of the diisocyanate compound
The reason why the ratio is set to 1.9 to 2.5 is because if the equivalence ratio is lower than 1.9, a remarkable thickening phenomenon occurs as the equivalence ratio decreases, and thermal stability is lost. On the other hand, at 2.5 or higher, am
Due to the presence of a large amount of isocyanate components, there is a problem of environmental pollution due to the significant generation of free isocyanate vapor during application work, and the possibility of oil and violent curing reactions occurring. The problem is that a foaming phenomenon occurs.

Another feature of the present invention is that the above-mentioned polycarbonate polyol, glycerin propylene oxide and/or
Or a urethane prepolymer (B ), and as a result of intensive research, it has been found that the stability of the reactive hot melt system containing the thermoplastic rubber component is not impaired, and the system is given appropriate rigidity and moisture permeability. It has been found that the present invention provides a composition exhibiting excellent reactivity that can greatly accelerate curability due to moisture.

Further, as the polyol of the present invention, the following known polyols such as ethylene glycol, diethylene glycol,
Glycerin, trimethylolpropane, pentaerythritol, sorbitol, monool, polyol made by graft polymerizing styrene and acrylonitrile to polyoxypropylene glycol, polypropylene glycol,
The combined use of -i polyols such as polyethylene glycol, polytetramethylene ether glycol, and polyoxybutylene glycol in small amounts is also covered by this patent.

In particular, the use of polycarbonate polyols, propylene oxide and/or ethylene oxide adducts of bisphenol A and/or bisphenol F, and propylene oxide and/or ethylene oxide adducts of glycerin, which have a weight average molecular weight of 2.000 or less, are as follows. This is preferred because the system containing the thermoplastic rubber component has high stability and the system has a good balance between toughness and heat resistance.

Most preferably, polyoxybutylene glycol, a propylene oxide and/or ethylene oxide adduct of glycerin with a weight average molecular weight of 12,000 or less, is used because it has good compatibility with the thermoplastic rubber component (uniform and It is a particularly preferred example because it has properties that allow it to form a cured film without foaming.

The reason why the polyol having a weight average molecular weight of 2,000 or less is used is that if the weight average molecular weight is 2,000 or more, the system lacks stability, the curability of the system decreases, and the heat resistance strength is impaired. Preferably, the weight average molecular weight is 300-1,000; if it is less than 300, the stability of the system tends to decrease somewhat.

On the other hand, examples of diisocyanate compounds for obtaining the urethane prepolymer CB) of the present invention include 2.4-tolylene diisocyanate, 2.6-tolylene diisocyanate, diphenylmethane diisocyanate, α, α, α
, α-tetramethylxylylene diisocyanate, metaxylylene diisocyanate, and hydrogenated compounds thereof, as well as isophorone diisocyanate, tetramethylene diisocyanate, and the like.

There is no problem in using one type or a mixture of two or more of these.

In addition, especially reactive materials that require long-term weather resistance.

When providing tomel, hydrogenated diphenylmethane diisocyanate, isophorone diisocyanate, etc. are preferred.

In the present invention, the reaction ratio (NCO/OH) between the hydroxyl group equivalent of the polyol of the urethane prepolymer (B) and the isocyanate group equivalent of the diisocyanate compound is 1.9 to 3.
The reason why it is set at 0 is because if it is less than 1.9, a remarkable thickening phenomenon occurs as the equivalence ratio decreases, and thermal stability is lost.

On the other hand, when the temperature is higher than 3.0, a large amount of free isocyanate components exist, which causes a problem of environmental pollution due to the generation of significant isocyanate vapor during application work, and a rapid curing reaction is likely to occur. One problem is that the moisture inside causes more foaming than necessary.

In the present invention, the total content of the urethane prepolymer (A) and urethane prepolymer (B) in the reactive real melt is limited to 20 to 80% by weight, because 20% by weight or less is sufficient for heat resistance. This is because, if the amount is 80% by weight or more, the initial adhesion retention is insufficient.

In addition, in the present invention, the blending ratio of urethane prepolymer (A) and urethane prepolymer (B) is 90/90/
10 to 50150 is because if the urethane prepolymer (B) in the urethane prepolymer is less than 10% by weight, it will lack heat-resistant rigidity and heat curing properties, and if it is more than 50% by weight, it will lack rubber elasticity, weather resistance, and compatibility. This is because it lacks stability.

The reason why a mixed composition of urethane prepolymer (A) and urethane prepolymer (B) is adopted in the present invention is as follows.

-a The compatibility between the urethane prepolymer consisting of the polyol component constituting the urethane prepolymer and the diisocyanate compound and the thermoplastic rubber component is often significantly influenced by the polyol skeleton structure. Therefore, saturated hydrocarbon type polyols have the best compatibility, followed by polyether type polyols and polyester type polyols, but polyether type polyols and polyester type polyols alone have extremely poor compatibility and cannot produce satisfactory results. I can't get it.

On the other hand, hydrocarbon polyols alone have their own hydrophobicity and
This is because it is difficult to obtain heat curing at a sufficient rate due to properties such as low moisture permeability.

Further, in the present invention, the urethane prepolymer (A) and the urethane prepolymer (B) can be obtained separately or simultaneously in the same system without any problem of equivalence. It also includes the preparation obtained by mixing the hydroxyl group-containing saturated hydrocarbon polyol and the above-mentioned bo-11ol in advance and then reacting the mixture with the above-mentioned diisocyanate compound.

Furthermore, in the present invention, the ratio and concentration of urethane prepolymer (A) and urethane prepolymer (B) are determined in consideration of the above-mentioned thermoplastic rubber component. It is customary to select the type of camphor that will ensure compatibility and increase the content.

The reactive hot melt composition of the present invention consists of the above-mentioned compositions, but in order to further improve the reactivity, if necessary, the following reaction curing accelerator may be added in an amount of 0.01 to 5% by weight.
It is highly preferable to add and blend within the range of .

As a preferable reaction curing accelerator for the present invention, as a result of intensive research, it has been found that dibutyltin dilaurate and tertiary amine can be used alone or in combination.

Especially as dibutyltin dilaurate and tertiary amine 1.
It has been found that it is particularly preferable to employ 3-dimethylimidazolidinone or 1,3-dimethylimidazolidinone alone, since both of the effects and odorlessness can be satisfied at the same time.

Furthermore, as a result of intensive research, the reactive hot melt composition of the present invention has the effect of improving the coloration and thermal stability of the cured product, adjusting the coefficient of thermal expansion and contraction, and relieving residual stress at the adhesive or coating interface. For effect purposes, 30% by weight of the following fillers:
It has been found that it is preferable to add and blend within the following range.

That is, the reactive hot melt of the present invention uses zinc oxide powder, magnesium oxide powder,
Metal powder, silica powder (including colloidal silica powder), calcium carbonate powder, titanium oxide powder, talc powder, alumina powder,
A filler formed by drying one or more selected from carbon black powder and the like is preferable. In particular, it has been found that the use of zinc oxide powder, calcium carbonate powder, titanium oxide powder, talc powder, carbon black powder, etc. is preferable because weather resistance is greatly improved and the system has high thermal stability. Using more than 30% by weight of the filler has disadvantages such as the system exhibiting high thixotropy in terms of viscosity, reducing workability, and significantly accelerating the wear and tear of the Hot Mel I applicator. Not desirable.

In addition to this, known organic pigments, organic dyes,
Inorganic pigments other than those mentioned above may also be blended.

In addition, in the reactive hot melt composition of the present invention, an antioxidant (antiaging agent) such as a conventionally known phosphite ester is used.
, ultraviolet absorbers such as benzotriazole, organic thixotropic agents, interface modifiers such as silane or titanate coupling agents, etc. may be used in combination as appropriate.

A suitable manufacturing device for preparing the reactive hot melt composition of the present invention is a kneader-Rougu type kneader. below 120°C, preferably 80°
A method of mixing within the range of C to loo''C is preferable.

At this time, there is no particular restriction on the order of mixing, and it is sufficient to ensure that each component of the present invention is sufficiently mixed, and to adjust by carrying out treatments such as deaeration and solvent removal as necessary.

[Example] The present invention will be specifically explained using Examples below.
These descriptions are equivalent and do not particularly restrict the present invention, and % 1 part described in the examples each means % 2 parts by weight.

Example 1 Two-handed ethyl acrylate copolymer resin: 150 parts of EVAFLEX A-703, a product of Mitsui Dayvon Polychemical Co., Ltd., and 150 parts of EVAFLEX A-703, a product of Mitsui Davon Polychemical Co., Ltd., and Escorez 5320, a product of tackifier Tonefuchs Co., Ltd. (hydrogenated dicyclopentadiene petroleum). After putting 100 parts of wax (resin), Nippon Seirosha product, 20 parts of Barafin Wanx HNP-3, and plasticizer: Nippon Petrochemical Co., Ltd. product, 5 parts of Nippon Seki Polybutene MV-300 into a horizontal Ni-Goo, The mixture was kneaded at 160°C for 120 minutes under vacuum to obtain a thermoplastic rubber component (1).

In addition, instead of the ethylene-ethylacrylate copolymer resin, styrene-isoprene-styrene block copolymer resin Nigiel Chemical Co., Ltd., Cariflex TR-11
A thermoplastic rubber component (2) was obtained in the same manner except that 150 parts of 12 was used.

On the other hand, the hydroxyl equivalent is 0.90 meq/g, the average molecular weight is 2
, 500 saturated hydroxyl group content at both ends Ethylene-a-pyrene copolymer polyol: Idemitsu Petrochemical Co., Ltd. product, P
300 parts of IF-H was charged into a reaction vessel, and after dehydration treatment under vacuum at 120°C, the temperature of the system was set to 85°C, and 55.6 parts of isophorone diisocyanate was added in a nitrogen stream (N
CO/OH-2,05) and reacted for 8 hours to form NGO
A urethane prepolymer (A-1) having a content of 3.3% was obtained. Also, instead of the isophorone diisocyanate,
4 of 80/20-tolylene diisocyanate in which the 2.4-position converter and the 2,6-position ll converter are present in a ratio of 80:20.
Urethane prepolymer (A-2) with NC0% of 3.0% was obtained in the same manner except that the amount was changed to 3.8 parts.

On the other hand, the hydroxyl equivalent is 4.19 meq/g, the average molecular weight T
OO glycerin propylene oxide adduct type polyol: Mitsui Toatsu Chemical Co., Ltd. product.

300 parts of MN-700 was charged into a reaction vessel, and after dehydration treatment under vacuum at 120°C, the temperature of the system was raised to 85°C, and 332 parts of hydrogenated diphenylmethane diisocyanate was charged in a nitrogen stream (NGO/OH- 2,00) and reacted for 5 hours to form a urethane prepolymer (B-
1) was obtained.

Moreover, instead of the hydrogenated diphenylmethane diisocyanate, a substituted product at the 2,4-position and a substituted product at the 2.6-position are substituted with 80:
Similarly, 229 parts of 80/20-tolylene diisocyanate present in a ratio of 20%
．． A 4% urethane prepolymer (B-2) was obtained.

On the other hand, the hydroxyl equivalent is 0.90 meq/g, the average molecular weight is 2
, 500 saturated ethylene containing hydroxyl groups at both ends
Propylene copolymer polyol: Idemitsu Petrochemical Co., Ltd. product, P
IF-) IQ 300 parts and hydroxyl group equivalent is 7.49 meq
/g, average molecular weight 400 glycerin propylene oxide adduct type polyol: Mitsui Toatsu Chemical Co., Ltd. product, MN
-400 was charged into a reaction vessel, and after dehydration treatment under vacuum at 120'C, the temperature of the system was raised to 85°C, and 645 parts of hydrogenated diphenylmethane schisocyanate was charged in a nitrogen stream (NCO/OH- 2,02) and reacted for 8 hours to form a urethane prepolymer (AB-
1) was obtained.

Next, place it in a closed type Niegu/Lugu with a temperature control of 85℃.
30 parts of thermoplastic rubber component (1), 50 parts of urethane prepolymer (A-1), and 20 parts of urethane prepolymer (B-1) were added, mixed for 1 hour in a nitrogen stream, and then defoamed under vacuum for 10 minutes. , No. (A) A reactive hot melt composition was prepared.

Next, thermoplastic rubber components (1) and (2) and urethane prepolymers (A-1) and (A-2).

(B-1), CB-2), and (AB-1) were similarly blended in the proportions shown in Table-1 to obtain reactive hot-melt compositions No. and (A) -No.

(ke) was obtained.

Reference Example The reactive hot-melt composition of Example 1 was evaluated as follows.

■j When adjusting raw materials, visual judgment and evaluation were performed. 1-2 when the mixture is at 85℃
A system in which layer separation was observed in a short period of time was designated as x, a system that was opaque and stable was designated as Δ, and a system that was transparent or translucent and stable was designated as O.

Before curing, one side of a glass plate (20 x 100 x 5 tmm) heated to 50"C was coated with the reactive hot-melt composition heated and melted at 90°C to a thickness of 1 mm. 20° (/RH65) It was left in a constant temperature and humidity chamber for 5 days and then taken out and observed for hardening.
, semi-hardened deep part is indicated by Δ, and deep hardened part is indicated by O.

1 bile At the same time as the curing state, the bubble generation state was observed and evaluated.

A system with many bubbles is marked as ×, and a system with some bubbles is marked as Δ.
A system in which almost no air bubbles were observed was designated as O.

The results are listed in Table-1.

Table 1 Example 2 Styrene-ethylene-butylene block copolymer resin produced by Nigel Chemical Co., Ltd., Kraton G-1726X
After putting 00 parts and tackifier: 200 parts of Clearon P-100 (hydrogenated terpene resin), manufactured by Yasushi Oil Co., Ltd., and 5 parts of Hiwax toop, manufactured by Japan Petrochemical Company, into a horizontal Ni-Goo, the mixture was heated at 160°C. The mixture was kneaded under vacuum for 60 minutes to obtain a thermoplastic rubber component (3).

In addition, instead of the ethylene-ethylacrylate copolymer resin, styrene-butadiene-styrene block copolymer resin y@; Shell Kagaku, Kaliflex TR-1
Same procedure except that 102S was changed to 100 parts, and calcium carbonate: Maruo Calcium Industries product, Super #2
000 to 330 parts and titanium oxide Nikihara Sangyo, R-830
100 parts of carbon black: Mitsubishi Chemical products,
After putting 2.5 parts of MA-200 into a horizontal Nigoo, 1
The mixture was kneaded at 50°C for 180 minutes under vacuum to obtain a gray thermoplastic rubber component (4).

On the other hand, the hydroxyl equivalent is 0.90 meq/g, the average molecular weight is 2
, 500 saturated ethylene containing hydroxyl groups at both ends
Propylene copolymer polyol: Idemitsu Petrochemical Co., Ltd. product, P
Hydroxyl equivalent of 300 parts of IF-H and bisphenol A type propylene oxide adduct is 5.00 meq/g
, 100 parts of KB-280, a product of Mitsui Toatsu Chemical Co., Ltd., and a hydroxyl equivalent of 1.87 meq as polycarbonate diol.
/g, a product of Toagosei Kagaku Co., Ltd.: 100 parts of polycarbonate polyol D-1,000 was charged into a reaction vessel, and heated at 120°.
After dehydration treatment under vacuum at C, the temperature of the system was set to 85 °C, and 55.6 parts of isophorone diisocyanate and 122 parts of 2.4-)lylene diisocyanate were added (
NGO/○H=2゜02) and reacted for 8 hours.
A urethane prepolymer (AB-2) with an O content of 57% was obtained.

Next, 30 parts of the thermoplastic rubber component (3) and 70 parts of the urethane prepolymer (AB-2) were placed in a closed kneader Rougu whose temperature was controlled at 85°C, and the mixture was mixed for 1 hour in a nitrogen stream. Foaming was carried out under vacuum for 10 minutes to prepare reactive hot melt compositions No. (2).

Next, the thermoplastic rubber component (3 or 4) and the urethane prepolymer (AB-2) were similarly blended in the proportions shown in Table-2 to form the reactive hot-melt composition N shown in Table-2.
I got o, (su) -No, (ce).

The reactive hot melt composition of Example 1 was evaluated as follows. Note that the compatibility 2 foaming term was evaluated in the same manner as in Example-1. Regarding the curability in Example-2, 50
An aluminum tray (30 mmφ x 7 mm depth) heated to 90° C. was filled with the reactive hot-melt composition heated and melted at 90° C. to a thickness of 5 mm. 20'C/
The sample was left in a constant temperature and humidity chamber at RH 65% for 10 days, then taken out, cut, and the curing depth (mm) was observed.

The results are listed in Table-2.

Table-2 Example 3 Hydroxyl group equivalent: 0.90 meq/g, average molecular weight: 2.50
Saturated ethylene-propylene copolymer polyol containing 0 hydroxyl groups at both ends: Idemitsu Petrochemical Co., Ltd. product, PIF-
400 parts of H and the hydroxyl equivalent are 4. 100 parts of MS-700, a product of Mitsui Toatsu Chemical Co., Ltd., was charged into a reaction vessel, and after dehydration treatment under vacuum at 120°C. , the system temperature was set at 85°C, and pure -
Diphenylmethane schisocyanate was prepared using the NGO10H ratio of 1.5 as described in experiment numbers (a-f) in Table 3.
Each urethane prepolymer was obtained by shaking to a temperature of ~4.0.

Measuring the NCO content of the urethane prepolymer, and further
The NCO content was measured after 2 days at 90°C and after 2 days at 130°C, and the results are listed in Table 3.

From the results in Table 3, it can be seen that when a tank-type applicator is used, the handling temperature of the reactive hot-melt composition is
Considering the stability of the urethane prepolymer, it has been found that an application temperature of 120°C or less, preferably 90°C or less is preferable.

Further, when the N COlo H ratio is less than 1.8, the 90°C melt viscosity is i,ooops or more, which is very high viscosity and is not favorable for handling. On the other hand, when the N COlo H ratio is 3. Below Q, there are many free diisocyanate components, which causes an abnormally high monomer odor when melted (problems with environmental pollution), and the melt viscosity at 90°C is as low as 100 PS or less, causing problems with initial adhesion. was.

In addition, when a storage stability test was conducted on the blocked urethane prepolymer (AB-2) obtained in Example 2,
Always! Even after being left at S~50°C for 3 months, no change was observed at all, and there was no change in viscosity.

Table 3 Example 4 The same as the thermoplastic rubber component (1) obtained in Example 1 <Using the urethane prepolymer (AB-1) obtained in Example 1, is 0.10,30,
50.80.100% of each reactive hot-melt composition (0% and 100% are blanks) were made, and the initial adhesion strength (20°C) and reactive hot-melt composition as effects of the reactive hot-melt composition were determined. The heat-resistant adhesive strength as an effect of the mold composition and the heat-resistant adhesive strength (90'C) after a heat aging test were measured.

2) Apply the reactive hot-melt composition to a thickness of 500 μm onto a 1-inch wide aluminum plate with a thickness of 0.5 mm using a hand gun controlled at 85° C., and immediately apply it to a dry cloth. The 0 composition was lightly pressed with a rubber roll and left to stand for 30 minutes until it reached room temperature, and then the initial adhesive strength was measured at 20°C. Further, the sample was left in a constant temperature and humidity chamber at 20°C/65% RH for one week, and then taken out to be used as a sample for measuring the heat-resistant adhesive strength at 90''C.

In addition, after being left in a constant temperature and humidity chamber at 20°C/65% RH for one week, a heat aging test was conducted at 90°C/10 days.
This was used as a sample to measure the heat-resistant adhesive strength at °C.

On the other hand, on a 5 mm thick 1 inch wide hard glass plate, on a 15 mm thick 1 inch wide lauan plywood plate, on a 5 mm thick 1 inch wide polypropylene plate, on a 0.8 mm thick 1 inch wide polyester plate. The reactive hot-melt composition was applied to a thickness of 150 μm on the white color coating vi4FL using a handgun controlled at 85°C, and then placed in a constant temperature and humidity bath at 20°C/65% RH for one week. The sample was taken out after being left to stand, and was used as a cross-cut cellophane peel test (adhesion test) sample under normal conditions.
This was used as a sample for weather resistance adhesion test after time irradiation.

The I constant adhesive strength was determined using a universal tensile tester (manufactured by Intesco) at a peeling rate of 200 mm/min and a temperature of 180 at each measurement temperature.
°The peel strength of the vinyl was determined.

The coating performance was measured by making an x-shaped cut on the coating film with a cutter blade, pasting cellophane tape on it, and peeling it off in a 45° direction to the adherend to measure the adhesion. 100℃
The presence or absence of tack was measured by touching the surface after leaving it in a 100°C dryer for 10 minutes.

The weather resistance adhesion test measured the adhesion strength after the weather resistance test.

benefit The adhesive force measurement results are shown in Table-4.

The heat-resistant adhesive strength after curing is sufficiently high, and the strength after heat aging does not decrease, but rather improves, albeit slightly, because there is almost no thermal deterioration, and the curing reaction progresses further and the strength improves. It was determined that

Therefore, it can be said that the cured product of the reactive hot melt type composition of the present invention is thermally stable, exhibits almost no thermal deterioration, and exhibits extremely good adhesive properties and reliability.

The coating film performance results are shown in Table-5.

In the table, glass refers to hard glass, PP refers to polypropylene plate, and PCM refers to polyester-based white colored steel plate.

In addition, in terms of adhesion, ``first'' refers to the initial results of the cured product, and ``later'' refers to the results after the weather resistance test of the cured product.

As a result of the coating film performance test, urethane prepolymer (AB-1
) The coating film of the reactive hot-melt composition containing no cracking or flaking, and almost no yellowing or deterioration, was in good condition! ! ! The membrane was maintained.

Therefore, it can be said that the cured product of the reactive hot-melt composition of the present invention is stable to light, exhibits almost no photodeterioration, and exhibits scratchable and good coating film weather resistance.

Table-4 Explanation of symbols Table-5 O side Akira was not even noticed.

O; 1mm I#P'c pole on the cut part (slight force) Δ: Force 7 Tobayashi 2mm to 5mm Nobunari 枦cho gobesushime 1ri bara sai υt.

×; The length of the haircut is 5mm, 1MtLh, and the length is 5mm.

Comparative Example No. 5 The thermoplastic rubber component (1) obtained in Example-1 and a hydroxyl value of 46. Average molecular weight 2800.
Polybutadiene polyol (Idemitsu Petrochemical Co., Ltd. product, R-
45HT) and hydroxyl value 235, average molecular weight 700, glycerin propylene oxide adduct type polyol 3:
The content of the urethane prepolymer is 3050.
80% of each reactive hot melt composition was prepared, and the initial adhesion strength as the effect of the reactive hot melt composition (20
°C), heat-resistant adhesive strength, and heat-resistant adhesive strength after a heat aging test.

Place the main soil on a 1 inch wide aluminum plate with a thickness of 0.5 mm at 85°C.
The reactive hot-melt composition was applied to a thickness of 500 μm using a hand gun whose temperature was controlled at The initial adhesion strength was measured. Further, the sample was left in a constant temperature and humidity bath at 20° C./65% RH for one week and then taken out to be used as a sample for measuring the heat-resistant adhesive strength at 90° C.

In addition, after being left in a constant temperature and humidity chamber at 20°C/65% RH for one week, a heat aging test was conducted at 90°C/10 days.
This was used as a sample to measure the heat-resistant adhesive strength at °C.

The results are shown in Table-6.

Table 6 Comparative example results show that a double-terminally unsaturated hydrocarbon-based (polybutadiene-based) polyol was used, but the composition showed a significant decrease in strength in the heat aging test, and was thermally unstable and deteriorated over time. A significant decrease in strength was observed. This result showed completely different trends in reactive hot-melt compositions using urethane polyols using polyisoprene polyols, indicating that unsaturated bonds remained in the main chain of the main component. It is thought that the most likely cause is that

In addition, samples were prepared by coating a glass plate with each of the reactive hot melt compositions of Comparative Example 6 to a thickness of 150 μm, and the samples were placed in an atmosphere of 20°C/60% RH for 1 hour.
After being left to cure for 0 days and irradiated for 2,000 hours using a Sunshine Weather Meter, the paint film showed general yellowing and cracks, indicating that the deterioration of the paint film was extremely problematic. It was.

[Effects of the Invention] The method of the present invention exhibits excellent initial adhesion (temporary adhesion) and initial coating adhesion dryness, and also improves heat-resistant adhesion, heat-resistant adhesion stability, and heat-resistant coating as reliability over time. It is possible to improve film adhesion drying properties, coating film stability in long-term weather resistance tests, etc., and in particular, it is possible to significantly improve the weather resistance and heat aging resistance of reactive real-melt compositions, which had not been possible until now. It is clear from the results in Tables 1 to 6 that no deterioration that would pose a practical problem was observed even after long-term environmental exposure tests, and that the material is highly practical for paint and adhesive applications. It is.

Applicant: Mitsui Toatsu Chemical Co., Ltd.

Claims (1)

[Claims] 1. (1) A urethane prepolymer (A) obtained by reacting a saturated hydrocarbon polyol containing hydroxyl groups at both ends with a diisocyanate compound; (2) a polycarbonate polyol and glycerin; Urethane obtained by reacting a diisocyanate compound with one or more mixed polyols selected from propylene oxide and/or ethylene oxide adducts, or propylene oxide and/or ethylene oxide adducts of bisphenol diols. Prepolymer (
A reactive hot-melt composition comprising as main components: B) and (3) a thermoplastic rubber component (C). 2. The urethane prepolymer (A) has an average molecular weight of 5.0
It is a reaction product of a diisocyanate compound and an ethylene-propylene copolymer polyol containing hydroxyl groups at both ends of 00 or less, and has an equivalent ratio of hydroxyl groups to isocyanate groups (NCO/OH) of 1.9 to 2. 5. The reactive hot-melt composition according to claim 1, wherein the total content of the urethane prepolymer (B) is 20 to 80% by weight. 3. The reactive hot melt composition according to claim 2, wherein the weight ratio of the urethane prepolymer (A) and the urethane prepolymer (B) is from 90/10 to 50/50. 4. The urethane prepolymer (B) has an average molecular weight of 2.0
A prepolymer obtained by reacting a polycarbonate polyol of 00 or less and a diisocyanate compound,
4. The reactive hot melt type composition according to claim 1, wherein the NCO/OH equivalent ratio is 1.8 to 3.0, and the content thereof is within 40% by weight. 5. Urethane prepolymer (B) is bisphenol A
A prepolymer obtained by reacting a polyol with an average molecular weight of 2,000 or less, which is an adduct of propylene oxide and/or ethylene oxide of bisphenol F-type diol, with a diisocyanate compound, and has an NCO/OH equivalent. 4. The reactive hot-melt composition according to claim 1, wherein the ratio is 1.8 to 3.0 and the content is within 40% by weight. 6. The urethane prepolymer (B) is a prepolymer obtained by reacting a glycol component with a weight average molecular weight of 2,000 or less, which is an adduct of glycerin with propylene oxide and/or ethylene oxide, and a diisocyanate compound. , and the NCO/OH equivalent ratio is 1.8 to 3
．． 4. The reactive hot-melt composition according to claim 1, wherein the content is within 40% by weight. 7. The urethane prepolymer (A) and/or (B) is
Diisocyanate compounds include (hydrogenated) tolylene diisocyanate, (hydrogenated) diphenylmethane diisocyanate, isophorone diisocyanate, tetramethylene diisocyanate, (hydrogenated) α, α, α′, α′-tetramethyl 7. The reactive hot-melt composition according to claim 1, comprising one or a mixture of two or more of xylylene diisocyanate and (hydrogenated) meta-xylylene diisocyanate. 8. The mixture of urethane prepolymer (A) and urethane prepolymer (B) is 30% to 80% by weight,
As a thermoplastic rubber component, butyl rubber, styrene-isoprene-styrene block copolymer, styrene-butidiene-styrene block copolymer, styrene-ethylene-butylene-styrene block copolymer, ethylene-ethylacrylate copolymer, ethylene - A mixture of one or more polymers selected from vinyl acetate copolymer and ethylene-propylene copolymer and tackifier is 7
The reactive hot-melt composition according to any one of claims 1 to 7, containing in a range of 0% to 20% by weight. 9. The reactive hot-melt composition according to claims 1 to 8, further comprising 0.01 to 5% by weight of dibutyltin dilaurate as a reaction curing accelerator. 10. A tertiary amine compound was used as a reaction curing accelerator.
10. The reactive hot-melt composition according to claim 1, wherein the reactive hot-melt composition is added in an amount of 0.01 to 5% by weight. 10. The reactive hot-melt composition according to claim 9, wherein the 11, tertiary amine compound is 1,3-dimethylimidazolidinone. 12. One or more types selected from zinc oxide powder, magnesium oxide, metal powder, silica powder, calcium carbonate powder, talc powder, alumina powder, carbon black powder, etc.
12. The reactive hot-melt composition according to claim 8, wherein the dry filler is used in an amount of not more than 30% by weight.