JP2000073037A - Reactive hot melt adhesive composition and adhesion - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a reactive hot melt adhesive composition capable of being cured by the irradiation of active energy rays, expressing excellent adhesive strength, excellent heat resistance, excellent water resistance, etc. after cured, and not requiring a special production installation, a special packaging materials, etc. SOLUTION: This reactive hot melt adhesive composition comprises an epoxy compound, a polycarbonate resin and an effective amount of a cation polymerization initiator capable of curing the composition by the irradiation of active energy rays. The reactive hot melt adhesive composition preferably further contains an ether compound, and an alicyclic epoxy resin and/or an epoxidized polyalkadiene compound. The epoxy compound preferably comprises an epoxy compound having a softening point of 40-200 deg.C by a ring and ball type measurement method and an epoxy compound liquid at the ordinary temperature.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a reactive hot-melt adhesive composition which is applied in a heated and melted state and whose curing proceeds by irradiation with active energy rays, and a bonding method using the same.

[0002]

2. Description of the Related Art Conventionally, paper, fiber, and paper have been used in various industrial fields such as bookbinding, wrapping, textile processing, woodworking, light electric, and transportation.
BACKGROUND ART Hot melt adhesive compositions are widely used for bonding various adherends such as wood, glass, plastic, and metal.

[0003] In bonding with a hot melt adhesive composition, the hot melt adhesive composition is usually heated and melted at a temperature of about 100 to 200 ° C in an applicator, and then the hot melt adhesive composition in a molten state is coated. Coating is applied to the body, and the adherends are attached to each other. Next, the adherends are adhered to each other by cooling and solidifying the hot melt adhesive composition, and the adhesive strength is developed.

In the case of a hot-melt adhesive composition, since the adhesive strength is rapidly increased by cooling and solidification, the time from bonding the adherends to developing sufficient adhesive strength is usually very short, within 1 minute. . Therefore, there is an advantage that the bonding operation can be completed in a short time.

[0005] However, since the hot-melt adhesive composition exhibits an adhesive strength by solidification upon cooling, even if the adherends are once adhered to each other, if the adhesive is left in a high-temperature atmosphere, the hot-melt adhesive composition is There is a problem that the material is softened or melted and the adhesive strength is significantly reduced, that is, the heat resistance is poor.

Various attempts have been made to cope with the above problems. For example, Japanese Patent Publication No. Sho 51-30898 discloses that "urethane prepolymer 20-73% by weight, ethylene-vinyl acetate copolymer 2-25%". % Reactive hot melt adhesive composition comprising 25% to 55% by weight of a specific tackifier.

[0007] The reactive hot melt adhesive proposed above exhibits excellent adhesive strength even under a high-temperature atmosphere, that is, excellent heat resistance because the urethane prepolymer forms chemical cross-links due to moisture in the air.

However, on the other hand, the moisture in the air causes the chemical crosslinking of the urethane prepolymer to proceed, so that it is necessary to shut off the moisture during production or packaging, and it is necessary to use special production equipment and packaging materials. There is a problem that there is.

To cope with the problems of the above-mentioned moisture-curable hot melt adhesive, for example, Japanese Patent Application Laid-Open No. 6-306346 discloses "about 2 to 95 parts of an epoxy-containing material and about 98 parts.
A reactive hot-melt adhesive composition comprising a composition comprising up to 5 parts of a polyester component and containing a photoinitiator and a hydroxyl-containing material for radiation-curing this composition "has been proposed.

The hot-melt adhesive composition proposed above has the advantage that it is not a moisture-curing type and therefore does not need to block moisture, and since it is a radiation-curing type, there is no need for heating or the like for forming crosslinks. However, there is a problem that the adhesive strength, heat resistance, water resistance, and the like are insufficient and the practicability is poor.

As described above, a hot-melt adhesive composition that exhibits excellent adhesive strength, heat resistance, water resistance and the like and does not require the use of special manufacturing equipment, packaging materials, and the like has not been put to practical use. is the current situation.

[0012]

SUMMARY OF THE INVENTION In order to solve the above-mentioned conventional problems, the present invention is intended to promote curing by irradiation with active energy rays, and to provide excellent adhesive strength, heat resistance and water resistance after curing. Provided is a reactive hot melt adhesive composition that exhibits various physical properties and does not require the use of special manufacturing equipment and packaging materials, and a bonding method using the reactive hot melt adhesive composition. That is the task.

[0013]

The reactive hot melt adhesive composition according to the invention described in claim 1 (hereinafter referred to as "first invention") is obtained by irradiating an epoxy compound, a polycarbonate resin and active energy rays. It is characterized in that the composition contains a cationic polymerization initiator in an amount capable of curing the composition.

The reactive hot melt adhesive composition according to the invention of claim 2 (hereinafter referred to as "second invention") is a reactive hot melt adhesive composition according to the first invention, wherein an ether compound is used. It is further characterized by including.

The reactive hot melt adhesive composition according to the third aspect of the invention (hereinafter referred to as "third invention") is a reactive hot melt adhesive composition according to the first or second aspect of the invention. , Further comprising an alicyclic epoxy resin and / or an epoxidized polyalkadiene.

The reactive hot melt adhesive composition according to the invention described in claim 4 (hereinafter referred to as "fourth invention") is characterized in that, in the first to third inventions, the epoxy compound is a ring-and-ball type measuring method. And an epoxy compound having a softening point in the range of 40 to 200 ° C. and a liquid epoxy compound at room temperature.

The reactive hot-melt adhesive composition according to the invention of claim 5 (hereinafter referred to as "fifth invention") comprises the reactive hot-melt adhesive according to any of the first to fourth inventions In the composition, as the epoxy compound,
Aromatic epoxy resins are used.

Further, the invention according to claim 6 (hereinafter referred to as “6
Invention), the reactive hot melt adhesive composition according to any one of the first to fifth inventions, wherein the polycarbonate resin is a polycarbonate resin having an aliphatic hydroxyl group. Features.

Further, the invention according to claim 7 (hereinafter referred to as "the invention")
The reactive hot melt adhesive composition according to the "seventh invention" is a reactive hot melt adhesive composition according to any one of the first to sixth inventions, wherein the cationic polymerization initiator is an aromatic iodonium complex salt. And at least one cationic polymerization initiator selected from the group consisting of aromatic sulfonium complex salts and metallocene salts.

The bonding method according to the invention described in claim 8 (hereinafter referred to as “eighth invention”) is to heat and melt the reactive hot melt adhesive composition according to any one of the first invention to the seventh invention, Applying one or both of the adherends in a molten state, and before or after laminating the adherends, irradiating the coated reactive hot melt adhesive composition with active energy rays, It is characterized in that the bodies are pressed together.

Hereinafter, the present invention (first to eighth inventions) will be described in detail. The epoxy compound contained in the reactive hot melt adhesive composition according to the present invention refers to an organic compound having at least one oxirane ring polymerizable by cationic polymerization.

The number of epoxy groups in the epoxy compound is preferably one or more per molecule, more preferably two or more per molecule. Where 1
The number of epoxy groups per molecule is determined by dividing the total number of epoxy groups in the epoxy compound by the total number of molecules in the epoxy compound.

The structure of the epoxy compound may be any of aliphatic, alicyclic and aromatic structures, and is not particularly limited. The form is monomeric,
It may be in any form such as an oligomer or a polymer, and is not particularly limited.

The epoxy compound may be in any form such as liquid, semi-solid or solid at room temperature, but has a softening point of 40 to 200 ° C. according to a ring and ball measurement method.
Is preferred.

If the above softening point of the epoxy compound is less than 40 ° C., it may become liquid at room temperature when blended with a polycarbonate resin described later, and may not show the shape as a hot melt adhesive composition. When the above softening point exceeds 200 ° C., the melt viscosity of the obtained reactive hot melt adhesive composition becomes too high,
Coating on an adherend may be difficult, and if the melt coating temperature is increased to improve coatability, the reactive hot melt adhesive composition may be liable to undergo thermal degradation.

The epoxy compound has a boiling point of 200.
Those having a temperature of not less than ° C are preferred. When the boiling point is lower than 200 ° C., the obtained reactive hot melt adhesive composition may volatilize when melted by heating.

The epoxy compound may have crystallinity or may not have crystallinity. However, the epoxy compound obtained after the reactive hot melt adhesive composition obtained by melt coating is obtained. When the tack free time is to be shortened or the initial strength after the adherends are bonded is to be quickly developed, 40
It is preferable to use a crystalline epoxy compound having a melting point of not less than ° C. Here, the term “crystallinity” refers to that which indicates a crystal melting point as measured by a differential scanning calorimeter (DSC).

Further, when the epoxy compound is a polymer, its weight average molecular weight is preferably about 50 to 100,000, and a reactive hot melt adhesive composition which can be cured at room temperature is desired. In this case, the glass transition temperature of the epoxy compound is preferably 20 ° C. or lower.

The epoxy compound is not particularly limited. For example, bisphenol type epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, bisphenol S type epoxy resin, etc. Novolak type epoxy resins such as phenol novolak type epoxy resin and cresol novolak type epoxy resin, aromatic epoxy resins such as trisphenol methane triglycidyl ether and the like, and hydrogenated and brominated products thereof;
4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-
2-methylcyclohexylmethyl 3,4-epoxy-2
-Methylcyclohexanecarboxylate, bis (3,
4-epoxycyclohexyl) adipate, bis (3,
4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexanone-meta- Dioxane, bis (2,3-epoxycyclopentyl) ether, trade name "EHPE-3150"
Alicyclic epoxy resins such as (softening point 71 ° C., manufactured by Daicel Chemical Industries, Ltd.); diglycidyl ether of 1,4-butanediol, diglycidyl ether of 1,6-hexanediol, triglycidyl ether of glycerin; Triglycidyl ether of trimethylolpropane, diglycidyl ether of polyethylene glycol, diglycidyl ether of polypropylene glycol, having 2 carbon atoms
Aliphatic epoxy resins such as polyoxyalkylene glycols containing up to 9 (preferably 2 to 4) alkylene groups and polyglycidyl ethers of long-chain polyols containing polytetramethylene ether glycol; diglycidyl phthalate Glycidyl ester type epoxy resins such as glycidyl ester of tetrahydrophthalic acid, diglycidyl ester of hexahydrophthalic acid, glycidyl ether-glycidyl ester of salicylic acid, diglycidyl-p-oxybenzoic acid, glycidyl ester of dimer acid, and hydrogenation thereof. Triglycidyl isocyanurate, N, N'-diglycidyl derivative of cyclic alkylene urea, N, N, O of p-aminophenol
A triglycidyl derivative, N-aminophenol;
Glycidylamine type epoxy resins such as N, O-triglycidyl derivatives and hydrogenated products thereof; glycidyl (meth) acrylate, ethylene, vinyl acetate,
Copolymers with radically polymerizable monomers such as (meth) acrylic acid esters; polymers mainly composed of conjugated diene compounds such as epoxidized polybutadiene and epoxidized SBS or partially hydrogenated polymers thereof. Epoxidized double bond of saturated carbon; urethane-modified epoxy resin or polycaprolactone-modified epoxy resin in which a urethane bond or polycaprolactone bond is introduced into the structure of each of the above epoxy compounds; NBR, C
Conventionally known various epoxy compounds such as a rubber-modified epoxy resin containing a rubber component such as TBN, polybutadiene, and acrylic rubber are exemplified and suitably used.

The above epoxy compounds may be used alone or in combination of two or more. Among the above epoxy compounds, an aromatic epoxy resin such as a polyglycidyl ether of a polyhydric phenol having two or more aromatic nuclei is particularly preferably used. By using such an epoxy compound, it is possible to impart various properties such as particularly excellent adhesive strength, heat resistance and water resistance to the obtained reactive hot melt adhesive composition.

The polycarbonate resin contained in the reactive hot melt adhesive composition according to the present invention refers to a high molecular compound having a repeating unit represented by the following general formula (1), and generally, bisphenol A And phosgene by a polycondensation reaction in a solution method.

[0032]

Embedded image

(Wherein, R represents a linear or branched hydrocarbon group and n represents a positive integer) The structure of the above polycarbonate resin is aliphatic, alicyclic,
Any structure such as aromatic may be used, and there is no particular limitation.

The shape of the polycarbonate resin is as follows:
At room temperature, it may be in any form such as liquid, semi-solid, or solid, but it has a softening point of 40
What is -200 degreeC is preferable.

The above softening point of the polycarbonate resin is 40
If it is less than ° C., it becomes liquid at room temperature when blended with the above-mentioned epoxy compound, it may not show the shape as a hot melt adhesive composition, and when the softening point of the polycarbonate resin exceeds 200 ° C., Melt viscosity of the resulting reactive hot melt adhesive composition is too high, it may be difficult to apply to the adherend, when increasing the melt coating temperature to improve coatability, In some cases, the reactive hot melt adhesive composition tends to undergo thermal deterioration.

The polycarbonate resin may have crystallinity or may not have crystallinity. However, after the reactive hot melt adhesive composition obtained is melt-coated. When it is desired to shorten the tack-free time or to quickly develop the initial strength after the adherends are bonded to each other, it is preferable to use a crystalline polycarbonate resin having a melting point of 40 ° C. or higher as measured by DSC.

Further, the weight average molecular weight of the above polycarbonate resin is preferably about 200 to 100,000. When it is desired to obtain a reactive hot melt adhesive composition which can be cured at room temperature, the polycarbonate resin is preferably used. The glass transition temperature is preferably at most 20 ° C.

The above-mentioned polycarbonate resin is not particularly restricted but includes, for example, ethylene glycol, diethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol, 1,4- Butanediol, α-methylbutanediol, α-dimethylbutanediol, 1,5-pentanediol, 2-methyl-2,4-pentanediol, 3-methylpentanediol, 1,6-hexanediol, 1,8- Octanediol, cyclobutane-
1,3-di (2'-ethanol), 1,4-dihydroxycyclohexane, cyclohexane-1,4-dimethanol, 1,10-decanediol, 1,12-dodecanediol, neopentyl glycol, having 2 carbon atoms Long-chain diols including polyoxyalkylene glycols containing up to 9 (preferably 2 to 4) alkylene groups and polytetramethylene ether glycol, phthalyl alcohol, p-xylene glycol, hydroquinone, resorcinol, dihydroxynaphthalene, bisphenol A and a polycarbonate resin obtained by a polycondensation reaction of a diol such as a derivative thereof with phosgene; the above-mentioned diol and dimethyl carbonate, diethyl carbonate, dipropyl carbonate, diisopropyl carbonate, dibutyl carbonate, ethylbutyl carbonate, ethylene carbonate Polycarbonate resin obtained by transesterification condensation of carbonic acid diesters such as carboxylate, propylene carbonate, diphenyl carbonate, dibenzyl carbonate, etc .; Copolymerized polycarbonate resin obtained by using two or more of the above diols; A polycarbonate resin obtained by an esterification reaction of a compound with a carboxyl group-containing compound; a polycarbonate resin obtained by an etherification reaction of the above various polycarbonate resins with a hydroxyl group-containing compound;
A polycarbonate resin obtained by subjecting the above various polycarbonate resins to an ester exchange reaction with an ester compound;
A polycarbonate resin obtained by subjecting the above various polycarbonate resins to a transesterification reaction with a hydroxyl group-containing compound; a modified polyester polycarbonate resin obtained by performing a polycondensation reaction between the above various polycarbonate resins and a dicarboxylic acid compound; Conventionally known various polycarbonate resins such as a copolymerized polyether-based polycarbonate resin obtained by copolymerizing with an oxide, and the like, are suitably used.

The above polycarbonate resins may be used alone or in combination of two or more. Apply the reactive hot melt adhesive composition to one or both of the adherends in a heated and molten state, and before bonding the adherends together,
Irradiating the coated reactive hot-melt adhesive composition with an active energy ray, and improving the workability when pressing the adherends together, the reactive hot-melt adhesive irradiated with the active energy ray When it is necessary to delay the progress of the curing of the composition to such an extent that the above-mentioned bonding operation can be performed without hindrance, or when it is necessary to improve the bonding strength, heat resistance, water resistance, etc., one or more per molecule ( (Preferably two or more) polycarbonate resins having an aliphatic hydroxyl group may be used. Here, the number of aliphatic hydroxyl groups per molecule is determined by dividing the total number of aliphatic hydroxyl groups in the polycarbonate resin by the total number of molecules in the polycarbonate resin.

When it is not necessary to delay the progress of the curing of the reactive hot melt adhesive composition irradiated with the active energy ray, or when it is not necessary to improve the adhesive strength, heat resistance and water resistance, The hydroxyl group in the polycarbonate resin having an aliphatic hydroxyl group may be esterified or etherified with a substituted phenol, an aliphatic hydroxyl compound, a carboxylic acid compound, or the like, and sealed.

When it is necessary to accelerate the progress of the curing of the reactive hot melt adhesive composition irradiated with the active energy ray, or when it is necessary to particularly improve the adhesive strength, heat resistance, water resistance and the like. For this, a polycarbonate resin having one or more (preferably two or more) epoxy groups per molecule may be used. Here, the number of epoxy groups per molecule can be determined in the same manner as in the case of the epoxy compound.

Further, the above polycarbonate resin is, for example, an aromatic hydroxyl group which can react with the epoxy group in the epoxy compound during storage of the reactive hot melt adhesive composition or during hot melt coating. And those having no functional groups such as carboxyl groups (anhydrous), and the like, which excessively suppresses the progress of cationic polymerization and inhibits the curing of the reactive hot melt adhesive composition. For example, it is preferable that the compound does not have a functional group such as an amino group.

The amount of the polycarbonate resin is not particularly limited as long as it can be appropriately set according to the required curing speed, adhesive strength, heat resistance, water resistance and the like. The amount of the polycarbonate resin is preferably 5 to 1000 parts by weight, more preferably 10 to 500 parts by weight, based on 100 parts by weight of the epoxy compound.

If the amount of the polycarbonate resin is less than 5 parts by weight per 100 parts by weight of the epoxy compound, the effect of improving the adhesive strength, heat resistance and water resistance may not be sufficiently obtained. If the amount of the polycarbonate resin is more than 1000 parts by weight, the adhesive strength, heat resistance, water resistance and the like will be reduced.

As the cationic polymerization initiator contained in the reactive hot melt adhesive composition according to the present invention, cations for curing the reactive hot melt adhesive composition by cationic polymerization are produced by irradiation with active energy rays. It is not particularly limited as long as it can be used, but is preferably an aromatic iodonium complex salt, an aromatic sulfonium complex salt, a metallocene salt, an arylsilanol.
An aluminum complex and the like can be mentioned, and are preferably used.

The above-mentioned cationic polymerization initiators may be used alone or in combination of two or more. By including these cationic polymerization initiators, the reactive hot melt adhesive composition becomes one in which curing can rapidly proceed by irradiation with active energy rays including light having a wavelength of 200 to 400 nm, and the reaction is improved. The storage stability when storing the reactive hot melt adhesive composition and the stability during heating when producing the reactive hot melt adhesive composition or applying the heat melt coating are improved.

The aromatic iodonium complex salt, aromatic sulfonium complex salt and metallocene salt effective as a cationic polymerization initiator are described, for example, in US Pat. No. 4,256,828, US Pat. No. 5,089,536, and JP-A-6-30.
It is disclosed in, for example, Japanese Patent No. 6346.

Among the above-mentioned cationic polymerization initiators, the aromatic iodonium complex salt and the aromatic sulfonium complex salt do not produce cations under light other than in the ultraviolet region, but are known in the art such as aromatic amines and colored aromatic polycyclic hydrocarbons. By using a sensitizer in combination, cations can be generated even with light in the near ultraviolet region or visible region.

The effective amount of the cationic polymerization initiator depends on the type and strength of the active energy ray, the types and amounts of the epoxy compound and the polycarbonate resin, the type of the cationic polymerization initiator, and is not particularly limited. However, in general, the cationic polymerization initiator is preferably 0.01 to 10 parts by weight, and preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the total amount of the epoxy compound and the polycarbonate resin.
More preferably, it is 10 parts by weight.

When the amount of the cationic polymerization initiator is less than 0.01 part by weight based on 100 parts by weight of the total amount of the epoxy compound and the polycarbonate resin, the reactive hot melt adhesive composition is irradiated with active energy rays. Curing may not proceed sufficiently, and conversely, if the amount of the cationic polymerization initiator added exceeds 10 parts by weight based on 100 parts by weight of the total amount of the epoxy compound and the polycarbonate resin, the reactive hot melt irradiated with active energy rays The curing of the adhesive composition may be too fast, the tack-free time may be too short, and it may be difficult to bond the adherends together.

Further, the adhesive strength, heat resistance, water resistance and the like may be rather lowered. The reactive hot melt adhesive composition according to the second invention further contains an ether compound. This ether compound broadly includes an organic compound having at least one ether bond.

The structure of the ether compound may be any of aliphatic, alicyclic, aromatic and the like, and is not particularly limited. Also, the form of the ether compound may be any form such as a monomer form, an oligomer form, and a polymer form, and is not particularly limited.

Further, the above-mentioned ether compound may be in any form such as liquid, semi-solid or solid at normal temperature. Further, the ether compound may have crystallinity or may not have crystallinity.

Specific examples of the above ether compound include, but are not particularly limited to, for example, polyethylene glycol, polypropylene glycol, containing an alkylene group having 2 to 9, preferably 2 to 4 carbon atoms. Conventionally known various ether compounds such as long chain polyethers including polyoxyalkylene glycol and polytetramethylene ether glycol can be exemplified.

One of the above ether compounds may be used alone, or two or more thereof may be used in combination. In the second invention,
The pot life is extended by further containing the ether compound. Here, the pot life refers to the time from when the reactive hot melt adhesive composition is heated and melted and irradiated with light until it can be bonded.

When it is necessary to particularly increase the adhesive strength, heat resistance or water resistance of the cured adhesive product, an ether compound having one or more, preferably two or more epoxy groups per molecule is used as the ether compound. It is desirable to use. Here, the number of epoxy groups per molecule is
It is calculated in the same manner as in the case of the epoxy compound.

When it is necessary to particularly increase the adhesive strength, heat resistance or water resistance of the cured adhesive, a polycarbonate resin synthesized from the above ether compound may be used.

The mixing ratio of the above ether compound is appropriately set according to the required curing speed and the like.
There is no particular limitation. Generally, 0.1 to 5 parts by weight of an ether compound is added to 100 parts by weight of an epoxy compound.
The amount is preferably in the range of 00 parts by weight,
It is more preferable to mix in a range of 0 parts by weight.

If the compounding ratio of the ether compound is less than 0.1 part by weight with respect to 100 parts by weight of the epoxy compound, the effect of delaying the curing rate may not be sufficiently obtained. If it exceeds 500 parts by weight, the heat resistance may not be sufficiently exhibited.

When the ether compound has an aliphatic hydroxyl group, the ratio of the number of the aliphatic hydroxyl group to the number of the epoxy group in the composition is 0.01 / 1 to 0.01.
It is preferable to mix the ether compound so as to be 10/1, and it is more preferable to mix the ether compound so as to be 0.1 / 1 to 3/1. When the ratio of the number of the aliphatic hydroxyl groups to the number of the epoxy groups exceeds 10/1, the heat resistance of the cured adhesive product of the reactive hot melt adhesive composition may be insufficient.

The reactive hot melt adhesive composition according to the third invention further contains an alicyclic epoxy resin and / or an epoxidized polyalkadiene. Curing time can be shortened by further containing such alicyclic epoxy resin and / or epoxidized polyalkadiene.

When the alicyclic epoxy resin and / or epoxidized polyalkadiene is used, as the above-mentioned epoxy compound, an epoxy compound other than these alicyclic epoxy resins and epoxidized polyalkadienes is used. .

Here, examples of the alicyclic epoxy resin include those exemplified as the alicyclic epoxy resin used as the epoxy compound described above, but are not particularly limited thereto.

The epoxidized polyalkadiene is not particularly limited. For example, a polymer mainly composed of a conjugated diene compound such as an epoxidized polybutadiene or a partially hydrogenated polymer thereof Epoxidized unsaturated carbon double bond; epoxidized S
A polymer block mainly composed of a vinyl aromatic compound such as BS (styrene-butadiene-styrene copolymer) and a polymer block mainly composed of a conjugated diene compound or a partially hydrogenated polymer block. A block copolymer having the same molecule in which the double bond of unsaturated carbon of the conjugated diene compound is epoxidized can be exemplified.

As the alicyclic epoxy resin and / or epoxidized polyalkadiene, those having a boiling point of 200 ° C. or more are preferably used. When the boiling point is less than 200 ° C., the reactive hot melt adhesive composition obtained may be volatilized when the composition is heated and melted.

The number of epoxy groups in the alicyclic epoxy resin and / or epoxidized polyalkadiene is preferably one or more per molecule, more preferably two or more per molecule. The number of epoxy groups per molecule can be determined by the method described above.

The alicyclic epoxy resin and / or the epoxidized polyalkadiene may be used alone or in combination of two or more. The compounding amount of the alicyclic epoxy resin and / or the epoxidized polyalkadiene may be appropriately set according to the time from the attachment of the adherend to the development of heat resistance, and is particularly limited. In general, the amount is preferably in the range of 1 to 500 parts by weight, more preferably 5 to 100 parts by weight, based on 100 parts by weight of the epoxy compound.

If the mixing ratio of the alicyclic epoxy resin and / or the epoxidized polyalkadiene is less than 1 part by weight, the effect of shortening the time until heat resistance is exhibited may not be sufficiently obtained. If it exceeds 500 parts by weight, the curing of the reactive hot melt adhesive composition irradiated with the active energy ray becomes too fast, and it becomes difficult to bond the adherends after the irradiation with the active energy ray. Sometimes.

In the reactive hot melt adhesive composition according to the fourth invention, as the epoxy compound, an epoxy compound having a softening point in the range of 40 to 200 ° C. according to a ring and ball measurement method, and an epoxy compound which is liquid at ordinary temperature are used. Is used, whereby the melt viscosity at the time of heating and melting the reactive hot melt adhesive composition can be reduced, and the coatability can be improved.

As described above, in the reactive hot melt adhesive composition according to the fourth invention, at least two types of epoxy compounds are used in combination. Softening point is 4 by ring and ball method
The epoxy compound in the range of 0 to 200 ° C is not particularly limited, and the epoxy compound having a softening point in the range of 40 to 200 ° C can be appropriately used.

When an epoxy compound having a softening point of less than 40 ° C. is used, when it is used in combination with an epoxy compound which is liquid at ordinary temperature, it becomes liquid when blended with a polycarbonate resin, and the shape as a hot melt adhesive composition becomes May not show, conversely, if the softening point exceeds 200 ℃,
When used in combination with an epoxy compound that is liquid at room temperature, the resulting reactive hot melt adhesive composition may have an excessively high melt viscosity, making it difficult to apply it to an adherend. The epoxy compound that is liquid at room temperature is not particularly limited as long as it is liquid at room temperature, and among the various epoxy compounds described above, those that are liquid at room temperature are appropriately used.

In the fourth invention, an epoxy compound having a softening point in the range of 40 to 200 ° C. according to the ring and ball measurement method,
About the mixing ratio with the epoxy compound which is liquid at room temperature,
The melt viscosity is required, the tack-free time after application, the properties after application, etc., are appropriately set and are not particularly limited, but generally, the softening point is 40 to 20.
It is desirable to mix the epoxy compound which is liquid at normal temperature in the range of 5 to 1000 parts by weight, more preferably 10 to 500 parts by weight, with respect to 100 parts by weight of the epoxy compound at 0 ° C.

If the mixing ratio of the epoxy compound liquid at room temperature is less than 5 parts by weight, the effect of reducing the melt viscosity of the reactive hot melt adhesive composition may not be sufficiently obtained. , Becomes liquid at room temperature,
The shape as a hot melt adhesive composition may not be exhibited.

In the reactive hot melt adhesive composition according to the fifth invention, an aromatic epoxy resin is used as the epoxy compound, and thus, as described above, as in the reactive hot melt adhesive composition, Various physical properties such as excellent adhesive strength, heat resistance and water resistance can be imparted. Such aromatic epoxy resins are not particularly limited, and include, for example, polyglycidyl ethers of polyhydric phenols having two or more aromatic nuclei, and hydrogenated and brominated products thereof. be able to.

The reactive hot melt adhesive composition according to the sixth aspect of the present invention is the reactive hot melt adhesive composition according to the first to fifth aspects, wherein a polycarbonate resin having an aliphatic hydroxyl group is used as the polycarbonate resin. Features.

The polycarbonate resin having an aliphatic hydroxyl group is not particularly limited. For example, an aliphatic diol or a long-chain aliphatic diol used as a raw material of the polycarbonate resin is mixed with phosgene. Aliphatic hydroxyl group-containing polycarbonate resin obtained by condensation reaction; aliphatic hydroxyl group-containing polycarbonate resin obtained by transesterification condensation of aliphatic diol, long-chain aliphatic diol, etc. with carbonic diesters; Copolymerized polycarbonate resin obtained by using two or more kinds of chain aliphatic diols or the like; aliphatic hydroxyl group-containing polycarbonate resin obtained by etherifying polycarbonate resin and aliphatic hydroxyl group-containing compound; polycarbonate resin and alkylene Copolymerized polyether of Kisaido and the like, is preferably used.

Specific examples of the polycarbonate resin having an aliphatic hydroxyl group are not particularly limited, but include polyhexamethylene carbonate diol, poly (3-methylpentene carbonate) diol, polypropylene carbonate diol, 1,6- Polycarbonate diol composed of hexanediol and 3-methylpentenediol, polycarbonate diol composed of 1,9-nonanediol and 2-methyl-1,8-octanediol, and copolymers and mixtures thereof. It is preferably used.

The polycarbonate resin having an aliphatic hydroxyl group may be used alone or in combination of two or more. The number of aliphatic hydroxyl groups in the polycarbonate resin having an aliphatic hydroxyl group is preferably one or more per molecule, more preferably two or more per molecule. Where 1
The number of aliphatic hydroxyl groups per molecule is determined by the method described above.

The compounding amount of the polycarbonate resin having an aliphatic hydroxyl group may be appropriately set according to the required curing speed, adhesive strength, heat resistance, water resistance and the like, and is not particularly limited. Is the epoxy compound 1 for the same reason as in the case of the polycarbonate resin.
The amount is preferably 5 to 1000 parts by weight, more preferably 10 to 500 parts by weight, of the polycarbonate resin having an aliphatic hydroxyl group based on 00 parts by weight.

The ratio of the number of the aliphatic hydroxyl groups to the number of the epoxy groups in the composition is 0.01 to 0.01.
It is preferable that the amount is 1 to 10/1,
The amount is more preferably 0.1 / 1 to 3/1. When the ratio of the number of the aliphatic hydroxyl groups to the number of the epoxy groups exceeds 10/1, the heat resistance of the obtained reactive hot melt adhesive composition may be insufficient.

Next, the reactive hot melt adhesive composition according to the seventh invention is the reactive hot melt adhesive composition according to any one of the first invention to the sixth invention, wherein an aromatic iodonium is used as a cationic polymerization initiator. It is characterized by using at least one kind of cationic polymerization initiator selected from the group consisting of salts, aromatic sulfonium salts and metallocene salts.

The aromatic iodonium salt, aromatic sulfonium salt and metallocene salt include, for example, those described in
The same ones disclosed in JP-A-306346 can be used, and are preferably used.

The aromatic iodonium salt, aromatic sulfonium salt and metallocene salt may be used alone or in combination of two or more. The effective amount of the at least one cationic polymerization initiator selected from the group consisting of the aromatic iodonium salt, the aromatic sulfonium salt and the metallocene salt is, for the same reason as in the case of the cationic polymerization initiator, an epoxy compound. And 0.01 to 10 parts by weight of the total amount of the polycarbonate resin.
It is preferably 0.1 parts by weight, more preferably 0.1 to 10 parts by weight.

When an aromatic iodonium salt and / or an aromatic sulfonium salt is used, a sensitizer such as an aromatic amine or a colored aromatic polycyclic hydrocarbon may be used in combination, and a metallocene salt may be used. When used, a reaction accelerator such as an oxalate ester of tertiary alcohol may be used in combination.

The reactive hot-melt adhesive compositions according to the first to seventh aspects of the present invention contain cationic polymerizable compounds (hereinafter referred to as epoxy compounds) other than epoxy compounds for the purpose of further accelerating the curing after irradiation with active energy rays. Or simply referred to as “cationically polymerizable compound”).

The cationically polymerizable compound is composed of an organic compound having a moiety that can be increased in molecular weight by cationic polymerization, and its structure can be any of aliphatic, alicyclic, aromatic and the like, similarly to the case of the epoxy compound. It may have a structure, and the form may be any form such as a monomeric form, an oligomeric form, and a polymeric form as in the case of the epoxy compound. In addition, the portion that can be increased in molecular weight by cationic polymerization may be present at any of the terminal of the molecular skeleton, the side chain, and any site within the molecular skeleton.

The form of the cationically polymerizable compound is
As in the case of epoxy compounds, at room temperature, liquid,
Any shape such as semi-solid, solid, etc.,
Those having a boiling point of 200 ° C. or more and a softening point of 40 to 200 ° C. according to a ring and ball measurement method are preferred.

If the boiling point of the cationically polymerizable compound is lower than 200 ° C., the resulting reactive hot melt adhesive composition may volatilize when melted by heating. The cationically polymerizable compound has a softening point of 40 measured by a ring and ball method.
When the temperature is lower than 0 ° C., the obtained reactive hot melt adhesive composition becomes liquid at room temperature, and may not show the shape as the hot melt adhesive composition. When the temperature exceeds ℃, the melt viscosity of the obtained reactive hot-melt adhesive composition becomes too high, and it may be difficult to apply the composition to an adherend. When the temperature is increased, the reactive hot melt adhesive composition may easily undergo thermal deterioration.

The cationically polymerizable compound may have crystallinity or may not have crystallinity. The resulting reactive hot melt adhesive composition was melt-coated. When it is desired to shorten the tack-free time at the time or to quickly develop the initial strength after bonding the adherends, use a crystalline cationic polymerizable compound having a melting point of 40 ° C. or more measured by DSC. Is preferred. Furthermore, when it is desired to obtain a reactive hot melt adhesive composition that can be cured at room temperature, the cationically polymerizable compound preferably has a glass transition temperature of 20 ° C. or lower.

The cationically polymerizable compound is not particularly restricted but includes, for example, cyclic ether compounds such as oxetane compounds and oxolane compounds, cyclic ester compounds, vinyl ether compounds and propenyl ether compounds. It is preferably used.

The above cationically polymerizable compounds may be used alone or in combination of two or more. First
The reactive hot melt adhesive composition according to any one of the inventions to the seventh invention may, if necessary, delay the progress of the curing after being irradiated with the active energy ray or melt the composition, as long as the object of the invention is not hindered. Aliphatic hydroxyl compound to reduce viscosity, thermoplastic resin to give shape as hot melt adhesive, adhesion improver to improve adhesion strength to various adherends, improvement of adhesion strength and melting Fillers, reinforcing materials, softeners, plasticizers, viscosity modifiers, thixotropic agents, stabilizers, antioxidants, coloring agents, dehydrating agents, flame retardants, charging for cost reduction by adjusting or increasing the viscosity One or more of various additives such as an inhibitor, a foaming agent, and a fungicide may be contained.

Examples of the aliphatic hydroxyl compound include, but are not limited to, polyhydroxyalkane, alkylene glycol, and polyoxyalkane having an alkylene group having 2 to 9 (preferably 2 to 4) carbon atoms. Long chain polyols including alkylene glycol and polytetramethylene ether glycol, hydroxyl group-terminated polyalkadiene, hydroxyl group-terminated polyester, hydroxyl group-terminated polycaprolactone, acrylic polyol, (partial) saponified ethylene-vinyl acetate copolymer, Examples thereof include polyvinyl alcohol, castor oil, ketone resin, xylene resin, copolymers and modified products of these aliphatic hydroxyl compounds, and one or more of these are suitably used.

The amount of the hydroxyl compound is not particularly limited, but the ratio of the number of aliphatic hydroxyl groups to the number of epoxy groups in the composition is 0.01 /.
It is preferable that the amount is 1 to 10/1,
The amount is more preferably 0.1 / 1 to 3/1. When the ratio of the number of the aliphatic hydroxyl groups to the number of the epoxy groups exceeds 10/1, the heat resistance of the obtained reactive hot melt adhesive composition may be insufficient.

Examples of the thermoplastic resin include, but are not limited to, polyolefin resins such as ethylene-vinyl acetate copolymer; block polymers such as styrene-butadiene and styrene block copolymer; -Based copolymers; polyester resins; tackifying resins such as rosin-based resins, terpene-based resins, styrene-based resins, petroleum-based resins, and the like; commonly used as hot-melt adhesive compositions such as waxes Various thermoplastic resins can be mentioned, and one or more of these are suitably used.

Examples of the adhesion improver include, but are not limited to, γ-chloropropyltrimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacrylic Roxypropyltrimethoxysilane,
β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane,
γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, N-β
Silane coupling agents such as-(aminoethyl) -β-aminopropylmethyldimethoxysilane; isopropyl triisostearoyl titanate, isopropyl tridecylbenzenesulfonyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate;
Tetraisopropyl bis (dioctyl phosphite) titanate, tetraoctyl bis (ditridecyl phosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (di-tridecyl) phosphite titanate, bis (dioctyl pyrophosphate) )
Titanium coupling agents such as oxyacetate titanate, tris (dioctyl pyrophosphate) ethylene titanate; various aluminum coupling agents;
Various types of conventionally known adhesion improvers are mentioned, and one or more of these are suitably used.

The filler is not particularly limited, but for example, calcium carbonate, magnesium carbonate,
Inorganic fillers such as clay, talc, asbestos, etc .; fibers such as rayon, acrylic fiber, nylon fiber, glass fiber, carbon fiber, etc .; hollow fillers such as glass balloon, shirasu balloon, etc .; urea melamine resin powder Synthetic resin powders such as acrylic resin powder, phenol resin powder and the like; natural product powders such as wood flour, fruit flour and the like and surface-treated products thereof, and various conventionally known fillers. Alternatively, two or more types are suitably used.

The above-mentioned various components contained in the reactive hot melt adhesive compositions according to the first to seventh aspects of the present invention are preferably those which are uniformly compatible with other components, and are preferably used in hot-melt coating. It is preferable that the resin does not have a functional group such as an aromatic hydroxyl group and a (anhydrous) carboxyl group which can react with an epoxy group during storage.

The above-mentioned various components are preferably those which do not decompose or volatilize during hot-melt coating or irradiation with active energy rays, and are capable of sufficiently transmitting the active energy rays necessary for the initiation of curing. Preferably, there is.

Further, the above-mentioned various components do not have a functional group such as an amino group, which excessively suppresses the progress of cationic polymerization and inhibits the curing of the reactive hot melt adhesive composition. It is preferred that

The method for producing the reactive hot melt adhesive composition according to the first to seventh aspects of the present invention is not particularly limited, and any method may be used as long as a predetermined amount of each component to be blended can be uniformly kneaded. May be employed, but it is necessary to produce the composition under appropriate heating conditions under which each component can be melted. In addition, kneading of each component at the time of production may be performed without a solvent, for example, may be performed in an inert solvent such as aromatic hydrocarbon, acetate, ketone, etc., but is performed in an inert solvent. In this case, it is necessary to remove the inert solvent by reduced pressure and / or heating after kneading. Specifically, one or two of a double helical ribbon bath or a gate bath, a butterfly mixer, a planetary mixer, a three roll, a kneader-ruder type kneader, an extruder type kneader-extruder, or the like.
The components can be kneaded using more than one kind, but the device for kneading each component is not limited to these.

In the above production, if the water content of each component is high, the progress of curing after irradiating the obtained reactive hot melt adhesive composition with active energy rays may be inhibited. Accordingly, it is preferable to remove water in each component in advance. The method for removing water is not particularly limited, and examples thereof include a method of dehydration by mixing with a molecular sieve, a method of heating and dehydrating with an oven or a heater, and a method of dehydrating under reduced pressure. However, the present invention is not limited to these methods.

The kneading of each component may be usually carried out under atmospheric pressure. However, when it is particularly desired to avoid mixing of water, the kneading is carried out under a reduced pressure atmosphere or an inert gas atmosphere such as nitrogen gas. Is preferred.

The order of preparation of each component is not particularly limited. However, in order to shorten the melting time or to prevent the resulting reactive hot melt adhesive composition from deteriorating, the components which are difficult to melt are used. It is desirable to charge them in order from those which are not easily degraded by heat or mechanical shearing force during melting.
In particular, since the cationic polymerization initiator is easily decomposed or deteriorated by heat, it is preferable that the cationic polymerization initiator is charged last.

In the above-mentioned production, it is necessary to carry out the production in a state in which the active energy rays effective for starting the curing are cut off. The method for storing the reactive hot melt adhesive composition according to the first invention to the seventh invention is not particularly limited as long as the active energy ray effective for initiating curing can be blocked. Pail, tin can,
Various containers that are opaque to active energy rays effective for initiating curing, such as drums, cartridges, release boxes, release trays, cardboard containers, paper bags, plastic bags (for example, composite films sandwiching aluminum foil) Is used, preferably used, but is not limited to these containers, and also about the material of these containers,
There is no particular limitation as long as the active energy rays can be blocked.

Further, the reactive hot melt adhesive compositions according to the first to seventh inventions may be used immediately after production without being stored. Next, in the bonding method according to the eighth invention, the reactive hot melt adhesive composition according to any one of the first invention to the seventh invention is heated and melted, and is applied to one or both of the adherends in a molten state. Before or after the adherends are bonded to each other, the coated reactive hot melt adhesive composition is irradiated with an active energy ray, and the adherends are bonded to each other by pressure bonding.

The method of applying the reactive hot melt adhesive composition by heating and melting it is not particularly limited. For example, the method may be carried out by using a usual hot melt applicator or hot melt coater. A method of applying the reactive hot-melt adhesive composition in a molten state to one or both of the adherends, and immersing one or both of the adherends in the reactive hot-melt adhesive composition in a heat-melted state Method, a method of spraying a hot-melt adhesive composition in a heat-melted state to one or both of adherends using a hot-melt air gun, a reactive hot-melt in a heat-melted state using an extruder or the like. A method in which the adhesive composition is extrusion-coated on one or both surfaces of the adherend, and the like, can be used, and any method is suitably employed.

In order to impart flexibility, sound insulation and the like to the adhesive layer, air, nitrogen gas, carbon dioxide gas and the like are mixed into the hot-melt reactive hot melt adhesive composition and foamed. You may apply | coat in the state of "form melt."
Examples of the foam melt applicator include, but are not particularly limited to, a "Fomelt applicator" manufactured by Nordson Corporation, and are suitably used.

Further, the reactive hot melt adhesive composition may be supplied to a coating device such as a hot melt applicator using a pail unloader or a cartridge dispenser, or may be a stick, pellet, slug, or the like.
It may be supplied to an application device such as a hot melt applicator in various shapes such as a block, a pillow, and a billet.

Further, as for the heating and melting, the entire reactive hot melt adhesive composition may be heated and melted,
The heating and melting may be partially performed only in the vicinity of the heating body. The coating thickness of the reactive hot melt adhesive composition is not particularly limited as long as a desired adhesive strength can be obtained, and may be appropriately set according to the type of the adherend and the coating method. The thickness is preferably such that the energy rays can sufficiently reach the inside of the adhesive layer.

In any case of using any of the above-mentioned melt coating methods, a sufficiently long coating time until after the reactive hot melt adhesive composition is applied to the adherends and the adherends are bonded to each other is set. When it is desired to perform the coating, it is preferable to perform the melt coating in a state in which the active energy rays effective for starting the curing are blocked, and to perform the irradiation with the active energy rays immediately before bonding.
The active energy ray irradiation may be performed when the coated reactive hot melt adhesive composition is in a molten state, or after the coated reactive hot melt adhesive composition is cooled and solidified. You may go.

Further, it is difficult to irradiate active energy rays when it is not necessary to particularly set the application time after the reactive hot melt adhesive composition is applied to the adherend or after the application. In this case, the reactive hot-melt adhesive composition is first irradiated with active energy rays and then heated and melt-coated, and the reactive hot-melt adhesive composition in the heated molten state is irradiated with active energy rays. After that, any method such as a method of applying a coating, a method of applying a reactive hot melt adhesive composition in a heated and molten state, and simultaneously irradiating an active energy ray may be employed.

The active energy ray for curing the reactive hot melt adhesive composition is not particularly limited as long as it can generate cations from the cationic polymerization initiator.
There is no particular limitation. The type of the active energy ray may be appropriately selected according to the type of the cationic polymerization initiator, and preferably, ultraviolet rays are used. Further, active energy rays containing light having a wavelength of 200 to 600 nm are preferably used. In particular, when an aromatic iodonium salt, an aromatic sulfonium salt, a metallocene salt, or the like is used as a cationic polymerization initiator, 200 to 400 nm is used. It is desirable to use an active energy ray containing light of a wavelength.

Regarding the method of irradiating the active energy ray, the reactive hot melt adhesive composition may be directly irradiated, or the reactive hot melt adhesive may be passed through a transparent or translucent adherend or a protective film. The composition may be irradiated indirectly.

The irradiation source of the active energy ray includes:
Although not particularly limited, carbon arc, mercury vapor arc, fluorescent lamp, argon glow lamp, halogen lamp, incandescent lamp, low-pressure mercury lamp, high-pressure mercury lamp, ultra-high-pressure mercury lamp, flash UV lamp, deep UV lamp,
Xenon lamps, tungsten filament lamps, sunlight and the like are mentioned, and one or more of these are preferably used.

The irradiation amount of the active energy ray varies depending on the kind and amount of each component constituting the reactive hot melt adhesive composition, the coating thickness, the irradiation source of the active energy ray, and the like. Although it cannot be determined, it is desirable that the irradiation amount at a wavelength effective for generating cations from the cationic polymerization initiator be in the range of 0.001 to 10 J / cm ² .

The bonding and pressure bonding of the adherends may be performed when the reactive hot melt adhesive composition irradiated with the active energy ray is in a molten state, or may be bonded to the reactive energy melt irradiated with the active energy ray. It may be performed after the hot melt adhesive composition is cooled and solidified. At this time, the reactive hot melt adhesive composition may be in a tacky state or a non-tacky state.

[0117] As a method for bonding the adherends and a method for pressure bonding, for example, after applying a reactive hot melt adhesive composition to one adherend, the other adherend is laminated, and How to pressurize for the required time at pressure and temperature,
After applying the reactive hot melt adhesive composition to both adherends, a method of applying pressure at an appropriate pressure and temperature for a necessary time, and the like may be mentioned, but the method is not limited to these methods. In the above method, a hot press, a hot laminator, or the like may be used, or sufficient heating may be performed at the time of bonding and pressing to complete the curing of the reactive hot melt adhesive composition.

The reactive hot melt adhesive compositions according to the first to seventh aspects of the present invention can be sufficiently cured by irradiating the above-mentioned active energy ray under normal temperature and normal pressure. However, when it is desired to further shorten the curing time, It may be heated to an appropriate temperature. In this case, as the heating method, the type and amount of each component constituting the reactive hot melt adhesive composition, the type and shape of the adherend, and the heating conditions, etc., cannot be uniquely determined, For example, how to blow hot air,
Examples thereof include a method of placing in a heated oven and a method of heating with a heater. One or more of these methods are suitably adopted, but the method is not limited to these methods. The heating temperature for shortening the curing time is preferably lower than the temperature at which the reactive hot melt adhesive composition itself softens. Otherwise, the reactive hot-melt adhesive composition may be softened to cause a displacement of the bonded portion.

The adherends to which the reactive hot melt adhesive compositions according to the first to seventh inventions are applied and the adherends used in the bonding method according to the eighth invention are not particularly limited. But, for example, iron, aluminum, copper,
Lead, tin, zinc, nickel, magnesium, titanium, gold,
Metals or alloys such as silver and platinum or their coated bodies, various plastics or plastic mixtures, inorganic materials such as glass, concrete, stone, mortar, ceramic, ceramics, etc., cellulosic materials such as wood and paper, leather, etc. Various adherends made of materials can be mentioned, and they can be suitably applied. In addition, the above-mentioned various adherends may be adhered with the same material adherend or with different material adherends.

The shape of the adherend may be any shape such as a plate, a lump, a rod, a sheet, a string, a fiber, a honeycomb, a tube, a particle, or the like. Alternatively, adherends having different shapes may be bonded.

The reactive hot melt adhesive compositions according to the first to seventh inventions can be used not only as a reactive hot melt adhesive which is generally and generally used, but also as a structural adhesive or an elastic adhesive. Further, it can be suitably used as a pressure-sensitive adhesive, a sealing agent, a coating agent and the like. Specific applications of such a reactive hot melt adhesive composition include, for example, door panels, partitions,
Adhesion of cores and surface materials of sandwich panels such as shutters, furniture, blackboards, whiteboards, and housing panels for office equipment; cores and surface materials such as door panels and ceiling materials as furniture, partitions, and car interior materials Adhesion; Adhesion of polyolefin resin foam used as cushioning material, sound insulation material, heat insulation material, etc. to automobiles, building materials, electric products, etc. and various base materials; Adhesion of lamp lens; Sponge abrasive, abrasive cloth paper, swash ,
Manufacture of foam mattresses, fittings, packaging materials, seats, electric carpets, tables, desks, system kitchens, televisions, speakers, etc .; bonding of plywood, decorative boards, etc .; application to tape bonding and flexible bonding; optical audio -Adhesion of video disks, magneto-optical disks, etc .; wide applications such as adhesion and sealing of automobile side moldings, body panel sealers, doors, instrument panel peripheral parts, headlamps, tail lamps, window peripheral parts, etc. Of course, it is not limited to these uses.

The reactive hot-melt adhesive compositions according to the first to seventh aspects of the present invention can be used not only as solid hot-melt adhesive compositions, but also as support-type or non-support-type film- or tape-type adhesives. It can also be used as an agent composition.

(Function) Since the reactive hot melt adhesive composition according to the first invention contains an epoxy compound, a polycarbonate resin and a cationic polymerization initiator, curing proceeds by cationic polymerization by irradiation with active energy rays. After curing, the epoxy compound and the polycarbonate resin exhibit various physical properties such as excellent adhesive strength, heat resistance, and water resistance due to a synergistic effect of the polycarbonate resin. Also, since it is an active energy ray-curable type and not a moisture-curable type, there is no need to block moisture, and therefore no special manufacturing equipment or packaging material is required.

In the reactive hot melt adhesive composition according to the second invention, the reactive hot melt adhesive composition according to the first invention further contains an ether compound. Not only the same effect as the reactive hot melt adhesive composition can be obtained,
Further, by the addition of the ether compound, the progress of curing after irradiation with active energy rays can be delayed. That is, the above-mentioned pot life can be extended, so that the adherends can be bonded to each other with a margin after the irradiation with the active energy ray. Therefore, it can be suitably used for bonding members that are difficult to bond.

The reactive hot melt adhesive composition according to the third invention is different from the reactive hot melt adhesive composition according to the first and second inventions in that an alicyclic epoxy resin and / or
Alternatively, since epoxidized polyalkadienes are contained, curing by cationic polymerization proceeds very quickly by the alicyclic epoxy resin and / or epoxidized polyalkadiene. Therefore, the curing time from bonding the adherends to developing heat resistance can be reduced.

In the reactive hot melt adhesive composition according to the fourth invention, as the epoxy compound, an epoxy compound having a softening point in the range of 40 to 200 ° C. by a ring and ball measurement method, and an epoxy compound which is liquid at ordinary temperature are used. To use
The melt viscosity when heated and melted prior to application can be reduced, so that the coating properties of the reactive hot-melt adhesive composition without deteriorating various physical properties such as adhesive strength, heat resistance or water resistance, and hence workability Can enhance the character.

In the reactive hot melt adhesive composition according to the fifth invention, since an aromatic epoxy resin is used as the epoxy compound, the adhesive cured product after the reactive hot melt adhesive composition has been cured has an adhesive property. Performance such as strength, heat resistance and water resistance can be further enhanced.

The reactive hot melt adhesive composition according to the sixth aspect of the present invention is the reactive hot melt adhesive composition according to the first to fifth aspects, wherein the polycarbonate resin having an aliphatic hydroxyl group is used as the polycarbonate resin. Since it is used, curing by cationic polymerization after irradiation with active energy rays is moderately delayed, the tack-free time is lengthened, and the workability when attaching and bonding the adherends is further improved. Further, various physical properties such as adhesive strength, heat resistance and water resistance are further improved.

Further, the reactive hot melt adhesive composition according to the seventh invention is the reactive hot melt adhesive composition according to any one of the first to sixth inventions, wherein an aromatic iodonium is used as a cationic polymerization initiator. Since at least one kind of cationic polymerization initiator selected from the group consisting of salts, aromatic sulfonium salts and metallocene salts is used, curing by cationic polymerization after irradiation with active energy rays proceeds at an appropriate rate.

The bonding method according to the eighth invention uses the reactive hot melt adhesive composition according to any one of the first invention to the seventh invention in a curing method by irradiating with active energy rays. It is possible to complete the work and obtain a joined body having various physical properties such as excellent adhesive strength and heat resistance and water resistance.

[0131]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In the examples, “parts” means “parts by weight”.

In the following Examples and Comparative Examples, reactive hot melt adhesive compositions were produced using the following raw materials. [Epoxy compound] Epoxy compound (A): trade name "Epicoat 1001"
(Bisphenol A type epoxy resin, softening point 64 ° C, epoxy equivalent 450-500, manufactured by Yuka Shell Epoxy Co.) Epoxy compound (B): trade name “Epicoat 1007”
(Bisphenol A epoxy resin, softening point 128 ° C,
Epoxy equivalent 1750-2200, manufactured by Yuka Shell Epoxy) Epoxy compound (C): trade name "ERL-4221"
(Alicyclic epoxy resin, liquid at normal temperature, epoxy equivalent 13
7, Union Carbide Co.) Epoxy compound (D): trade name "Eporide PB470
0 "(epoxidized polybutadiene, liquid at normal temperature, epoxy equivalent 172, manufactured by Daicel Chemical Industries, Ltd.) Epoxy compound (E): trade name" Epicoat 828 "
(Bisphenol A type epoxy resin, liquid at normal temperature, epoxy equivalent 184-194, manufactured by Yuka Shell Epoxy Co.) Epoxy compound (F): trienemethylolpropane triglycidyl ether (liquid at normal temperature, epoxy equivalent 13
5, ACI Japan Co., Ltd.) [Polycarbonate resin] Polycarbonate resin (a): trade name "Polylight CD"
2001 ”(melting point 46 ° C., hydroxyl value 56 KOHmg /
g, manufactured by Dainippon Ink and Chemicals, Inc.) Polycarbonate resin (b): trade name “Placcel CD
220 "(melting point 47-53 ° C, hydroxyl value 56KOHmg
/ G, manufactured by Daicel Chemical Industries, Ltd.) Polycarbonate resin (c): Trade name “Placcel CD
220HL "(liquid at room temperature, hydroxyl value 56KOHmg /
g, manufactured by Daicel Chemical Industries, Ltd.) Polycarbonate resin (d): Trade name “Placel CD
220PL "(liquid at normal temperature, hydroxyl value 56KOHmg /
g, manufactured by Daicel Chemical Industries, Ltd.) Polycarbonate resin (e): trade name “PNOC-10”
00 ”(melting point 50 ° C., hydroxyl value 112 KOH mg / g,
(Kuraray Co., Ltd.) [Ether compound] Ether compound (1): trade name "PG-207" (polypropylene glycol-diglycidyl ether, liquid at normal temperature, epoxy equivalent of 300 to 330, manufactured by Toto Kasei Co., Ltd.) Ether compound (2): Product Name "Rica Resin BEO-6"
0E "(polyethylene glycol-added bisphenol A type diglycidyl ether, liquid at normal temperature, epoxy equivalent 3
56, manufactured by Nippon Rika Co., Ltd.) Ether compound (3): trade name “Placcel CD221
T "(polyether-modified polycarbonate resin, normal temperature paste, hydroxyl value 56 KOHmg / g, manufactured by Daicel Chemical Industries, Ltd.) [Cationic polymerization initiator] As the cationic polymerization initiator, Asahi Denka Kogyo KK, trade name:" ADEKAOPTO " Mer SP-170 "(cationic polymerization catalyst, aromatic sulfonium salt compound, liquid at normal temperature). [Aliphatic hydroxyl compound] Trade name: "G-700" (polyether polyol, liquid at normal temperature, hydroxyl value of 205 to 245 KOH mg / g, manufactured by Asahi Denka Kogyo Co., Ltd.) [Thermoplastic resin] Trade name: "Dynapol S-1402" (Crystalline polyester resin, softening point 102 ° C, manufactured by Huls)

Example 1 (1) Production of Reactive Hot Melt Adhesive Composition A planetary mixer equipped with a jacket capable of circulating a heating oil through 70 parts of an epoxy resin (A) and 30 parts of a polycarbonate resin (a). At a temperature of 150
The mixture was mixed at 30 ° C. and a rotation speed of 30 rpm for 30 minutes. Then
After covering the whole with aluminum foil, 1 part of cationic polymerization initiator “ADEKA OPTOMER SP-170” was added,
The mixture was mixed at 30 ° C. and a rotation speed of 30 rpm for 10 minutes to obtain a reactive hot melt adhesive composition.

(2) Evaluation The performance (peeling adhesive strength and heat resistance) of the reactive hot melt adhesive composition obtained above was evaluated by the following methods. The results were as shown in Table 1.

Peeling adhesive strength: Using a roll coater set at 120 ° C., the reactive hot melt adhesive composition obtained above was used to make a No. 9 cotton canvas (25 mm × 150 mm).
Coating area is 25mm x 100mm, coating thickness is 100
After coating so as to have a coating thickness of ２００200 μm (coating amount of 10 to 20 mg / cm ² ), it was cured in a dark place at 23 ° C.-60% RH for 7 days. Next, using a high-pressure mercury lamp (trade name “Jetlight JL2300”, manufactured by ORK Mfg. Co., Ltd.), 365 nm was applied to the surface of the reactive hot melt adhesive composition of the coated product.
Was irradiated for 30 seconds at an illuminance of 25 mW / cm ² and then cured in a dark place at 23 ° C.-60% RH for 10 minutes. Next, a zinc steel plate (25 mm × 12
(5 mm x 0.8 mm) were superimposed, and heated and pressed under the conditions of a temperature of 80 ° C, a pressure of 0.5 kg / cm ² , and a time of 10 minutes to prepare a 90-degree square peel test piece. After the 90-degree angle peel test specimen obtained above was cured for 12 hours in an atmosphere of 23 ° C. and 60% RH, the 90-degree angle peeling test was performed in accordance with JIS K-6854 “Testing method for peel strength of adhesive”. A peel test was performed to determine a peel adhesive strength (kg / 25 mm).

Heat resistance: The coated surfaces of No. 9 cotton canvas, which were prepared under the same conditions as in the above case and were irradiated with light, were superposed on each other, and were subjected to a temperature of 80 ° C., a pressure of 0.5 kg / cm ² and a time of 10 minutes. And a T-peel test piece was prepared. Then, immediately, a 200 g weight was attached to one end of the cotton canvas of the T-peel test specimen obtained above, and the other end of the cotton canvas was fixed to the ceiling surface of a gear oven set at 100 ° C. Then, a T-peel type thermal creep test was performed,
The time until all the bonded portions of the test piece were peeled was determined.

(Example 2) As shown in Table 1, the composition of the reactive hot melt adhesive composition was as follows: 50 parts of the epoxy compound (A), 50 parts of the polycarbonate resin (a), and the cationic polymerization initiator "ADEKA Optomer SP-170 "
Except having set it as 1 part, it carried out similarly to Example 1, and obtained the reactive hot melt adhesive composition.

(Example 3) As shown in Table 1, the composition of the reactive hot melt adhesive composition was changed to 70 parts of the epoxy compound (B), 30 parts of the polycarbonate resin (a), and the cationic polymerization initiator "ADEKA Optomer SP-170 "
Except having set it as 1 part, it carried out similarly to Example 1, and obtained the reactive hot melt adhesive composition.

Example 4 As shown in Table 1, the composition of the reactive hot melt adhesive composition was changed to 50 parts of the epoxy compound (B), 50 parts of the polycarbonate resin (a), and the cationic polymerization initiator “ADEKA Optomer SP-170 "
Except having set it as 1 part, it carried out similarly to Example 1, and obtained the reactive hot melt adhesive composition.

Example 5 As shown in Table 1, the composition of the reactive hot melt adhesive composition was changed to 70 parts of the epoxy compound (B), 30 parts of the polycarbonate resin (b), and the cationic polymerization initiator “ADEKA Optomer SP-170 "
Except having set it as 1 part, it carried out similarly to Example 1, and obtained the reactive hot melt adhesive composition.

(Example 6) As shown in Table 1, the composition of the reactive hot melt adhesive composition was changed to 50 parts of the epoxy compound (B), 50 parts of the polycarbonate resin (b), and the cationic polymerization initiator "ADEKA Optomer SP-170 "
Except having set it as 1 part, it carried out similarly to Example 1, and obtained the reactive hot melt adhesive composition.

(Comparative Example 1) As shown in Table 1, the composition of the reactive hot melt adhesive composition was 100 parts of the epoxy compound (A) and 1 part of the cationic polymerization initiator "ADEKA OPTOMER SP-170". Then, a reactive hot melt adhesive composition was obtained in the same manner as in Example 1 except that the polycarbonate resin was not contained.

(Comparative Example 2) As shown in Table 1, the composition of the reactive hot melt adhesive composition was 100 parts of the polycarbonate resin (a) and 1 part of the cationic polymerization initiator "ADEKA OPTOMER SP-170". Then, a reactive hot melt adhesive composition was obtained in the same manner as in Example 1 except that the epoxy compound was not contained.

Comparative Example 3 As shown in Table 1, the composition of the reactive hot melt adhesive composition was 35 parts by weight of the epoxy compound (A) and 35 parts by weight of the aliphatic hydroxyl compound "G-70".
0 ", 12 parts, thermoplastic resin" Dynapol S1402 "
53 parts and a cationic polymerization initiator "ADEKA OPTOMER SP
A reactive hot melt adhesive composition was obtained in the same manner as in Example 1 except that 1 part of -170 "was used and the polycarbonate resin was not contained.

The performances (peeling adhesive strength and heat resistance) of the eight reactive hot melt adhesive compositions obtained in Examples 2 to 6 and Comparative Examples 1 to 3 were the same as in Example 1. Was evaluated. The results were as shown in Table 1.

[0146]

[Table 1]

The heat resistance in Table 1 was ">12".
Indicates that it did not peel after 12 hours. As is clear from Table 1, the reactive hot melt adhesive compositions of Examples 1 to 6 according to the present invention can easily adhere adherends even after irradiation with active energy rays,
Moreover, after curing, they exhibited excellent peel adhesive strength and heat resistance.

On the other hand, the reactive hot-melt adhesive composition of Comparative Example 1 containing no polycarbonate resin had a brittle cured product and extremely low peel adhesion strength.

The reactive hot melt adhesive composition of Comparative Example 2 containing no epoxy compound and the reactive hot melt adhesive composition of Comparative Example 3 containing no epoxy resin and containing no polycarbonate resin were used. All of the hot melt adhesive compositions had extremely poor heat resistance and low peel adhesion strength.

Example 7 (1) Production of Reactive Hot Melt Adhesive Composition A planetary mixer equipped with a jacket capable of circulating a heating oil through 70 parts of an epoxy resin (A) and 30 parts of a polycarbonate resin (a). At a temperature of 150
The mixture was mixed at 30 ° C. and a rotation speed of 30 rpm for 30 minutes. Then
After covering the whole with aluminum foil, 1 part of cationic polymerization initiator “ADEKA OPTOMER SP-170” was added,
The mixture was mixed at 30 ° C. and a rotation speed of 30 rpm for 10 minutes to obtain a reactive hot melt adhesive composition.

(2) Peeling adhesive strength and heat resistance were evaluated in the same manner as in Example 1 as the performance of the reactive hot melt adhesive composition obtained as described above. or,
The water resistance was evaluated by the following method. The results are shown in Table 2 below. Water resistance: A 90-degree square peel test specimen prepared under the same conditions as in the case of evaluating peel adhesive strength was cured for 12 hours in an atmosphere of 23 ° C. and 60% relative humidity, and then added to ion-exchanged water in a glass bottle. It was immersed and cured in a gear oven set at 100 ° C. for 3 days. Thereafter, the sample is taken out of the ion-exchanged water, and is taken out under an atmosphere of 23 ° C. and a relative humidity of 60%.
After curing for 2 hours, a 90-degree angle peeling test was performed in accordance with JIS K-6854 "Testing method for peeling adhesive strength of adhesive" to determine peel adhesive strength (kg / 25 mm), which was used as an index of water resistance. .

The following Examples 8 to 15 and Comparative Examples 1 to 3 were evaluated in the same manner as in Example 7. The results are shown in Table 2 below.

(Example 8) As shown in Table 2, the composition of the reactive hot melt adhesive composition was as follows: epoxy compound (A) 50 parts, polycarbonate resin (a) 50 parts, and cationic polymerization initiator "ADEKA Optomer SP-170 "
Except having set it as 1 part, it carried out similarly to Example 7, and obtained the reactive hot melt adhesive composition.

(Example 9) As shown in Table 2, the composition of the reactive hot melt adhesive composition was as follows: 70 parts of the epoxy compound (B), 30 parts of the polycarbonate resin (a), and the cationic polymerization initiator "ADEKA Optomer SP-170 "
Except having set it as 1 part, it carried out similarly to Example 7, and obtained the reactive hot melt adhesive composition.

(Example 10) As shown in Table 2, the composition of the reactive hot melt adhesive composition was as follows: 50 parts of the epoxy compound (B), 50 parts of the polycarbonate resin (a), and the cationic polymerization initiator "ADEKA Optomer SP-17
A reactive hot melt adhesive composition was obtained in the same manner as in Example 7 except that “0” was changed to 1 part.

(Example 11) As shown in Table 2, the composition of the reactive hot melt adhesive composition was 70 parts by weight of the epoxy compound (B), 30 parts by weight of the polycarbonate resin (b) and the cationic polymerization initiator "ADEKA Optomer SP-17
A reactive hot melt adhesive composition was obtained in the same manner as in Example 7 except that “0” was changed to 1 part.

(Example 12) As shown in Table 2, the composition of the reactive hot melt adhesive composition was as follows: 50 parts of the epoxy compound (B), 50 parts of the polycarbonate resin (b), and the cationic polymerization initiator "ADEKA Optomer SP-17
A reactive hot melt adhesive composition was obtained in the same manner as in Example 7 except that “0” was changed to 1 part.

(Example 13) As shown in Table 2, the composition of the reactive hot melt adhesive composition was as follows: 60 parts of the epoxy compound (B), 40 parts of the polycarbonate resin (c), and the cationic polymerization initiator "ADEKA Optomer SP-17
A reactive hot melt adhesive composition was obtained in the same manner as in Example 7 except that “0” was changed to 1 part.

(Example 14) As shown in Table 2, the composition of the reactive hot melt adhesive composition was as follows: 60 parts of the epoxy compound (B), 40 parts of the polycarbonate resin (d), and the cationic polymerization initiator "ADEKA Optomer SP-17
A reactive hot melt adhesive composition was obtained in the same manner as in Example 7 except that “0” was changed to 1 part.

(Example 15) As shown in Table 2, the composition of the reactive hot melt adhesive composition was as follows: 60 parts of the epoxy compound (A), 40 parts of the polycarbonate resin (e), and the cationic polymerization initiator "ADEKA Optomer SP-17
A reactive hot melt adhesive composition was obtained in the same manner as in Example 7 except that “0” was changed to 1 part.

[0161]

[Table 2]

The heat resistance in Table 2 was ">12".
Indicates that it did not peel after 12 hours. In addition, "x" of the water resistance indicates that the sample was spontaneously peeled off during the immersion in the ion-exchanged water.

As is clear from Table 2, Examples 7 to 1
In the reactive hot melt adhesive composition of 5, the adherend can be easily bonded even after irradiation with active energy rays, and after curing, it exhibits excellent peel adhesive strength, heat resistance and water resistance. I understand.

On the other hand, in Comparative Example 1, since no polycarbonate resin was contained, the peel adhesive strength was extremely low. Further, the reactive hot melt adhesive composition of Comparative Example 2 containing no epoxy compound, and the reactive hot melt adhesive composition of Comparative Example 3 containing a small amount of epoxy compound and not containing a polycarbonate resin In each case, heat resistance and water resistance were extremely poor, and peel adhesion strength was low.

(Example 16) Epoxy compound (A) 70
Example 7 except that 10 parts of the ether compound (1) and 1.1 part of the cationic polymerization initiator “Adeka Optomer SP-170” were used in addition to 10 parts and 30 parts of the polycarbonate resin (a). And a reactive hot melt adhesive composition was obtained.

(Evaluation) As the performance of the reactive hot melt adhesive composition obtained in Example 16, the peel adhesive strength, heat resistance and water resistance were evaluated in the same manner as in Example 7.
The curing retardation was evaluated by the following method. The results are shown in Table 3 below.

Curing delay property: A reactive hot melt adhesive composition was applied to No. 9 cotton canvas under the same conditions as those for the peel adhesive strength, and after irradiation with light, the No. 9 cotton canvas was cooled to 23 ° C. and a relative humidity. Cured for 12 hours in 60% darkness. Next, a zinc steel plate (25 mm × 125 mm × 0.8 mm in thickness) was superimposed on the light-irradiated coated surface, and the temperature was 80 ° C. and the pressure was 0.1 mm.
Heat press under conditions of 5 kg / cm ² and time of 10 minutes.
A 0-degree angle peel test specimen was obtained. The 90-degree square peel test specimen thus obtained was subjected to 1-hour test at 23 ° C. and 60% relative humidity.
After curing for 2 hours, a 90-degree angle peel test was performed in accordance with JIS K-6854 "Testing method for peeling adhesive strength of adhesive" to determine peel adhesive strength (kg / 25 mm).

Example 17 As shown in Table 3, the composition of the reactive hot melt adhesive composition was as follows: 70 parts of the epoxy compound (A), 30 parts of the polycarbonate resin (a),
A reactive hot melt adhesive composition was obtained in the same manner as in Example 16, except that 20 parts of the ether compound (1) and 1.2 parts of the cationic polymerization initiator “Adeka Optomer SP-170” were used.

Example 18 As shown in Table 3, the composition of the reactive hot melt adhesive composition was as follows: 70 parts of the epoxy compound (A), 30 parts of the polycarbonate resin (a),
A reactive hot melt adhesive composition was obtained in the same manner as in Example 16 except that 20 parts of the ether compound (2) and 1.2 parts of the cationic polymerization initiator “Adeka Optomer SP-170” were used.

Example 19 As shown in Table 3, the composition of the reactive hot melt adhesive composition was as follows: 70 parts of the epoxy compound (A), 30 parts of the polycarbonate resin (a),
A reactive hot melt adhesive composition was obtained in the same manner as in Example 16, except that 20 parts of the ether compound (3) and 1.2 parts of the cationic polymerization initiator “Adeka Optomer SP-170” were used.

The reactive hot melt adhesive compositions of Examples 17 to 19 and Comparative Examples 1 to 3 were evaluated in the same manner as in Example 16. The results are shown in Table 3 below.

[0172]

[Table 3]

The heat resistance “> 12” in Table 3 indicates that
It shows that it did not peel after the time. In addition, "x" of the water resistance indicates that the sample was spontaneously peeled off during the immersion in the ion-exchanged water. As is clear from Table 3, in each of the reactive hot melt adhesive compositions of Examples 16 to 19, the adherend can be easily adhered even after irradiation with active energy rays, and excellent peeling after curing. It exhibited adhesive strength, heat resistance and water resistance. Further, the progress of curing after irradiation with active energy rays can be sufficiently delayed, and as described above,
Even in the case of bonding after a lapse of time, sufficient peeling adhesive strength was exhibited.

(Example 20) Epoxy compound (A) 30
Part of the epoxy compound (C) and 60 parts of the polycarbonate resin (a) were charged into a planetary mixer, to obtain a reactive hot melt adhesive composition in the same manner as in Example 7.

As the performance of the reactive hot melt adhesive composition obtained as described above, the peel adhesive strength, heat resistance and water resistance were evaluated according to the methods described above. or,
The initial heat resistance was evaluated by the following method. The results are shown in Table 4 below.
Shown in

Initial heat resistance: Two pieces of No. 9 cotton canvas prepared under the same conditions as in the case of peel adhesive strength and irradiated with light were prepared, and the coated surfaces of the No. 9 cotton canvas were overlapped with each other, and at room temperature. Pressing was performed under the conditions of a pressure of 0.5 kg / cm ² and a time of 10 minutes to prepare a T-peel test specimen. Next, after curing for 3 hours in an atmosphere of 23 ° C. and a relative humidity of 60%, a 200-g weight was attached to an end of one cotton canvas of the T-type peel test specimen,
After fixing the other end of the cotton canvas to the ceiling surface of the gear oven set at 23 ° C., the temperature was raised at a rate of 2 ° C./5 min.
A temperature rise creep test of a mold peeling type was performed, and a temperature at which all the bonded portions of the test piece peeled was obtained.

Example 21 As shown in Table 4, the composition of the reactive hot melt adhesive composition was 30 parts of the epoxy compound (A), 20 parts of the epoxy compound (C), and 60 parts of the polycarbonate resin (a). A reactive hot-melt adhesive composition was obtained in the same manner as in Example 20, except that the parts were changed to 1.1 parts and the cationic polymerization initiator “ADEKA OPTOMER SP-170” was changed to 1.1 parts.

(Example 22) As shown in Table 4, the composition of the reactive hot melt adhesive composition was as follows: 30 parts of the epoxy compound (A), 10 parts of the epoxy compound (D), and 60 parts of the polycarbonate resin (b). A reactive hot-melt adhesive composition was obtained in the same manner as in Example 20, except that 1 part by weight and 1 part of a cationic polymerization initiator “Adeka Optomer SP-170” were used.

Example 23 As shown in Table 4, the composition of the reactive hot melt adhesive composition was 30 parts of the epoxy compound (A), 20 parts of the epoxy compound (D), and 60 parts of the polycarbonate resin (b). A reactive hot-melt adhesive composition was obtained in the same manner as in Example 20, except that the parts were changed to 1.1 parts and the cationic polymerization initiator “ADEKA OPTOMER SP-170” was changed to 1.1 parts.

With respect to the reactive hot melt adhesive compositions of Examples 21 to 23 and Comparative Examples 1 to 3 described above,
Evaluation was performed in the same manner as in Example 20. The results are shown in Table 4 below.

[0181]

[Table 4]

In Table 4, the heat resistance “> 12” is 1
It shows that it did not peel after 2 hours. Further, "x" of the water resistance indicates that the sample was spontaneously peeled off during the immersion in the ion-exchanged water. As is clear from Table 4, in each of the reactive hot melt adhesive compositions of Examples 20 to 23, the adherend can be easily bonded even after irradiation with active energy rays, and excellent peeling after curing. It exhibited adhesive strength, heat resistance and water resistance. Further, the time from bonding the adherend to developing heat resistance could be reduced.

On the other hand, the reactive hot melt adhesive composition of Comparative Example 2 containing no epoxy compound and the reactive hot melt adhesive composition of Comparative Example 3 containing little epoxy compound and containing no polycarbonate resin were used. In each case, the heat and water resistance of the melt adhesive composition was extremely poor, and the peel adhesive strength was low.
In addition, the time from bonding the adherend to developing heat resistance was long.

(Example 24) Epoxy compound (B) 50
The reaction was carried out in the same manner as in Example 7 except that 20 parts by weight of the epoxy compound (E), 50 parts of the polycarbonate resin (a) and 1.2 parts of the cationic polymerization initiator “Adeka Optomer SP-170” were used. A hot-melt adhesive composition was obtained.

As the performance of the reactive hot melt adhesive composition obtained as described above, the peel adhesive strength, heat resistance and water resistance were evaluated according to the methods described above. Further, the melt viscosity was evaluated in the following manner. The results are shown in Table 5 below.

Melt viscosity: Melt viscosity (cps) was determined at 120 ° C. according to the method B of JIS K-6862.
(Example 25) As shown in Table 5, the composition of the reactive hot melt adhesive composition was changed to the epoxy compound (B) 50
Example 2 except that 40 parts by weight of an epoxy compound (E), 50 parts of a polycarbonate resin (a) and 1.4 parts of a cationic polymerization initiator "ADEKA OPTMER SP-170" were used.
In the same manner as in Example 4, a reactive hot melt adhesive composition was obtained.

Example 26 As shown in Table 5, the composition of the reactive hot melt adhesive composition was as follows: 50 parts of epoxy compound (B), 20 parts of epoxy compound (F), and 50 parts of polycarbonate resin (b). Parts and a cationic polymerization initiator "ADEKA OPTOMER SP-170" 1.2 parts, except that a reactive hot melt adhesive composition was obtained in the same manner as in Example 24.

(Example 27) As shown in Table 5, the composition of the reactive hot melt adhesive composition was as follows: 50 parts of the epoxy compound (B), 40 parts of the epoxy compound (F), and 50 parts of the polycarbonate resin (b). Parts and a cationic polymerization initiator "Adeka Optomer SP-170" were changed to 1.4 parts to obtain a reactive hot melt adhesive composition in the same manner as in Example 24.

The reactive hot melt adhesive compositions according to Examples 25 to 27 and Comparative Examples 1 to 3 described above were evaluated in the same manner as in Example 24.

[0190]

[Table 5]

The heat resistance “> 12” indicates that the film did not peel off even after 12 hours. In addition, "x" of the water resistance indicates that the sample was spontaneously peeled off during the immersion in the ion-exchanged water. As is clear from Table 5, in each of the reactive hot melt adhesive compositions of Examples 24 to 27, the adherend can be easily bonded even after irradiation with active energy rays, and excellent exfoliation after curing. It exhibited adhesive strength, heat resistance and water resistance. Also, the melt viscosity was low.

On the other hand, the reactive hot melt adhesive composition of Comparative Example 2 containing no epoxy compound and the reactive hot melt adhesive composition of Comparative Example 3 containing little epoxy compound and containing no polycarbonate resin were used. In each case, the heat and water resistance of the melt adhesive composition was extremely poor, and the peel adhesive strength was low.
Also, the melt viscosity was high.

[0193]

As described above, the reactive hot-melt adhesive composition according to the present invention can be heated at a temperature not lower than the melting temperature,
The composition can be cured in a state where the curing speed, the application time, the tack-free time, and the like can be adjusted widely by irradiating active energy rays without the necessity of mixing the components and the like.

Further, the present invention can be applied to adherends that do not transmit active energy rays or non-moisture-permeable adherents, so that selectivity to adherends is low, and after curing, excellent adhesive strength, heat resistance and water resistance are obtained. Because it expresses various physical properties such as for automobiles, electrical products,
It is suitably used as a reactive hot melt adhesive for various industrial products including building materials.

Further, the reactive hot melt adhesive composition according to the present invention is of the active energy ray-curable type and not of the moisture-curable type, so that it is not necessary to strictly shut off the moisture. It is economical because there is no need to use packaging materials.

Furthermore, the bonding method of the present invention using the above reactive hot melt adhesive composition can easily obtain a bonded body having excellent physical properties such as excellent adhesive strength, heat resistance and water resistance with good workability. It can be suitably used for various industrial applications.

Continued on the front page F term (reference) 4J040 EC001 EC002 EC041 EC042 EC051 EC052 EC061 EC062 EC211 EC212 EC261 EC262 EE022 EL021 EL022 HB06 HB14 HB42 HB44 HD18 HD43 JB01 JB07 KA11 LA01 LA02 LA06 LA07 LA08 MA02 MA03 MA05 MA06 MA05 MA06 MA05 MA06 NA11 NA12 NA15 NA19 PA30 PA32 PA33

Claims (8)

[Claims] 1. A reactive hot melt adhesive composition comprising an epoxy compound, a polycarbonate resin and an effective amount of a cationic polymerization initiator capable of curing the present composition upon irradiation with active energy rays. 2. The reactive hot melt adhesive composition according to claim 1, further comprising an ether compound. 3. The reactive hot melt adhesive composition according to claim 1, further comprising an alicyclic epoxy resin and / or an epoxidized polyalkadiene. 4. The epoxy compound according to claim 1, wherein the epoxy compound comprises an epoxy compound having a softening point in the range of 40 to 200 ° C. according to a ring and ball measurement method, and an epoxy compound which is liquid at room temperature. Reactive hot melt adhesive composition. 5. The reactive hot melt adhesive composition according to claim 1, wherein the epoxy compound is an aromatic epoxy resin. 6. The reactive hot melt adhesive composition according to claim 1, wherein the polycarbonate resin is a polycarbonate resin having an aliphatic hydroxyl group. 7. The cationic polymerization initiator according to claim 1, wherein the cationic polymerization initiator is at least one cationic polymerization initiator selected from the group consisting of an aromatic iodonium complex salt, an aromatic sulfonium complex salt, and a metallocene salt. 7. The reactive hot melt adhesive composition according to any one of 6. 8. The reactive hot melt adhesive composition according to claim 1, which is heated and melted, applied to one or both of the adherends in a molten state, and adhered to each other. A bonding method comprising irradiating the coated reactive hot melt adhesive composition with active energy rays before or after bonding, and pressing the adherends together.