JPS61188478A - Adhesive composition - Google Patents

Abstract

PURPOSE:To provide the titled composition having excellent handling characteristics and shelf stability and capable of providing stable, easy-to- measure and rapid application, which comprises a bisphenol epoxy resin which is solid at ordinary temperature, a compound containing an oxirane group and a carboxylic acid hydrazide. CONSTITUTION:A bisphenol epoxy resin (A) of the formula I (wherein A is H or an alkyl; X is a group of the formula II or III; Y is H, a halogen etc.) which has at least one oxirane group in a molecule and a molecular weight of 800-1,500 and is solid at ordinary temperature (25 deg.C) is mixed with a compound (B) having at least one oxirane group in a molecule which is liquid at ordinary temperature (e.g. 3,4-epoxycyclohexylmethyl 3,4- epoxycyclohexanecarboxylate) in a weight ratio of 10:1-5:5. in the mixture a carboxylic acid hydrazide (C) of the formula IV (wherein R is an alkyl, aralkyl or aromatic hydrocarbon group; and n is a natural number) having a melting point of 150-250 deg.C to obtain an adhesive composition having a melting point of 60-120 deg.C and a viscosity of 50-500pas is incorporated.

Description

Detailed Description of the Invention (a) Object of the Invention [Field of Industrial Application] The present invention relates to an epoxy resin-based thermosetting adhesive composition. This type of material can be used for adhesively bonding various base materials such as metal, glass, ceramics, wood, and heat-resistant plastics.

[Conventional technology]

Epoxy resin thermosetting adhesives are widely used in many fields due to their excellent properties. However, with conventional adhesive compositions of this type, it is difficult to apply them to a substrate in a hot molten state, and it is also difficult to process them into any desired shape, so the methods of application are limited. The scope of application is limited.

In other words, thermosetting adhesives have characteristics such as high adhesive strength, high adhesive heat resistance, and excellent adhesive durability, and the typical epoxy adhesive is widely used in various fields. Among them, one-component epoxy adhesives are often used as industrial adhesives in adhesive bonding lines because they have high reliability in adhesive performance and are easy to manage during use. Conventional adhesives of this type are ■Liquid
It has been tested in the form of ■ Paste, ■ Film, etc., and has the following drawbacks. □ In the case of the above Φ liquid and ■ paste adhesives, it is relatively easy to apply them to the base material at room temperature or under slight heating, but because the adhesive has fluidity and tackiness, , it is not easy to store and handle the substrate after coating, and there is a risk of problems such as staining, spilling, adhesion to other objects, or adhesion to workers during the adhesion process. . In addition to the above, when a solvent is used in (■), there is a sanitary problem due to volatilization of the solvent. In the case of the film adhesive described above, cutting, positioning, and fixing operations according to the shape are essential in the pasting process to the base material, but these operations are difficult to implement with equipment and require a lot of manual labor. The problem is that we have to rely on

Furthermore, since these adhesives are essentially obtained based on a mixture of liquid epoxy resin and a hardening agent or a solution mixture of an epoxy resin and a hardening agent, the reaction between the epoxy resin and the hardening agent does not occur at room temperature. This is likely to occur, and it is common sense to store it in a sealed container at a low temperature, and long-term heating coating is impossible because the adhesive will deactivate.

As described above, conventional adhesive compositions of this type could not be melt-coated onto substrates, and it was common knowledge among those skilled in the art that such adhesive compositions could not be melt-coated onto substrates. No attempt was made at all to develop a composition suitable for melt coating. In other words, epoxy resin functions as an adhesive by polymerizing and polymerizing by opening the oxirane ring, and the reaction in this case is as follows:
Since this is a ring-opening reaction of the oxirane ring, which is a three-membered ring with a high degree of strain energy, the activation energy for the polymerization reaction of epoxy resin is, for example, 10Kca11 in the reaction of a typical bisphenol A type epoxy resin and an acid anhydride. Around the mole,
The reaction between the same epoxy resin and amine produces 10 to 18 Kcal.
As low as 1 mole. The activation energy for the reaction between alkylphenol and formaldehyde, such as the polymerization of phenol resin, is 20 to 24 Kca 11 mol, the activation energy for the thermal polymerization initiation reaction of styrene is 32 Kca 11 mol, and the thermal decomposition of an azo compound is 2 mol.
7-40Kca 11 mol, thermal decomposition of organic peroxide is about 3
It can be seen that the activation energy for the polymerization reaction of the epoxy resin is low even when compared to 0Kca11 moles.

This low activation energy means that the temperature dependence of the reaction rate is low, and indicates that the reaction progresses at low temperatures even in systems that are completely cured at high temperatures.

Even from this theoretical background, epoxy-based
It was unconventional to apply liquid adhesives under heating, and conversely, even epoxy-based liquid adhesives that cure at temperatures above 150°C can be applied at temperatures below room temperature, usually below 4°C. It is common knowledge to store adhesive compositions in a molten state, and it has never been thought of to apply such adhesive compositions in a molten state, and no compositions capable of such molten coating have been developed. There wasn't.

In addition to the above-mentioned circumstances, conventional adhesive compositions of this type are relatively unstable when heated as described above, and therefore it is difficult to melt and process the composition into shapes. As described above, it is difficult to process conventional compositions of this type into various shapes, so it is difficult to supply them as adhesives in various shapes.
It cannot be used depending on the shape of the part to be bonded, and therefore its uses are limited.

[Problem that the invention seeks to solve]

As mentioned above, conventional adhesive compositions for rice seeds are difficult to apply to substrates in a hot molten state, so the methods of application are limited. Since it is difficult to apply the coating to a specific shape and to process it into any shape, there are restrictions on its uses and applications.

The present invention has been made to solve the problems of conventional adhesives, and the purpose of the present invention is to be stable, capable of melt coating on base materials, and capable of being applied in various shapes. Therefore, roll coating and other coating equipment similar to hot melt adhesives can be used, and quick coating with good metering is possible. Moreover, it is easy to handle and store. The object of the present invention is to provide an advantageous adhesive composition that has a wide range of uses.

(B) Structure of the invention [Means for solving the problems and their effects] The adhesive composition of the present invention comprises (A) a bisphenol-type epoxy resin that is solid at room temperature (25°C); (B) A compound that is liquid at room temperature and has at least one oxirane group in one molecule, and (C) a melting point of 150 to
It is characterized by containing a carboxylic acid hydrazide within a range of 250°C.

Due to the composition described above, this adhesive composition can exhibit an effect that meets the above-mentioned purpose.

That is, according to the present invention, it is possible to provide an adhesive composition that melts at, for example, 60 to 120° C. and is stable for a long time in a fluid state with a relatively low viscosity of 50 to 500 Pascal·sec. Such compositions can be applied to substrates in a low-temperature molten state by various methods, and can be used in the same application equipment as true melt adhesives. It is also possible to employ a method of roll coating onto the substrate between rolls.

Conventionally, hot-melt adhesives that utilize the heat-melting and cooling-solidifying properties of thermoplastic resins have features such as ease of installation, cleanliness after installation, hygiene, and short-time adhesion, and have been widely used in industrial adhesives. In recent years, it has become widely used as a material with excellent adhesion line suitability, but as mentioned above, it is difficult to melt-coat conventional epoxy resin-based adhesives, and such hot-melt adhesion methods cannot be adopted. However, the adhesive composition of the present invention can be applied to a substrate by a method similar to that used for hot melt adhesives, as described above.

Further, since the adhesive composition of the present invention becomes a solid state with no tackiness by cooling or standing to cool after coating, the substrate coated with the composition of the present invention is easy to store and handle.

After incorporating the coated base material into the part to be bonded, the adhesive composition of the present invention can be reheated for several minutes to several tens of minutes by heating at a temperature of 200°C or higher. Since curing and adhesion can be performed manually, automation of the adhesion process can be realized by configuring the line configuration.

Further, according to the present invention, it is possible to obtain a composition that maintains a stable molten state as described above, so that it can be melt-processed. Therefore, it can be used in various forms. For example, it can be supplied as an adhesive in the form of a film, sheet, rod, fiber, etc., and in this case, unlike conventional film-like epoxy resin adhesives, it can be obtained as an adhesive without tank properties (see above). Advantageous in terms of adhesive handling and other aspects. For example, the composition of the present invention processed into a film adhesive has good storage stability at room temperature, and conventional film epoxy adhesives contain an epoxy resin and a curing agent in a liquid or solution state. Since it is made into a solid film by impregnating cloth etc. and then drying and semi-curing (B stage), there are problems with storage stability and the need for refrigerated or frozen storage, and conventional products Some / Tl, 1: Kyotoru station 1. A28 Suner Jump Zuno II/), Suicide is made into a product through funagishi, etc., and even the pasted products cannot be stacked and stocked. Furthermore, the composition of the present invention solves the problem that the operations of cutting the film according to the shape of the adherend material, positioning and pasting the film are difficult to do mechanically and require much manual labor. As mentioned above, the film adhesive obtained from the above is easy to store and handle after application.
Moreover, since it can be processed into various shapes in a molten state, it is of course easy to match the film to the shape of the adherend, and the adhesion process can also be mechanized.

Furthermore, the composition of the present invention is not only in the form of a film, but can also be melted and processed into any shape, so it can be supplied as a solid adhesive in various shapes, and can therefore be applied to various shapes of joints. . It can also be crushed into granules or powder.

Next, each component of the adhesive composition according to the present invention will be explained.

(A) Bisphenol-type epoxy resin that is solid at room temperature (25°C).
The bisphenol type epoxy resin that is solid at 25° C. has one or more oxirane groups in one molecule and is represented by the following formula (1).

However, in formula-(1), as the bisphenol type epoxy resin of formula-(11),
Those with relatively low molecular weight are preferred. However, specifically, the molecular weight of the epoxy resin may be determined in consideration of various conditions such as ensuring that its softening point temperature is appropriate for construction and maintaining a high level of durability after adhesion. Generally, for this condition, the molecular weight is preferably 1,500 or less, and in order to be solid at room temperature, coarsely pulverizable, and less tanky, it is preferably 800 or more.

(B) is liquid at room temperature and contains at least 1 in 1 molecule
Compounds having oxirane groups at room temperature (25°C), which is another component of the adhesive composition of the present invention,
), which is liquid and has at least one oxirane group in one molecule (hereinafter referred to as an epoxy compound), is crosslinked and cured by reacting with a curing agent together with the bisphenol type epoxy resin (A). This epoxy compound, which is liquid at room temperature, plays the role of a melting point regulator that makes it easier to melt the bisphenol type epoxy resin (A), and also acts as a viscosity regulator when melted.

In order to react with a curing agent, the epoxy compound must have one or more oxirane groups in one molecule. Preferably, those having 1 to 3 oxirane groups in one molecule are suitable. By appropriately selecting such an epoxy compound, the heat resistance strength and durability of the adhesive after curing can be improved. Examples of preferred epoxidation and metal materials include low molecular weight bisphenol type epoxy resins, alicyclic epoxy compounds (e.g. 3,4-epoxycyclohexylmethyl-3,4-'epoxycyclohexanecarboxylate, 3,4-epoxy-6- methylcyclohexylmethyl-3,4-epoxy-6-methylcitalohexanecarpoxylate, bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate, etc.)
・Low molecular weight epoxy novolak resin (shown in formula-(2)) glycidylamine type epoxy compound (formula-(
3)), (Formula-(2), (R in 31: alkyl, aralkyl, aromatic hydrocarbon, etc.).

In the present invention, the blending ratio of the epoxy compound (B) that is liquid at room temperature and the bisphenol type epoxy resin (A) is preferably 10.
The ratio is 1:1 to 5:5 (weight ratio). With this blending ratio, it is possible to secure a melt application temperature of 60 to 120 degrees Celsius, a viscosity at that time (50 to 500 Pa・sec), and the adhesive layer after melt application has no tackiness at room temperature. It can be made to become solid. More preferably, (A) vs. (B
) is in a weight ratio of 9:1 to 7:3.

(C) Galponic acid hydrazide having a melting point within the range of 150 to 250°C The carboxylic acid hydrazide in the adhesive composition of the present invention serves as a curing agent. In the present invention, the melting point is 1
A carboxylic acid hydrazide within the range of 50 to 250°C (preferably 180 to 220°C) is used. The carboxylic acid hydrazide is preferably one that is substantially incompatible with the above-mentioned (A) and (B) for the composition of the present invention.

゛This carboxylic acid hydrazide has the structure of the following formula-(4).

n-4-C0NHNH*) n(4) (R: alkyl, aralkyl, aromatic hydrocarbon, etc.; n: natural number) The compound of formula-(4) is obtained by a reaction between an organic carboxylic acid and hydrazine. In the composition of the present invention, it is preferable to use a substance that is substantially incompatible with the above-mentioned epoxy resin (A) and epoxy compound (B) at room temperature as the hydrazide compound, and the compound of the above formula-(4) and the number of carbon atoms in the skeleton other than the carboxylic acid hydrazide group is 2 to 16 (
which may contain 2 to 3 heteroatoms),
Compounds that are incompatible with such epoxy resins and epoxy compounds at room temperature and have a melting point of 150° C. or higher are 120° C.
The present inventors have discovered that the epoxy resin and epoxy compound are substantially incompatible with each other even when heated up to 120°C, and hardly initiate a reaction as a curing agent for at least 3 hours at low temperatures up to 120°C. As a latent curing agent for epoxy resins and epoxy compounds, such carboxylic acid hydrazides can maintain a stable state for a long time even when the adhesive composition is heated and melted, and are useful for melt-applying adhesives. I found out that it is possible to obtain aptitude.

Note that known curing agents other than the carboxylic acid hydrazide of the present invention, such as guanidine derivative compounds represented by dicyandiamide, or high melting point derivative compounds such as imidazole and imidacillin, do not have the same performance as the carboxylic acid hydrazide of the present invention. First, it has disadvantages such as decomposition when heated, gelation in a short period of time when heated and melted, and poor hot water resistance after curing and adhesion, making it impossible to achieve the object of the present invention. .

The carboxylic acid hydrazide used in the present invention preferably has 2 to 3 acid hydrazide groups in one molecule. By using a material with 2 to 3 acid hydrazide groups, it has excellent short-time curing performance, and has excellent adhesion heat resistance after curing.
It has good adhesive durability and can be widely and effectively used as an adhesive layer to which stress is applied. In addition, when the number of acid hydrazide groups exceeds 3 in one molecule, adhesive peel strength tends to be poor. This is probably because the rigidity of the cured product is too high and the curing shrinkage is too large. It is estimated that there is no such thing.

As the carboxylic acid hydrazide used in the present invention, dibasic acid dihydrazide is a preferable compound, and specifically, for example, adipic acid dihydrazide, succinic acid dihydrazide,
Sepatic acid dihydrazide, isophthalic acid dihydrazide,
These include dodecanoic acid dihydrazide.

Note that hydrazides other than carboxylic acid hydrazide, such as phenolic hydrazide compounds (such as bisphenol A dihydrazide), have drawbacks such as slow curing speed and cannot achieve the sixth objective of the present invention.

The amount of carboxylic acid hydrazide in the adhesive composition of the present invention is preferably in the following proportions. That is, the amount of the carboxylic acid hydrazide compound in the composition depends on the amount of the epoxy resin (A) and the epoxy compound (B).
The number of acid hydrazide groups is 0.4 per oxirane group in
It is preferable to mix them in a proportion of 5 to 2.0. Within this range, good adhesive strength can be achieved, whereas if the number of acid hydrazide groups per oxirane is less than 0.45, the composition will not be sufficiently cured and will tend to become brittle. If the number exceeds <2.0, problems will arise in the water resistance and durability of the cured adhesive, whereas within this range, good water resistance and durability can be obtained. In addition, when the number of acid hydrazide groups exceeds 2.0, the water resistance
It is presumed that the tendency for durability problems to occur is due to the presence of a large amount of unreacted hydrazide groups in the cured product.

(D) Other compounds The adhesive composition of the present invention may contain various compounds other than the above-mentioned (A) epoxy resin, (B) epoxy compound, and (C) carboxylic acid hydrazide. for example,
A curing accelerator may be added to accelerate the curing rate and improve the degree of polymerization, and other components that are blended as ordinary adhesives, such as organic and inorganic fillers, viscosity modifiers, flame retardants, pigments, etc. It is also possible to incorporate dyes, stabilizers, etc.

As the curing accelerator, a latent curing accelerator is preferable.

This is because a latent type curing accelerator is suitable in order to be compatible with a construction method in which the adhesive composition of the present invention is applied to a base material in a hot molten state. Examples of latent curing accelerators include high melting point tertiary amine compounds, high melting point imidazole compounds, phosphine compounds, alkyl metal compounds, guanidine compounds, supercoordinated silicate compounds, and compounds of Group 5B elements of the periodic table. Examples include ionic adducts, sulfonium compounds, and iodonium compounds. Incidentally, the periodic table Group 5B element compounds include N, P, As, Sb,
It refers to a compound containing each element of Bi, and its ionic adducts include quaternary onium salt compounds of the above elements, and are preferred compounds for the present invention. Specific compounds include, for example, benzyltrimethylammonium iodide, penzyltrimethylammonylazyltriphenylphosphonium chloride, and triphenylphosphonium propionate.

Other compounds include organic fillers such as polyvinyl chloride, polyolefin, modified polyolefin, polyester, polyamide, polystyrene, and PMM.
A. Thermoplastic and/or thermosetting resin powders such as various rubbers, epoxy resins, phenol resins, urea resins, and melamine resins.

Inorganic fillers include calcium carbonate, barium carbonate,
Talc, kaolin, bentonite, white carbon,
Alumina, silica sand, carbon black, graphite,
Various powders such as shirasu balloon, glass, aluminium, copper, iron, zinc, ferrite, aluminum hydroxide, calcium hydroxide, iron hydroxide, iron oxide, etc., viscosity modifiers, flame retardants, pigments, dyes, Various stabilizers and the like are also suitable, and each component of the adhesive composition according to the present invention has been explained. Next, 1, a method of applying the adhesive in a molten state, which is a preferred embodiment when using the composition of the present invention, will be explained. As mentioned above, the adhesive composition of the present invention can be suitably embodied as a hot-melt adhesive composition, particularly as an adhesive composition for roll coating. A specific method for applying the method to a drug composition will be outlined below.

One of the characteristics of the adhesive composition of the present invention is that it is stable in a molten state. For example, 60-120
℃, with a viscosity of 50 Pa · seconds to 500 Pa · seconds,
Stable in molten state. Such a stable adhesive can be easily applied using a normal hot melt adhesive application device.

In this case, the coating temperature is generally 60 to 120°C (preferably 100°C or less), but the adhesive composition of the present invention is stable and easily applicable within this temperature range.

Soil, L±-su kidney 11 on the frost test snow of Tome J Reto Kyopei Aoi s■
There are nozzle type (gun type) devices, roll type (or foil type) devices, and slot orifice coaters. The nozzle type device has an adhesive application viscosity of 10 Pa.
When using a low viscosity adhesive of less than a second, the adhesive is supplied through a heated melting tank and a heated hose (using a gear, screw, pump, air pressure, etc.). In this case, the adhesive wetting liquid and adhesive circulation time are long. on the other hand,
A high viscosity adhesive of 500 Pa·sec or less can also be used, in which case a stick or cord adhesive is supplied and melted with a heating foil (short adhesive residence time).

Next, roll-type (foil-type) devices are capable of supplying high-viscosity adhesives, and when supplying adhesives using a heated melting tank, adhesives with a viscosity of 200 Pa·sec or less can be used ( In this case, if the adhesive residence time is long), and if the supply method is a melting method between heated rolls (the adhesive is supplied in the form of granules or powder), an adhesive with a viscosity of 500 Pa·sec or less can be used (in this case, the adhesive agent residence time (short). next,
Slot orifice coater can use high viscosity materials.
An adhesive having an applicable viscosity of 100 Pa·sec or less is supplied through a heated melting tank and a heating hole (in this case, during the adhesive wetting time).

In addition, curtain flow coater (applicable viscosity 10Pa
・seconds or less), extrusion coater (applicable viscosity 1000 Pa・seconds or less). The adhesive composition of the present invention can be applied using any of the above-mentioned hot melt coating devices depending on its viscosity (however, if the applied viscosity is 10 Pa·sec or less (if the applied viscosity is low, it may not be applicable). Since the adhesive composition of the present invention has a viscosity of 50 to 500 Pa·sec at 60 to 120°C when melted, an apparatus capable of applying an adhesive in this range can be used.The composition of the present invention As a coating device, a nozzle-type (gun-type) device is preferable from the viewpoints of short wetting time and no retention zone of molten adhesive in the device, and stick-type or A system that uses a method of supplying cord-shaped adhesive and melting it with a heating foil, and a system that uses a method of supplying adhesive in the form of particles or powder and melting it between heated rolls using a roll-type (foil-type) device. In short, considering the long-term stability of use, the shortness of the melt supply route, and the fact that the adhesive composition of the present invention contains an insoluble curing agent component during melt application, two Most preferred is a hot melt roll coating method in which the coating is applied to the substrate between the above rolls.

The composition of the present invention can be hot-melted, that is, melt-applied as described above, and after the composition of the present invention is melt-applied to a substrate, the adhesive layer becomes a solid state without tackiness by cooling or leaving it to cool. Since the coated base material can be returned to its original state, storage and handling of the coated base material can be simplified.

The heating temperature during coating depends on the applicable viscosity range of the equipment and the composition.
As mentioned above, the coating temperature is preferably 60-120°C (preferably 100°C or less).

On the other hand, the curing temperature is preferably 150℃ or higher, but it can be set according to the melting point curing characteristics of the curing agent used. Cured adhesion can be performed in a time of . The heating method used in the bonding process may be a conventional hot air oven, heat press, infrared oven, high frequency induction heating, high frequency dielectric heating, microwave heating, ultrasonic method, etc.

No epoxy adhesive has been found that can be melt coated.
No attempt was made to develop it. Rather, as mentioned above, the temperature dependence of the curing rate of the reaction between an epoxy resin and a curing agent is inherently low compared to other polymerization and curing reactions.
For example, one-component compositions whose main components are epoxy resin and curing agent have poor storage performance even if the standard curing conditions are 120°C to 200°C, and they must be stored at a low temperature of usually a few degrees Celsius or less. Conventionally, it has been unthinkable to keep such a composition stable for a long time under heating and melt-apply it, and no attempt has been made to do so. The fact that the adhesive composition of the present invention enables melt coating of such an epoxy adhesive is of great significance, providing a new adhesive application technology and opening up a new field. It's something you get.

The characteristics of the adhesive composition of the present invention described above are summarized as follows. In other words, like thermoplastic resins, it is possible to maintain a stable molten state without curing, and it is possible to perform stable coating and processing in the molten state. It has good storage stability even after being heated and melted, and is a solid solvent-free thermosetting epoxy resin adhesive with no tackiness (1) It is used as a thermosetting adhesive that is melt-coated to a base material. (n) The composition is characterized in that it can be processed and supplied as a thermosetting adhesive in the form of seeds.

The advantages of (I) above are as follows: (, 1-a) Since a coating device similar to that for hot melt adhesives can be used, rapid coating with good metering is possible (, I-b) The adhesive film after coating is at room temperature (25℃)
Since it is a solid with no tank properties, it is easy to handle and stock (1-c) As it is a thermosetting adhesive, it has superior adhesive strength, heat resistance, and durability compared to other adhesives. Therefore, it can be used for strong adhesion of ceramics, metals, FRP, and various structural composite materials, and can bring great flexibility and advantages to industrial adhesive construction lines.

Furthermore, the above (II) can be used as follows: a) By pulverizing, it can be supplied as a granular or powdered thermosetting adhesive.

b) By melt processing, it can be supplied as a film or sheet thermosetting adhesive that does not contain a carrier or contains a carrier. This adhesive is easier to handle after application because it is less sticky than conventional thermosetting adhesives manufactured from solutions or liquids through B-stage (semi-curing) processing, and it does not require release paper. It is advantageous in that it is economical to produce, and it can be stored well at room temperature, so it is advantageous in that it can eliminate the need for refrigerated or frozen storage equipment and labor.

C) It is inferior to melt processing and can be supplied as a solid thermosetting adhesive in all kinds of complicated shapes such as rods, strings, tablets, cylinders, ribbons, and boxes. This allows for a variety of joint shapes! can be done.
.

(, 1l-d) By performing melt spinning or the like, it can be supplied as a thermosetting adhesive in the form of fibers or webs.

(II-e) It can be melt-mixed into a number of heat-processable materials such as other thermoplastic resins, and can be used to impart various performance-improving properties.

This makes it possible to apply it to a wide range of uses, including fields where it has not been used conventionally, such as industrial adhesives and modifiers.

[Embodiments of the invention]

The details of the embodiments of the present invention will be explained below.

It should be noted that, as a matter of course, the present invention is limited only to the following examples! There isn't.

Comparative examples are also shown. .

Example 1 Pisufue 5), which is solid at room temperature, -ru type epoxy resin (A
), (a) bisphenol A type epoxy resin Epicoat 1002 (trade name, oil-based shell epoxy ■ product, average molecular weight of 1060, epoxy equivalent weight 650) 10
0 parts by weight, as an epoxy compound (B) that is liquid at room temperature, (b) bisphenol A type epoxy resin Epicor) 834- (trade name. Yuka shell epoxy ■ product).

Epoxy equivalent average 250) 20 parts by weight, as curing agent (C) (c) sebacic acid dihydrazide, which has a melting point of 187°C and is incompatible with the above (a) and (b) (acid hydrazide/oxirane equivalent ratio = 1.25) 28.3 parts by weight, 8 parts by weight of polycaprolactone resin Plaxel 308 (trade name, Daicel Chemical Industry ■ product, average molecular weight 850), which is a flexibility imparting agent and is liquid at room temperature;
5.0 parts by weight of talc powder was added.

The mixture having the above composition ratio was processed using a two-wheel extruder equipped with a liquid material press-in device (shaft rotation in the same direction, cylinder diameter 30 mm, L/D=
25) and further pulverized to obtain the desired adhesive.

The melting point of the obtained adhesive was 60-70°C, its initial viscosity at 80°C was 200 Pa·s, and the viscosity was 50°C.
The time required for the temperature to exceed 0 Pa·sec is 10 hours or more (hereinafter, this time is referred to as pot life).

Even after being stored at 40°C for one month, this adhesive melts uniformly with a viscosity of 230 Pa·sec at 80°C, and has good storage properties.

The adhesive of this example could be used by applying it with a roll as follows. That is, this adhesive is supplied as a set of a rubber roll and an iron doctor roll to a tin redder coating machine (manufactured by Tanouchi Tekko), which is capable of hot coating and consists of two sets of upper and lower heating rolls. After melting at a roll temperature of
00 at a speed of 10 m/min, it was possible to apply the adhesive uniformly on both sides of the plywood in an amount of about 50 g/n. It cooled within a few minutes, had no tackiness, could be stocked and laminated, and was easy to handle.

In addition, the tensile shear strength of a test piece was measured using a commercially available bonded steel plate (0.6 mm thickness) as an adherend using the adhesive at 180°C for IO minutes, and the tensile shear strength was measured.
Good performance was shown, with 142 kgf/- or more at ℃ (lit material deformation) and 139 ksrf/ca1 or more at 82 ℃ (steel material deformation).

Example 2 In this example, (a′) was used as the epoxy resin (A).
) average molecular weight 900, bisphenol A type epoxy resin Epicoat 1001 (trade name, Yuka shell epoxy special product. Epoxy equivalent weight 475) and average molecular weight 1600
, bisphenol A type epoxy resin Epicoat 1004
(Product name. Yuka shell epoxy special product. Epoxy equivalent average 925) 67733 weight ratio mixture 100 parts by weight,
As epoxy compound (B) (b') Epicor) 828
(Product name: Yuka Shell Epoxy ■Product.

Epoxy equivalent average 188) 20 parts by weight, as curing agent (C) (C') isophthalic acid dihydrazide (acid hydrazide/oxirane equivalent ratio -1.0), which has a melting point of 219°C and is incompatible with these epoxy resins and epoxy compounds. An adhesive was obtained in the same manner as in Example 1 using 0.1 part by weight and 0.5 part by weight of dibutyltin dilaurate as a curing accelerator. The melting point of this product is 60-70°C, and 80°C.
Initial viscosity at °C is 180 Pa・sec, pot life is 10
It was more than an hour. In the same manner as in Example-1, a phenol-impregnated paper honeycomb core with a cell size of 374 inches, paper, basis weight of 160 g/rrl, and a height of 20 fins was coated using a heated spray gun. The adhesive could be applied satisfactorily in an amount of 80 to 120 g/rrr (one side). The coated honeycomb core could be stocked and laminated without tackiness after being left to cool. 50 as a face material
Ryukaku, Q, using bonded steel material with a thickness of 5 mm, combined with the double-sided coated honeycomb core obtained above, and heated to 180 mm.
℃ for 10 minutes and then measured at 23℃. 10. A good value of 9ksrf/cnl was obtained.

Example 3 In this example, the adhesive obtained in Example-1 was used and applied to another coating method.

That is, in this example, the adhesive of Example-1 was extruded at a temperature of 90±5°C using a Minimatic 777 Super Gun (manufactured by Chiyoda Plant ■), which is a hot melt gun with a melting chamber, and preheated to 50°C. When applied in the form of a bead onto a steel plate, the coating was successful. The coated product did not tack after being left to cool, and stock lamination was possible.

Comparative Example Unlike the present invention, trimellitic anhydride was used as the curing agent instead of carboxylic acid hydrazide.

That is, in this comparative example, 100 parts by weight of Epicote 1002 (described above) was used as the epoxy resin, and 30 parts by weight of Epicote 828 (described above) as the epoxy compound. (acid/oxirane equivalent ratio = 1.8), and using 0.5 parts by weight of benzyltrimethylphosphonium iodide as a curing accelerator, an adhesive was obtained in the same manner as in Example 1. The melting point of this product was 65 to 70°C, the initial viscosity at 80°C was 290 Pa·sec, and the pot life was 1 hour. When it was fed to the same heated spray device as in Example 1, gelation progressed within 2 hours at 80 to 90°C, making it impossible to coat.

(c) Effects of the invention As mentioned above, the adhesive composition of the present invention is stable, can be applied to a substrate in a molten state, and can be processed into various shapes and supplied. . Therefore, it can be applied as a hot melt adhesive such as a roll coating adhesive, has good handling and storage properties, and has a wide range of uses.

Patent applicant: Toagosei Kagaku Kogyo Co., Ltd. Agent, Patent attorney Toru Takakumi (1) In the specification (the same applies hereinafter), page 4, line 8: Displayed in 1985 Shinsaku No. 28222 3゜ Ugliness with Amended Person Hanyu Patent Applicant Address 1 Nishishinbashi-chome 14-chome, Minato-ku, Tokyo Name (Name) (303) Toagosei Kagaku Kogyo Co., Ltd. 4. Agent (8) On page 13, line 1, amend "necessary" to "necessary" to "adhesive."

(2) Correct "Energy" to "Energy" in line 10 of page 4, line 2 of page 5, and line 3 of page 5.

(3) In the last line of page 8, change “200′℃ or higher” to “200°C or higher.”
0℃ or below.''

(4) "Epoxy resin adhesive" on page 9, line 9 is corrected to "epoxy adhesive."

(5) Written in parentheses on page 11, lines 5-6 from the bottom.

(6) In the fourth line from the bottom of page 11, "halogen element" written in parentheses is corrected to "halogen atom."

(7) Correct “applicable” in the 2nd line from the bottom of No. 12 to “applicable”.

Yes,” he corrected.

(9) "Water resistance and durability" on page 19, line 8 is corrected to "water resistance, durability."

(10) Correct “filler” in line 2 of page 20 to “filler.”

(11) “Alkyl metal compound” on page 20, line 11
is corrected to "alkyl metal compound."

(12) Page 20, line 13 and line 1, line 7, 9 “ionic adduct” are corrected to “ionic adduct” respectively.

(13) 22nd line 5th line from the bottom - 2nd line from the bottom, "In this case... we can handle it." is corrected as follows.

"In other words, the adhesive composition of the present invention is 60 to 120°C (
Melt coating is possible at a temperature of preferably lσ0° C. or less, and a typical true melt adhesive coating device can be used at such a temperature. ” (14) “It’s a lot of time” on page 23, line 8 is corrected to “It’s a long time.”

(15) "(Adhesive residence time is short)" on page 23, line 11 is corrected to "(adhesive wetting time is short in this case)."

(16) On page 23, lines 15-16, "(In this case, the adhesive dwell time is long)" is corrected to "(In this case, the adhesive wetting time is long)."

(17) On page 23, lines 18-19, "(In this case, the adhesive residence time is short)" is corrected to "(The adhesive wetting time is short in this case)."

(18) In lines 2 and 3 of page 24, "(in this case, the adhesive wetting time is in the middle)" is corrected to "(in this case, the adhesive wetting time is medium)".

(19) Delete "(However,...it may not be possible)" in lines 9 to 10 on page 24.

(20) "Insoluble" on page 25, line 4 is corrected to "insoluble."

(21) Correct the ``degree of the object'' in the 6th line from the bottom of page 25 to ``the viscosity of the object.''

(22) Correct "melting point" in the second row from the bottom of No. 25 to "melting point."

(23) "Characteristics" in line 4 of page 27 is corrected to "features."

(24) Change “a)” on page 28, line 12 to r (II-
a) Correct as J.

(25) Change “b)” on page 28, line 14 to r (ff-
b) Correct with J.

(26) Change “C” in line 3 of page 29 to r(II-c)
Correct with J.

(27) "Various types of performance" on page 29, line 12 is corrected to "Various types of performance."

(28) Page 30, line 13, rl, 25J, rl, 0
Correct to 5J.

(29) Page 33, line 4 rl, o J to rO, 53
Correct to J.

1. Indication of the case 1985 Patent Application No. 28222 2. Title of the invention Adhesive composition 3. Relationship with the person making the amendment Patent applicant's address Tokyo Nishishinbashi-chome 14-1, Miyakominato-ku Name (
303) Toagosei Chemical Industry Co., Ltd. 4, Agent 6, Subject of amendment: '7-M-\ in specification g', h,,,'zl.

Claims (1)

[Claims] 1. (A) a bisphenol-type epoxy resin that is solid at room temperature (25°C); (B) a compound that is liquid at room temperature and has at least one oxirane group in one molecule; (C) a carboxylic acid hydrazide having a melting point in the range of 150 to 250°C;