JPS59204611A - Thermoplastic, epoxy-suspended and urethane-containing compound - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides adhesives, sealants or coatings which, in combination with a heat-responsive epoxy curing agent, are cross-linked by heating, preferably applied in an accelerated manner, to provide a thermoset bond, seal or coating. This invention relates to novel compounds that can be used as compositions.

First, the technology in the United States in the field of this invention will be explained in the following passage.

Conventional hot melt adhesive compositions are solid at room temperature, but become soft and fluid as the temperature is raised, with good wettability with adherends. These adhesives can be easily applied between adherends in molten form and, upon cooling and solidification, result in a strong thermoplastic adhesive bond.

Thermoplastic adhesives used in solution suspension or solid form usually perform the bonding task by purely physical means.

Perhaps the most traditional means of applying thermoplastic adhesives is the hot melt process, in which a bond is formed as the polymer melt solidifies in place between the adherends. Bonds obtained by this method reach final strength more quickly than those obtained from solution-based adhesives. Obviously, the thermal stability of a thermoplastic material determines its potential usefulness as a hot melt adhesive. For a thermoplastic resin to be used as a hot melt adhesive, the resin must also have a low melt viscosity such that the adhesive can be applied to the adherend at acceptable speeds. Usually this means that the polymer must have a low molecular weight. However, many thermoplastic materials at low molecular weights cannot be used as hot melts because they do not have sufficient cohesive strength to be safely applied to substrates. For example, low molecular weight polyolefins, particularly low molecular weight and low viscosity polyolefins, are widely used as hot-melt adhesives for sealing corrugated paperboards, piecing multi-partitioned bags, etc., and for the production of polywood. does not have sufficient strength to be used in structural applications. Furthermore, low molecular weight polyolefins have sufficient heat resistance required for bonding components that are exposed to intermittent high temperatures, such as components located in or around automatic military internal combustion engines. do not have. In other words, thermoplastic adhesives cannot be used in locations where the location will be exposed to high temperatures again, as the adhesive will sag and break the bond at high temperatures. be.

The concept of thermoset or crosslinkable resin binders is also well known in the art. A number of resin adhesives are known that undergo irreversible chemical and physical changes to become essentially insoluble. Thermosetting adhesives containing both condensed heavy metals and addition polymers are also well known, examples include urea formaldehyde.

Phenol formaldehyde and melamine formaldehyde adhesives: epoxies, unsaturated polyesters
and polyurethane adhesives. More specifically, U.S. Pat. No. 3,723,568 teaches the use of polyepoxides and optional epoxy polymerization catalysts. The use of thermosetting resins obtained from polyamphitrites and polyepoxides is described in US Pat. Crosslinking in these patents is accomplished by reaction of available sites on the paste polymer with a crosslinking agent. US Percent Liver No. 4,157,364 describes inphthaloyl chloride.

Crosslinking of terpolymers of ethylene/vinyl acetate/vinyl alcohol using biscaprolactum or vinyltriethoxysilane has been taught; however, crosslinking with these crosslinking agents 1. This is achieved prior to thermal activation with addition crosslinking induced by heating. U.S. Pat. No. 4,116,937 further teaches thermal crosslinking using flexible polyimides of the polyamino bis-maleimide class, which compounds are hot-melt extruded at temperatures up to 150°C. Both can be cross-linked at high temperatures. In these last two patents, thermal crosslinking is achieved by reaction of reactive sites in the base polymer with specific crosslinking agents.

U.S. Pat. No. 6,934,056 describes ethylene-
He teaches a tacky resin composition comprising a vinyl acetate copolymer, a chlorinated or -chlorosulfonated polyethylene, an unsaturated carboxylic acid, and an organic peroxide. Other thermosetting adhesives are disclosed in U.S. Pat. No. 3,945,877.
Although it is taught in the book, here is the call cool pitch,
Compositions of ethylene/vinyl acetate copolymers and ethylene/acrylic acid copolymers with added crosslinking agents such as dicumyl peroxide have been described.

In many of these prior art thermoset adhesive compositions, mixing of two, three or four components is necessary to obtain a thermoset bond. The resulting bond is thus dependent on the uniformity of the mixing. Furthermore, in many cases, for example in the case of epoxy adhesives, two or more components must be mixed immediately before bond formation. This requires that the application of the adhesive be done quickly. This is because the crosslinking reaction starts immediately upon mixing.
This is because it cannot be reversed.

Further, U.S. Pat. No. 3,505,283 teaches that in the presence of a carboxylic acid anhydride as a curing agent,
Chemical thickener (chemical
It teaches the use of single organic di- and polyisocyanates as thickners.

Those produced in this way are not suitable as reactive hot melt adhesives. This is because the high application temperatures necessary to make the process possible cause a premature crosslinking reaction of the thermoset material. Similarly, U.S. Patent No. 3.424
, 719, the use of single diisocyanates to react dihydric phenols with glycidyl polyethers in a solvent enhances crosslink density, which results in improved heat distortion temperatures. Solvents are necessary for the polymerization in order to treat the glycidyl ether of dihydric phenol in solid form and can lead to not only processing problems but also instability of the reactant mixture after blending with the latent curing agent. It is also necessary to avoid high temperature conditions.

Next, the purpose of the present invention will be described.

Structural adhesives as well as sealants are necessary to bond substrates that are subject to significant mechanical stresses at their interfaces. Such adhesive materials must meet the following requirements:

When used on an assembly line, the time required for each operation should be short and constant, allowing high production rates, and the cleaning of surfaces to be joined that are exposed to sudden or gradual contamination. Based on these considerations, thermosetting materials such as epoxy Resins, phenolic resins, polyesters and polyurethanes are used as structural adhesives. After the crosslinking reaction, the adhesive becomes part of the structural components and provides the necessary bonding strength and heat resistance. Structural adhesives typically consist of a liquid resin and a hardener, whether in a two-pack or a single-pack, depending on the reaction between the resin and the hardener under storage conditions.

Liquid structural adhesives have the advantage of being easier to apply to substrates than solid adhesives. However, liquid adhesives require a pot life (this is the amount of time it takes to remain liquid for the purpose of the application) which is comparable to the two-pack form after mixing. As a result, it is not possible to rapidly increase the minimum strength required to keep a plurality of substrates in close contact with each other with good non-driving strength.

Furthermore, from a safety and health hazard perspective, liquid adhesives usually cause more contamination than solid adhesives. Thus, two-pack structural adhesives require very precise measurements and extremely good mixing to achieve consistent control over their properties.

One-pack liquid adhesives were devised to solve the problems of mixing and weighing difficulties. - To achieve the purpose of producing packaged reactive adhesive compositions, techniques such as chemical blocking and phase separation are used in the adhesive industry. The crosslinking reaction must be induced by heating or other techniques.

This reaction is difficult to suppress and results in increased handling strength over a long period of time.

Two types of adhesives, solid type and hot melt type, can be used in place of liquid adhesives.

Because of the phase separation between the resin powder and the curing agent powder, one-pack adhesives can be obtained very easily. However, their application, handling costs and safety considerations make powder adhesives less attractive to the adhesive industry.

Other solid forms of adhesives are hot melt types;
It is generally thermoplastic.

Hot melt adhesives provide a bond between substrates when the hot melt adhesive is cooled to room temperature. The binding process is fast and simple. A disadvantage of thermoplastic hot melt adhesives is the rapid decrease in bond strength upon reheating due to the properties of the thermoplastic resin.

Conventional solid adhesives such as high molecular weight epoxy resins can be applied as reactive hot melt adhesives. This type of solid adhesive can be used to react with carboxyl-terminated poly(butadiene-co-acrylonitrile) to materials that would otherwise have poor adhesive properties, such as impact resistance and lap shear strength. The impact resistance and lap shear strength increase when the material undergoes a metamorphic process. However, since this modification is carried out in the presence of a catalyst at a high temperature of 100 to 150°C, it is difficult to add latent hardeners and hardening accelerators, such as dicyandiamide, because the hardening reaction is thermally activated. This is because that. Therefore, the combination of their high cost and manufacturing difficulties makes this type of adhesive commercially unattractive.

The present invention relates to the development of a family of reactive hot melt adhesives that provide rapid growth in handling strength and maximum bond strength and heat resistance as thermoset adhesives. Furthermore, the present invention simplifies the adhesive production method and improves the polymer backbone concept (desigr+
) and the plasticization of polymers by adding reactive plasticizers to suppress the application temperature. The present invention also utilizes the reaction between diisocyanates, diol hydroxy groups, and epoxy resins to provide latent curability, long shelf life, internally modified adhesive properties, and the advantage of suppressing its plastic flow. The present invention relates to a method for producing reactive hot melt adhesives that can be used in various applications. Materials for the production of B's unique reactive hot melt adhesives include polyinsyanate, a hydroxyl-containing epoxy resin that introduces reactive pendant groups and improves the physical properties and reduces the viscosity of the bulk polymerization medium. The reducing diol preferably includes a difunctional-hydric alcohol. Reactive plasticizers can optionally be added to the system to reduce the viscosity of the bulk polymerization and to adjust the application temperature.

One object of the present invention is to obtain a solvent-free composition that can be used as an adhesive, sealant or coating. Another object of the invention is to obtain a composition that can be applied as a hot melt. Yet another object of the invention is to obtain a composition which can be thermocured within a minimum time. Yet another object of the present invention is to prepare new compounds which, when heated in combination with heat-reactive epoxy hardeners, can yield heat-cured coatings, adhesives or sealants. It is a further object of the present invention to be applied as a heat melt and then further cured with a heat activated initiator at a higher temperature to give a heat cured adhesive, sealant or coating. The objective is to produce thermoplastic compositions that can be used. Yet another object of the present invention is to provide one or more methods for producing thermoplastic compositions that can be used as hot melt adhesives. Purposes other than these will become clear from the description below.

Next, the present invention will be explained.

The present invention relates to thermoplastic, epoxy-suspending urethane-containing compounds that are the reaction products of epoxy resins containing one or more, preferably two, hydroxyl groups and diisocyanate-terminated diols.

The compound, preferably prepared in the presence of a heat-reactive, epoxy hardener, is heated to form a one-component material that can be used as a heat-cured adhesive, sealant, or coating.

Some of the epoxy resins used herein as reactants to make the new compounds are commercially available materials. Such materials include several of Shell's "Epon" resins having the general formula:

where n is approximately 1.
It can range from 1 to about 3. Another epoxy resin that can be used as the reactant itself is the methylolated version of a conventional bis-epi resin sold by M-End T Chemical Co. under the trade name Apogen-101J and having the ideal formula: .

CH.

In another example, the hydroxyl-containing epoxy resin reactant may be made by reacting a bis-epi resin, such as the diglycidyl ether of resorcinol, with a diol, such as bisphenol A, to form a hydroxyl-containing epoxy resin having the formula:

H3 Depending on the end use of the new compound, any diol can be used in the reaction with the bis-epi resin. In this way aliphatic diols such as diethylene glycol, polyethylene glycol, polypropylene glycol and the like can be used as well as aromatic polyols.

The hydroxyl-containing epoxy resin (1) is reacted with the isocyanate groups remaining on the hydroxyl-terminated diol to obtain the novel thermoplastic, urethane-containing compound with pendant epoxy groups of the present invention. That is, 1 + R-(Nco)2 ↓ ■ Here, R is an organic group remaining after diincyanate is added to the terminal of the diol.

The reaction between the hydroxyl-containing epoxy resin reactant and the incyanate groups remaining on the diol in this invention is necessary to uniformly disperse the latent epoxy curing agent throughout the solid reaction product. Preferably it is carried out in the presence of a curing agent and optionally an absorption promoter. The reaction is thus carried out at a temperature below the decomposition temperature of the latent epoxy hardener, for example in the range from 20 to 120C. The reaction is preferably carried out in the presence of a known urethane-producing catalyst in an amount sufficient for catalytic reaction, ie, from 0.01 to 5 parts by weight based on the weight of the reactants. Such catalysts include, but are not limited to, triphenylphosphine, dibutyltin dilaurate, tin(II) octoate, and the like.

If the decomposition temperature of the latent epoxy curing catalyst is lower than the reaction temperature of the urethane-forming reaction, the addition of the epoxy curing agent to the urethane-containing compound that is thermoplastic and suspends the epoxy will be at the temperature of the urethane-containing compound described above. Wait until it has cooled to room temperature. This is accomplished by milling the compounds with the epoxy hardener to obtain a homogeneous mixture thereof.

The latent epoxy hardener can be any chemical that causes crosslinking of the adhesive and does not destabilize the adhesive at temperatures lower than its application temperature. Addition of the epoxy curing agent of the compound is epoxy resin 1
00 parts A is carried out prior to urethane formation in amounts ranging from 4 to 50 parts. Well known thermally activated latent epoxy curing agents include, but are by no means limited to, dicyandiamide, RF, amine adducts, 4,4'-methylenebis(phenyl dianamid) and the like. do not have.

A curing accelerator may also be present in the hot melt adhesive composition to increase the speed of curing. Such accelerators for epoxy curing are well known and include phenylureas and the like.

Epoxy resins to be used include materials having at least one and preferably more than one epoxy group. These compounds may be saturated or unsaturated aliphatic, cycloaliphatic, aromatic or heterocyclic compounds and may be substituted with substituents such as chlorine, hydroxyl groups, ether groups and the like. Good too.

These compounds may be monomeric or polymeric.

Apparently, many polyepoxides and especially their polymeric forms are described using the term epoxy equivalent value.

The polyepoxides used in the compositions and methods of this invention are those having an epoxy equivalent weight value of at least 1.0.

Various examples of polyepoxides that may be used in the compositions and methods of the present invention are described in US Pat. No. 2,633,458. and the teachings of that patent regarding examples of polyepoxides are to be understood to be incorporated herein by reference.

Other examples include epoxidized esters of polyethylenically unsaturated monocarboxylic acids such as epoxidized linseed oil, soybean oil, soybean oil, mustard oil, tung oil, walnut oil and dehydrogenated castor oil, linoleic methyl acid, butyl linoleate.

9.12-Ethyl octadecadienoate, 9°12.
Butyl 15-octadecatrienoate.

Butyl eleostearate, tung oil fatty acid monoglycerides: soybean oil, sunflower oil, rapeseed oil.

Contains monoglycerides such as hemp oil, sardine oil, and cottonseed oil, as well as the same effects.

Another group of epoxy-containing materials used in the compositions and methods of this invention include epoxidized esters of unsaturated-hydric alcohols and polyhydric fatty acids. An example of this is the following passage. Di(2,3-epoxybutyl) adipate, di(2,3-epoxybutyl) oxuate-
1 moss (di(2,3-epoxyhexyl) acid, di(6,4-epoxybutyl) maleate, di(2,4-epoxybutyl) pimelate)
3-epoxyoctyl), di(2,3-epoxybutyl) phthalate, di(2,3-epoxyoctyl) tetrahydrophthalate, malz(di(4,5-epoxy-dodecyl) phosphate, tetraphthalic acid: ) (2,3-epoxybutyl), di(2,3-epoxybutyl) thiodipropionate, di(5,6-) dienyldicarboxylate.

epoxy-tetradecyl), sulfonyldibutyric acid di(3,
4-epoxyheptyl), 1', 2, 4-butane-tritricarboxylic acid tri(2,6-epoxybutyl), di(5,6-nipoxybentadecyl) tartrate, malein v:
) (4,5-epoxytetradecyl), azelaic acid)
C2,3-epoxybutyl), di(6,4-epoxybutyl) citrate, di(5,6-epoxyoctyl) cyclohexane-1,2-dicarphonate, malonic acid) (4
, 5-epoxyoctylcyl).

Furthermore, another group includes epoxidized 2,2-bis(2-
Included are epoxidized polyethylenically unsaturated hydrocarbons such as cyclohexenyl)propane, epoxidized vinylcyclohexene, and epoxidized dimers of cyclobutadiene.

Another group includes epoxidized polymers and copolymers of diolefins such as butadiene. Examples of these include inter alia butadiene-acrylonitrile copolymers (Hycar rubbers);
Includes butadiene-styrene copolymers and equivalents.

Another group includes glycidyl group-containing nitrogen compounds such as diglycidylaniline and di- and triglycidylamines.

Particularly preferred polyepoxides for use in the compositions of the invention are glycidyl ethers, especially glycidyl ethers of polyhydric phenols and polyhydric alcohols. Glycidyl ethers of polyhydric phenols can be obtained by reacting epichlorohydrin with the desired polyphenol in the presence of an alkali. Polyether-A and Polyether-B, described in U.S. Pat. No. 2,633,458, cited above, are good examples of this type of polyepoxide. Other examples include 1.1
．． 2.2-tetrakis(4-hydroxyphenyl)ethane (epoxy value: 0.45 eq, / 10 (1y
-1 m, p: 85°C), 1.1.5; 5-tetrakis (
hydroxyphenyl) is methane (epoxy value: 0.51
4eq, /1oo! ip) and their equivalents and mixtures thereof.

Further examples of epoxy resins that can be used in the present invention are (
However, the epoxy resins are not limited to the following. diglycidyl isophthalate, diglycidyl phthalate, 0-glycidyl phenylglycidyl ether,
Diglycidyl ether of resorcinol, triglycidyl ether of phloroglucinol, triclicidyl ef of methylphloroglucinol /', 2T6-(2,3
-epoxypropyl) phenyl glycidyl ether,
[,4-(2,6-epoxy)propoxy-N,N-
Bis(2,6-epoxypropyl)aniline, 2,2-
bis[p-2,3-epoxypropoxy)phenyl)-
) Lopan Diglycidyl ether of bisphenol-A, diglycidyl ether of bisphenol-hexafluoroacetone, diglycidyl ether of 2,2-bis(4-hydroxyphenyl)nonadecane, diglycidyl phenyl ether, triglycidyl 4,4- Bis(4-
hydroxyphenyl) hamethanoic acid, diglycidyl ether of tetrachlorbisphenol-A, diglycidyl ether of tetrabromobisphenol-A, triglycidyl ether of trihydroxybiphenyl, tetraglycidoxybiphenyl, [tetrakis(2,3-epoxypropoxy)] diphenylmethane], (2,2', 4
.

4'-tetrakis(2,3-epoxypropoxy)benzophenone, 6.9-bis[2-(2,3-epoxypropoxy)phenylethyl J-2゜4.8.10-tetraoxaspiro[5,5] Undecane, triglycidoxy-1,1,! +-triphenylpropane, tetraglycidoxy-tetraphenylethane, phenol formaldehyde polyglycidyl ether of novolak, 0-
Polyglycidyl ether of cresol-formaldehyde novolak, diglycidyl ether of butanediol, di(2-methyl)glycidyl ether of ethylene glycol, polyepichlorohydrin di(2,3-epoxy-propyl) ether, diglycidyl ether of polypropylene glycol, Epoxidized polybutadiene, epoxidized soybean oil, triglycidyl ether of glycerin, triglycidyl ether of trimethylol-propane, polyallyl glycidyl ether, 2,4,
6,8゜10-hantakisu(3-(2,3-epoxypropoxy)-zolopyl J 2 , 4 , 6 , 8.1
0-Pentamethylcyclopentasiloxane, diglycidyl ether of chloreneditsch diol, diglycidyl ether of dioxanediol, diglycidyl ether of endomethylene cyclohexane diol, -)-)cycloether of hydrogenated bisphenol-A, Vinyl cyclohexene, #-'F'/do, limonene dioxide, dicyclopenc diene dioxide, p-epoxycyclobentenylphenyl cricidyl ether, epoxydicyclobentenylphenyl cricidyl ether,
0-Epoxycyclopentenyl phenylcricidyl ether, bis-epoxy-dicyclopanthyl ether of ethylene glycol, [(2,,3,4-epoxy)cyclohexyl-5°5-spiro(3,4-epoxy)-cyclohexane -m-dioxane], 1,3-bis[3-
(2,3-epoxypropoxy)propyl]tetramethyldisiloxane, epoxidized polybutadiene, triglycidyl ester of linoletameric acid, epoxidized soybean oil, diglycidyl ester of linoletameric acid,
2.2-bisxyl]propane, 2.2-(4-(3-
Chlor-2-(2,ri-epoxypropoxy)furopyrrolecocyclohexyl)propane, 2,2-bis(3,
4-epoxycyclohexyl) furo/gun, bis(2,
3-Epoxycyclobentyl)ether (i-isomer)
, bis(2,3-epoxycyclobentyl)ether (
solid isomer), 1,2-epoxy-6-'(2,3-epoxypropoxy)hexahydro-4,7-methanoindam, 6,4-epoxycyclohexylmefk-(5,
4-epoxy) cyclohexanecarboxilade, 6,
4-Epoxy-6-methylcyclohexylmethyl-4-
Epoxy-6-methylcyclohexane carboxylade and bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate. Tri- and tetrafunctional epoxides such as triglycidyl isocyanurate and tetraphenylolethane epoxy can also be used in the present invention.

The reaction to create hydroxyl groups on the epoxy resin is carried out in the presence of a catalyst at a temperature in the range of 80-150°C, preferably 90-125°C. Well-known catalysts Nf'lj) Riphenylphoshine, triisoprobylamine, [):3- (p
-chlorophenyl)-1,1-dimethylurea. These catalysts are added to the reaction in amounts ranging from 0.1 to 1.2 parts per 100 parts of epoxy resin.

When making a solid hot melt adhesive from a liquid reaction mixture, it is possible, and sometimes preferred, for a liquid reactive plasticizer to be present in the mixture. Reactive plasticizers have two functions. First of all, this reduces the viscosity of the reaction mixture and improves its processability. Second, it improves physical properties such as lap shear strength of the cured product. The selection of a liquid reactive plasticizer is such that it does not react with either the NCO or OH groups during the polymerization reaction to form the true melt adhesive, but participates in the crosslinking reaction when the adhesive is used and cured. Based on something. Any of the above liquid epoxides used to obtain the hydroxyl group-containing epoxy resin can be used as the reactive plasticizer in the present invention. If a reactive plasticizer is used, it is added in an amount up to 40 parts by weight based on the final polymerized adhesive.

The polyincyanates used in this invention to terminate the diols and react with the hydroxyl groups in the epoxy resin can be aromatic, aliphatic, cycloaliphatic, and combinations thereof. Incyanates are preferred, but tri- and tetra-incyanates can also be used. More specifically, examples of diincyanates include 2.4-1 diincyanate 1
m-phenylene diisocyanate, xylene diisocyanate, 4-chloryl-1,3-phenylene diisocyanate, 4゜4'-biphenylene diisocyanate, 1
．． t-tetramethylene diinsyanate and 1,6-
These include hexamethylene diisocyanate, 1,4-cyclohexylene diisocyanate, 1,5-tetrahydronaphthalene diisocyanate and methylene dicyclohexylene diisocyanate. Diincyanates in which any of the diincyanate groups are attached directly to the ring are preferred because they react more rapidly than others.

Preferably, the diol terminally substituted with a diincyanate is a primary alcohol that is difunctional, since the primary alcohol has a higher concentration of diincyanate groups than the tertiary alcohol present on the epoxy resin. This is because it has a faster reaction rate. Thus, in a one-step process in which all the reactants, diincyanate, difunctional primary alcohol, and hydroxyl-containing epoxy 411 are mixed simultaneously, the diincyanate is selectively added to the terminal end of the difunctional primary alcohol. The incyanate groups remaining on the terminally substituted rethanol interact with the hydroxyl groups on the epoxy resin.

In a two-step process in which in the first step the diisocyanate acts with the diol, it is then possible to use a primary alcohol, a tertiary alcohol or a tertiary alcohol. The incyanate thus obtained is substituted '; o = k t'i in a second step h and is treated with an epoxy resin containing hydroxyl groups.

In the foregoing reactions, whether it is a one-step reaction or a two-step reaction, the amount of diisocyanate used is sufficient to react with all the hydroxyl groups on the diol. There is no such thing as more than quantity. Thus, the molar ratio of diol to diisocyanate is 1:
It is within the range of 1.2 to 2. The diols terminally substituted with incyanate must now have a molecular weight in the range 400 to 6000. Diols with molecular weights lower or higher than this range can also be used but do not result in processability.

The viscosity of diols at operating temperatures must be low to reduce processing requirements. Hydroxyl-terminated polymers such as polycaprolactone diol, polypropylene glycol, polyethylene glycol and hydroxyl-terminated polybutadiene have low viscosities at operating temperatures. Any material having the above-mentioned physical properties and hydroxyl-terminated can be used as the diol in the present invention.

As will be seen in the examples given later, the use of a diol having an incyanate at its end improves processability during production, flexibility and high durability of the cured product, compared to the use of diincyanate itself. This is important for obtaining impact resistance. For example, some diisocyanates and epoxy resins are solid at room temperature, so to improve their mixing and processability, it is necessary to use a solvent or heat them to a high temperature to achieve uniform mixing. is necessary. This is avoided by the use of incyanate-terminated liquid diols, which allow uniform mixing with the epoxy resin even when the resin is solid.

Additionally, the use of diisocyanates themselves, due to their rigid structure, results in products that are more brittle than the pliable products obtained from inocyanate-terminated diols.

In addition, the use of terminally substituted diols results in cured products with high impact resistance due to their pliability, which is not achieved by the rigid diisocyanates themselves. Furthermore, the pliability of the terminally substituted diols also allows the application temperature of the hot melt adhesive to be lowered, which allows for the use of a wide range of application temperatures. In addition to this, a suitable choice of diol makes it possible to improve the adhesive properties, ie open time and handling strength, compared to the diisocyanate itself.

Reactive hot melt adhesives can be made in a one-step or two-step process as described above. In the one-step method,
All reactants, diisocyanate, difunctional primary alcohol, hydroxyl-containing epoxy resin, latent curing agent, and optionally reactive plasticizer and curing accelerator are mixed together to form a liquid reaction mixture. The polymerization reaction is 20
It is carried out at a temperature of ˜60° C. with high speed stirring for the first 10-15 minutes over a period of 1 hour to 2 days depending on the temperature. Optionally, a urethane-forming catalyst such as diptyltin dilaurate is added in an amount of 0.1 to 5% of the total reaction weight.
It can be added to the system in amounts ranging from t% by weight. The solid hot melt adhesive yields a solid idealized cyclic polymer used as a hot melt adhesive by the following reaction equation.

In the two-step process, the diisocyanate is heated at 20-50°C.
The diol is first reacted with the primary, secondary or tertiary diol in the presence or absence of a urethane-forming catalyst at a temperature in the range of . i.e. 20CN-R-NCO+HO-R-OH In the second step, the incyanate-terminated diol is then exposed to a latent curing agent through its -NCO group and optionally to the presence of a reactive plasticizer and curing accelerator. The epoxy below reacts with the hydroxyl groups on the resin to create a solid hot melt adhesive with the following idealized repeating structural formula: That is, 111+H0-几-OH 000 The heating step for curing the hot melt adhesive compound containing urethane and suspending epoxy groups to obtain a thermosetting material is usually carried out at 100 to 300°C, preferably 1200 to 300°C, for 10 seconds to 30 minutes. It is carried out at a temperature of 200 DEG C., conditions which are sufficient to fully cure the composition into a solid heat-cured adhesive, sealant or coating.

The heating step for curing the compounds of this invention using latent epoxy curing agents can be accomplished in several ways. In single-adhesive systems, the adhesive composition is applied by hand to the adherends, brought into contact with other adherends, and then the combined system is placed in a forced air oven until a thermoset bond is created. Heat it up.

Additionally and preferably, electromagnetic heating is used as a faster and more effective means of curing, especially when the substrates to be bonded are plastic materials. In addition to producing high strength bonds, electromagnetic coupling techniques aid in (a) rapid bond completion times, and (b) automated part-time work and assembly.

In practicing the present invention, the adhesive compositions of the present invention may be used to bond (1) plastic to plastic, (2) plastic to metal, and (3) electromagnetic heating to bond metal to metal. You can. For example, if the adhesive composition contains sufficient polar groups to cause rapid heating of the adhesive composition to bond the adherends, the dielectric heating method described in (1) and ( It can be used for the connection of 2). The induction heating method also includes (1) and (2) above.
It can be used to combine each of 1 and (3).

That is, when at least one of the adherends is an electrically conductive metal or a ferromagnetic metal, the heat generated therein is carried to the adhesive composition by conduction and begins to harden, forming a thermoset adhesive. form an agent.

If the double wave kimono is plastic, it is necessary to add an energy absorbing material, ie an electrically conductive or ferromagnetic material, preferably in the form of fibers or granules (10-400 mesh) to the adhesive composition. Energy absorbing materials are typically added in amounts ranging from 0.1 to 2 parts by weight per part by weight of the adhesive composition. Particles of energy absorbing material can also be included in the plastic deposit at the bond seam to use induction heating, but care must be taken to avoid bending the plastic.

The particulate electromagnetic energy absorbing material used in the adhesive composition when using the induction heating process can be (1) a magnetic metal containing iron, cobalt and nickel, or (2) a magnetic alloy of nickel and iron or nickel and chromium. or oxide, and (3
) ferric oxide, above (1).

It can be one of (2) and (3). These metals and alloys have a high Curie point of about 388° to about 11
It has a temperature of 16°C ('7300-2040''F).

Electrically conductive materials that can be used in the present invention when using induction heating methods include, but are not limited to, precious metals, copper, aluminum, nickel, zinc and carbon black, gelaphite and inorganic oxides. do not have.

There are two types of high-frequency heating methods that can be used in the present invention, and which one to choose depends on the material to be bonded. The main difference between the two is whether the deposited material is electrically conductive or not. If the deposited material is one that conducts electric current, such as iron or steel, induction heating is used. If the substance is wood 9 paper.

When the fabric 2 is an electrical insulator such as synthetic resin, rubber, etc., a dielectric heating method can also be used.

Most natural and synthetic polymers are non-conducting and therefore suitable for dielectric heating. These polymers may contain a variety of dipoles and ions that are oriented in an electric field and rotate as the electric field oscillates to remain aligned in the direction of the electric field. The polar groups may be incorporated into and integral with the polymer backbone, or may be pendant side groups.

It can be additives, spreading agents, pigments, etc. For example, lossy fillers such as carbon blanks can be used as additives at one level to enhance the dielectric response of the adhesive. When the polarity of the electric field reverses by hundreds of gals per second,
The high frequency of the resulting polar units generates heat in the material. The uniqueness of dielectric heating lies in its uniformity, rapidity, specificity and effectiveness. Most plastic heating methods, such as conduction heating, convection heating or infrared heating, are surface heating methods, which require establishing a high temperature inside the plastic and then transferring the heat by conduction. Heating of plastics by these methods is therefore relatively slow and involves temperature inhomogeneities resulting in surface overheating.

In contrast, dielectric heating generates heat within the material, so heating is uniform and rapid, and no conduction heat transfer is required. The electric frequency of the electromagnetic field in the dielectric heating system of the present invention is within the range of 1 to 3,000 MHz (with or without
The electromagnetic field is generated from a 0.5 to 1.000 kilowatt power source.

Induction heating is similar to, but not identical to, dielectric heating. The differences are as follows.

a) It has magnetic properties instead of dielectric properties.

b) A coil rather than a pole or plate is used to apply the load (Ioad). and C) the induction heater applies maximum current to the load.

The generation of heat due to the dielectric is due to the 1 of the conductor with each reversal of the alternating current source.
The rise and fall of the eagle's magnetic field causes it to rise. The actual deployment of such a magnetic field is achieved by appropriate placement of conductive coils. When other electrically conductive materials are exposed to this magnetic field, dielectric currents are generated. These currents can be of the type of random or eddy currents, and these currents result in the generation of heat. Materials with both magnetic and conductive properties have a higher resistance than materials with only conductivity. and easily generate heat. The heat generated as a result of the magnetic component is the result of hysteresis or work that occurs when rotating magnetic molecules, and as a result of the flow of eddy currents.Polyolefins and other plastics are in their natural state. It is neither magnetic nor conductive. These polymers therefore do not generate heat within themselves as a result of dielectric properties.

The use of electromagnetic induction heating for adhesively bonding plastic structures has proven to be advantageous through the incorporation of selected electromagnetic energy absorbing materials into the hot melt adhesive compositions of the present invention. It was done. These ``electromagnetic energy absorbing materials'' can be added to the liquid hot melt reaction mixture prior to its solidification or can be milled with the hot melt adhesive after assimilation.

Neighbors unrelated to such energy-absorbing materials
'The electromagnetic energy passing through the abutting plastic structure is concentrated and absorbed into the adhesive composition by such energy absorbing materials, thus rapidly initiating the curing of the adhesive composition and completing the curing of the adhesive. .

Various types of electromagnetic energy absorbing materials have been used in electromagnetic dielectric heating techniques for some time. For example, inorganic oxides and metal powders have been incorporated into bonding layers and then exposed to electromagnetic radiation. In either case, the choice of energy absorbing material is influenced by the type of energy source. If the heat-absorbing material does not consist of ferromagnetic fine powder particles, and such powder particles are effectively insulated from each other by a non-conductive matrix material containing the fine particles, the heating effect will be substantially reduced. is limited to heating effects derived from hysteresis effects. As a result, heating is limited to the Curie temperature of the ferromagnetic material, or the temperature at which the material ceases to be magnetic.

The electromagnetic adhesive compositions of the present invention may be in the form of extruded ribbons or tapes or cast gaskets or cast sheets. In liquid form, it may be applied with a brush to the surfaces to be bonded, or may be sprayed onto the surfaces or may be used for dip coating of the surfaces.

The adhesive compositions described above, when used in excess as described below, result in solvent-free adhesive compositions that make it possible to bond metal or plastic surfaces without expensive pre-treatments. The electromagnetically induced binding reaction occurs rapidly, which makes it suitable for automated molding methods and equipment.

In accordance with the present invention, the electromagnetic adhesive composition is preferably heated for about 5 to about 60 megacycles of an electromagnetic field to ensure that a focused and localized heating zone is achieved by dielectric heating for bonding. It has been found that activation and bonding can be created by a dielectric heating system operating at electrical frequencies of about 15 to 60 megacycles. Thus, the electromagnetic field is about 1 to about 30
KW, preferably from a power source of about 2 to about 5 KW.

The electromagnetic field is applied to the articles to be bonded for less than about 2 minutes.

As described above, the electromagnetic inductive coupling system and improved electromagnetic adhesive composition of the present invention can be applied to thermoset materials, including metals, thermoplastic materials, and fiber reinforced thermoset materials. You can.

Prior to using the epoxy-suspended and urethane-containing hot melt adhesive compounds of this invention with latent epoxy hardeners, it is important that the compounds are linear or cyclic, ie, thermoplastic. In this way, the number of OH groups contained in the Epon resin prior to reaction with the diol terminally substituted with incyanate depends on the functionality of the polyisocyanate used to terminate the diol and during the reaction. can be any number, preferably 2, depending on the equivalent ratio of 10H to -NCO. For example, polyurethane can be produced by reacting bisphenol with a monoepoxide having a xyl group, that is, a diol having an isocyanate substituted at the end.0 Here, n is an arbitrary number that exists in the molar ratio of ■ and incyanate. I can do it.

The resulting thermoplastic, epoxy-suspended and urethane-containing material is then mixed with a latent epoxy curing agent, such as dicyandiamide, and upon heating the paint, sealant or adhesive becomes one cured by the epoxy groups. Additionally, dihydroxyl diepoxides can be used. For example, H3 is reacted again with a diol having an incyanate substituted at the end to form a polyurethane.

0 0 Here, n resides in the molar ratio of ■ and isocyanate.

The resulting thermoplastic (■) has a terminal epoxide formed by the reaction of the bisphenol with epichlorohydrin, which when heated with a latent epoxy curing agent yields a thermoset useful as an adhesive, sealant or coating. A polymeric material containing more than two OH groups, such as the Epon resin commercially available from Shell Chemical Co., where n is 2,2, may also be reacted with the amount of diisocyanate. can be used when the amount is less than the stoichiometric amount. Thus, in systems containing difunctional monomers, a high degree of polymerization is achieved only if the reaction is forced to near completion. Introducing a trifunctional monomer into the reaction causes a rather surprising change that is best explained using a modification of Carothers' equation. We introduce a more general functionality factor, fav, which is defined as the average number of functional groups present per monomer unit. First N. For a system with a molecule and the same number of two functional groups A and B, the total number of functional groups is N. It is fav. The number of groups that react in time to yield N molecules is therefore 2 (No-N) and B, = 2 (No N)/Nofav, therefore X.

is expressed as follows.

xn=2/(2-pfaJ However, this formula is valid only when the same number of two functional groups are present in the system.

In a fully bifunctional system, such as a mixture of equimolar amounts of an epoxy resin and a diisocyanate containing two hydroxyl groups, fav=2, and when p=Q, 95, X
n=20. However, if the trifunctional alcohol is added and the mixture consists of 2 moles of diincyanate, 1.4 moles of diol and 0.4 moles of triol, faV increases and fav=(2X2+1.4X2+0.4X3)/ 6
．． 8 = 2.1. X after the conversion rate reaches 95%. The value of is 200, but only a slight increase in the conversion rate to 95.23% is required for Xn to approach infinity. This small fha is the most dramatic increase.

This is a direct result of the incorporation of trifunctional units into the linear chain where unreacted hydroxyls provide additional sites for chain growth. This results in the formation of a highly branched structure, and the greater the number of polyfunctional units, the faster the growth into an insoluble three-dimensional network. When this occurs, the system is said to have reached its gel point or thermoset. In the present invention,
It is important that the composition remains thermoplastic and that it does not reach its gel dead point before it is used as a coating, sealant or hot melt adhesive.

It is clear that the following examples are only intended to illustrate the invention and are not intended to limit it. Unless otherwise noted, all parts and percentages are by weight.

Adhesive tensile shear bond strength (metal-to-metal) is 6.45
Adhesive area (overlapping area/
・・1apped area) ASTMDI
A test was conducted according to the test method 002-64.

Example 1 Production of isocyanate-substituted diol Polypropylene glycol (molecular weight = 72!M1 mol) 1278F was added dropwise to a flask containing 61.49 g of toluene diisocyanate over 6 hours in a nitrogen atmosphere. The reaction was continued with stirring for 4 days at room temperature. The resulting chain-grown and incyanate-terminated product will be referred to hereinafter as incyanate-substituted diol A.

Example 2 To a flask containing 58 t of toluene diisocyanate in a nitrogen atmosphere was added dropwise 1002 of commercially available polyethylene glycol (molecular weight 600 y 1 mol) over 6 hours. The reaction continued overnight at room temperature. The product having an extended chain with an incyanate end will be referred to hereinafter as incyanate-substituted diol B.

Example 6 Commercially available hydroxyl-terminated polybutidiene (2,800 g.
mol) 100f was added dropwise. The reaction was continued overnight with stirring at room temperature. The inocyanate-terminated, extended chain product will be referred to hereinafter as isocyanate-substituted diol C.

Example 4 Preparation of epoxide Epoxy resin 502, which contains 257 r/eq of OH and is commercially available from Shell Chemical Company under the trade name Epon-1001F, 1.8 r/eq of dicyandiamide, and 0.9 M' triphenylphosphine. To the mixture containing 1002 of Incyanate-substituted diol B from Example 2 was added. After heating to 80° C. for 1 hour, the adhesive was cooled to room temperature and then solidified. After standing at room temperature for 4 days, this The reactive hot melt adhesive was applied to glass fiber reinforced polyester (SMC) substrates at 125°C and cured at 170°C for 6°0 min. A bond with an overlap of 2.54 m indicated substrate rupture. Ta.

Example 5 To a mixture of Epon-1001F 1002 and dicyandiamide 61 was added isocyanate-substituted diol C 1002 from Example 6. After heating to 80° C. for 60 minutes and standing at room temperature for 4 days, the resulting adhesive was applied to a polyester substrate reinforced with glass fibers with an overlap of 2,54 cm and then cured at 170° C. for 60 minutes. An effective adhesive bond was obtained.

Example 6 Into a flask containing 100 t of diglycidyl ether of bisphenol A, 152 bisphenol A and 0.12 r of triphenylphosphine were added in 4 equal amounts over 60 minutes at a reaction temperature of 120°C. added. The reaction continued for 2.5 hours at 120°C. The epoxide equivalent weight of the modified reaction product was 2929/eq based on titration.

Modified epoxy reaction product 1001 was combined with incyanate-substituted diol A from Example 1 and dicyandiamide 6? and mixed at room temperature to obtain a tacky hot melt adhesive containing reactive epoxy F groups. This hot melt adhesive was applied between cold rolled steel adherends at 100°C, and both were placed in a press 111 and an air oven at 180°C for 30 minutes. The tensile shear adhesive strength obtained was 3,500 p.
, 5-i- This adhesive was similarly used between glass fiber and polyester composite adherends. The adherend failed prior to adhesive bonding in a tensile shear bond strength test.

Example 7 From Ciel Chemical Co., Ltd. under the trade name “Epon-10DIFJ”
Epon-1001F), 657t/
Isocyanate-substituted diol A from Example 1 is added to a mixture containing eq of OH-containing epoxy resin 100f, dicyandiamide 61 and triphenylphosphine 1t.
71.6F was added. After heating to 80° C. for 1 hour, the adhesive was cooled to room temperature and solidified to form a reactive hot melt adhesive.

After being applied to the substrate at 125°C and cured for 60 minutes at 160°C, the adhesive exhibited a tensile shear bond strength of 3,200 psi to steel, but no adhesive strength to the substrate to glass fiber reinforced polyester. brought about its own destruction.

Example 8 Epoxy resin 25 containing 1 mole of 0.20H groups and commercially available from Shell Chemical Company under the tradename Epon-828.
Inocyanate-substituted diol A71,69 from Example 1 was added to a mixture containing f1 Epon-10,'01 F1002 and dicyandiamide 7,5t. After heating to 80°C overnight, the adhesive was applied to the substrate at 125°C and cured for 60 minutes at 3°C. The adhesive had a tensile shear bond strength of 4,400 psi to steel and a tensile υ shear bond strength of 460 psi to glass fiber reinforced polyester.

Example 9 Bisphenol A212 to 1002 of Epon-828
and triphenylphosphin 0.14F mixture at 120%
Added at °C. After reaction for 6 hours at 120° C., the epoxy-terminated hydroxyl-containing product 1002 was dissolved in methylene chloride 1002 and then converted to the incyanate-substituted diol from Example 1 with 61t in the presence of 0.52 dibutyltin dilaurate. Made it react. The reaction was monitored by IR until no isocyanate was detectable. Di-cyandiamide 62 and triphenylphosphine 22 were added to the reaction mixture. The solvent methine chloride/was removed under vacuum.

Apply the final true melt adhesive to the substrate at 125°C,
It was cured at 60°C for 60 minutes. This adhesive had a tensile shear bond strength of L50 D psi to steel and a same bond strength of 900 psi to glass fiber reinforced polyester.

To the melted 100f of Example 10, 48.9f of σ) incyanate-substituted diol A from Example 1 and 0.75F of dibutyltin dilaurate as a catalyst were added. The reaction continued until traces of isocyanate could be detected from the IR spectrum.

Example 11 100 t of the product solution from Example 6 was charged with
Ancamine-87D J
40 tons of amine adducts commercially available under the trade name 0)
added. After vacuum drying, this material was heated to 100 amps for 2
It was cured in a radio frequency (RF) oven for 90 seconds to a thermosetting solid.

Example 12 To the product solution 1002 from Example 10, 5or of Standard-06 iron powder (supplied by EMABond) and 40f of Ancamine Y-870 were added.
added. After drying in vacuum, the final adhesive was cured by induction heating in an electromagnetic field for 75 seconds, resulting in a thermoset solid. It is something.

Example 16 Solid epoxy resin that is not modified Epon-1001F, a hydroxyl group-containing solid epoxy resin commercially available from Shell Chemical Co., Ltd.
1 was melted at 80°C, then dicyandiamide 0
, 6t and triphenylphosphine 0.42. 'JA adhesive after applying to three pieces of steel substrate with surface area 5, 23 c, a (1/2 inch square)
It was cured at 60°C for 60 minutes.

59.4 r of Epon-1001F was melted at 80°C and mixed evenly with 3.6 f of diisocyanate and 2.41 of triphenylphosphine, then 4.
Due to the high treatment temperature of O reacted with MDI of 12, the mixture quickly became mushy and the mixing uniformity was low.

The application temperature of this solid adhesive was above 100°C.

After applying this adhesive to two pieces of steel with an overlapping area of 3.23 crl (1/2 inch square), the adhesive was heated to 160°C for 6 hours.
The adhesives treated for 0 minutes were cured 0594T Epon-1001F, 12.49% PC'P-240 (a polycaprolactone diol having a molecular weight of 2,000 f1 mole and commercially available from Union Carbide) and reactive 23.89 wcc-s o 06 as plasticizer
It is a liquid epoxy resin modified with poly(butadiene-co-acrylonitrile) having a C carboxyl group at the end and is commercially available from Wilmington Chemical Co.]
were uniformly mixed at 80°C. After obtaining a homogeneous mixture3.
A mixture of 6 t of dicyandiamide and 2.42 t of triphenylphosphine was stirred for 2 hours, cooled to 60°C, and adjusted to an MDI of 4, 5? until a homogeneous solution was obtained. Blended with. The reaction mixture was allowed to stand at room temperature overnight to complete the reaction.

PCP-240--20,9 WCC-8006--40,1 MDI 6.9 7.6 Dicyandiamide 6 6 6 Triphenylphosphine 4 4 4
Initial processing conditions - 7X10' (cps) 70°C 57.9 57.9 2.880°C
12.5 12.5 0.89
0℃ 4.0' 4.0 0.
3 Applicable conditions '7X10' (cps) 80℃ 12,5 Solid 62690℃
4.0 Solid 66.2100℃
Solid 12.8 Another important property obtained by using diols having mono-terminated isocyanate in the present invention is the property of extending the open time by proper selection of the diol. Thus, by incorporating a crystalline backbone into the polymer, the working time of the reactive hot melt adhesive composition can be increased after application. Such crystallinity is imparted by the diol; in fact, prior to crystallization, the molten adhesive is deformable and provides reliable no-undling strength at room temperature. After crystallization, the adhesive regains its mechanical strength and becomes stiff, unyielding, and tough, increasing its handling strength.

The time between application of the molten adhesive and its crystallization is called the open time. The open time depends on the rate of crystallization of the adhesive. In short, the open-time is controlled by the structure of the polymer, its molecular weight, the content of crystalline segments and the amount of crystalline nuclei. In the next few examples, a crystalline diol, polycaprolactone diol, was used to illustrate this concept.

Example 17 100t Epon-1001F and 701 PCP-
230 (a polycaprolactone diol having an average molecular weight of 1,250 and commercially available from Union Carbide) was heated to 80°C and then 14.8F diphenylmethane-f) + p'- was added to the mixture. (MD I) was added and then blended with 62 dicyandiamide and 4t triphenylphosphine. After stirring to obtain a homogeneous solution, the reaction mixture was cooled and left at room temperature until the disappearance of incyanate in the I-temperature spectrum. A white, firm solid with a melting point of 80° C. was obtained.

The adhesive remained in a tacky transparent form for 2 minutes and 60 seconds after application to the oiled steel surface.

The adhesive was cured for 20 minutes at 170°C and then applied to the adherend at an overlap of 1.27 cm.
00 psi tensile shear bond strength and 24 inch-bond side impact resistance.
Example 18 1002 Epon-1001F, 10090PCP-2
An adhesive prepared using the same procedure as described in Example 17 from 30.62 dicyandiamide, 42 triphenylphosphine, and 15.6 brocade MDI had a 1.27 brocade steel sheath in the overlap area. About the body 1.700
It had a tensile shear bond strength of psi and a side impact resistance of 24 in-lbs.

Example 19 1001 Epon-1001F, 701 PCP-24
0 (polycaprolactone diol having a molecular weight of 2.00 and commercially available from Union Carbide), 6
An adhesive synthesized from 9 dicyandiamide, 4t triphenylphosphine, and 12.2r MDI using the same procedure as in Example 17 had an overlap of 1.2
It had a tensile shear bond strength of 3,300 psi on a 7 t:m steel adherend and a side impact resistance of 65 inch-bond. Open time was over 25 minutes. This adhesive also had a tensile strength of 6,740 psi and an elongation of 97 cm.Additional Relationships This invention relates to its original invention in the relationship defined in Section 61(1) of the Patent Law. This is an invention.

Procedural amendment (formality) September 8, 1980 Director-General of the Patent Office Kazuo Wakasugi 1, Indication of case Patent application 1973-773632, Title of invention Thermoplastic, epoxy suspension, urethane-containing compound 3, Amendment Relationship with the case of a person who does
Agent: 4F, 5, Doho Building, 1-18-6 Nishi-Shinbashi, Minato-ku, Tokyo Date of amendment: August 10, 1980 August 30, 1988 (Shipping field 6, Subject of amendment 7, Amendment) Contents (1) Submit a power of attorney.

(2) Submit a clearly typed application and specification.

8. List of attached documents (1) Power of attorney and translation (1 copy each) (2) Application form and specification (1 copy each) (or more)

Claims (1)

[Scope of Claims] (1) A thermoplastic resin that is a reaction product of an epoxy resin containing more than one hydroxyl group and a diol terminally substituted with polyisocyanate, and has dangling epoxy groups. A urethane-containing compound with (2) The compound according to claim (1), wherein the molecular weight of the diol before terminal substitution is in the range of 400 to 000. f31(al heat-reactive epoxy curing agent and (1)
1. A thermoplastic urethane-containing compound having pendant jepoxy groups that is the reaction product of an epoxy resin containing more than one hydroxyl group and a polyisocyanate-terminated diol. Curable composition. (4) The molecular weight of the diol before terminal substitution is 200
Claim No. 6 within the range of 20,000 to 20,000
) Composition of section. (5) The molecular weight of the diol is 400 to about 3,000
The composition according to claim (4). (6) The composition of claim (6) additionally containing up to 40% by weight of a liquid reactive plasticizer. (7) The composition according to claim (6), wherein the reactive plasticizer is an epoxy resin. (8) At least one of the two substrates is coated with the following compositions: (a) a heat-reactive epoxy curing agent; and (b) a 7fT epoxy resin containing more than one hydroxyl group; a thermoplastic, urethane-containing compound with pendant jepoxy groups, which is the reaction product of a diol terminally substituted with a polyisocyanate, and the coated substrates are brought into contact with each other. Then, the board in this contact state is
A method for fixing two substrates, characterized in that the fixation is induced by heating at a temperature in the range of ~300°C. (9) The method of claim (8), wherein the composition additionally contains up to 40% by weight of a liquid reactive plasticizer. The method of claim 9, wherein the QO liquid reactive plasticizer is an epoxy resin. (1) The method according to claim (8), wherein the heating step is performed by a 1M magnetic heating method. (12) The method according to claim 4, wherein the electromagnetic heating is performed by induction heating. U■ Quantity 1 The method according to claim α0, wherein the magnetic heating is performed by dielectric heating. (14) The curable composition according to claim (6) as a sealant. (151 The curable composition according to claim (3) as a coating material. The curable composition according to claim (6) as an αe adhesive. (17) There are many more than just one. An epoxy resin having hydroxyl groups of A process for the preparation of a thermoplastic urethane-containing compound with pendant epoxy groups, characterized by reacting at a temperature in the range of for a time sufficient to form the desired compound. An epoxy resin containing more than 100 hydroxyl groups in the presence of a urethane production catalyst of 0.1 to 5 parts by weight based on the weight of the reactants is sufficient to give the desired compound at a temperature in the range of 20 to 120°C. A method for producing a thermoplastic urethane-containing compound with suspended epoxy groups, characterized by reacting for a period of time. (L91 The molecular weight of the difunctional primary alcohol is 40
0 to 3,000.