JPH07173399A - Long-term storage in one pack of multicomponent reactive resin and its curing method - Google Patents

Abstract

PURPOSE:To improve the operability by storing the individuals of multiple high-reactive components for a curing resin in one vessel, so-cold in one pack, to save the labor work for weighing and mixing a plurality of the components, and also to realize the rapid curing by heating for a shortened tide whereby the labor and time can be saved without remains of unused resins. CONSTITUTION:For example, the high reactive components for a curing resin such as a diisocyanate and a diamine cannot be stored in one can and they are separately stored in different vessels and mixed immediately before use. Such components are substantially made in the form of fine phases, respectively and the fine phases are mutually dispersed and mixed to enable them to be storable in a single vessel. When used, the dispersion is irradiated with high-frequency electromagnetic waves or laser beams whereby a needed amount of the fine-phase mix is dissolved with heat to effect homogenization, diffusion and curing in a short time.

Description

Detailed Description of the Invention

[0001]

The present invention relates to a multi-component reaction-curable composition which is substantially separated and dispersed and mixed and stored as one component. When used, it is treated with a high frequency electromagnetic field or a laser beam to diffuse-mix and cure. The present invention relates to a new storage / curing method. Storage in a single container makes it easy to handle, and there are a wide variety of compounding combinations.
Maintains the advantages of multi-component resins, such as softness, high strength, high elasticity, toughness, chemical resistance, and a wide range of other physical properties.
The present invention relates to a one-pack storage method of a widely applicable reaction-curable resin such as paints, adhesives, various molded products, and the curing method thereof.

[0002]

2. Description of the Related Art So-called multi-component reactive resins comprising a main agent such as epoxy resin, urethane resin, unsaturated polyester resin, etc. and a curing agent are widely used in the fields of adhesives, paints and various molded articles. These so-called reaction-curable resins are prepared by storing multiple components in separate containers, mixing and mixing the components at the time of use, and curing at room temperature or under heating. Usually, both liquid components are weighed and put in one container, well mixed by using a manual or electric stirrer to dissolve uniformly, and applied during so-called pot life before the compounded liquid is cured.

As a special mixing method, a method of spraying and mixing two liquids with a two-headed gun, or, for example, a static method, in which liquid components are mixed and passed through a pipe containing a spiral baffle plate, is mixed. There is a mixing method with a mixer. However, these are used separately after being stored separately in different containers and mixed, and are called two-component type and multi-component type, and both are applied in liquid form.

Further, a method is also known in which multi-components which do not react at room temperature are mixed in advance and heated and melted during use to react and cure. Further, there is also known a so-called B stage which is mixed and stored at a reaction quiescent state or below the reaction start temperature of components such as a catalyst that work at a certain temperature or higher, and heated at the time of molding. An unsaturated polyester resin called a prepreg mat is typical of this type. All of these are those which suppress the reaction at low temperature to normal temperature and have a preservative property, and are restarted or started by heating with a heated mold or the like.
In this case, the reaction components are uniformly dissolved, and the reaction starts immediately when heated to the activation temperature. That is, even though they are reactive multi-component resins, they are stored at a temperature at which they do not essentially react, that is, they are inactive resins at the storage temperature.

By the way, a part of the components may be solid-dispersed, which gives an impression similar to that of the present invention. However, in the prior art, when the components are cured, a fixed amount is put together in a mold, for example. Alternatively, a required amount is heated by a hot press and heated for a certain period of time to be cured, which is a batch heating method in a methodological term.

[0006]

[Problems to be Solved by the Invention] The above-mentioned multi-component liquid reaction curable resin starts to react immediately after being mixed, and the reaction proceeds even in an appropriate application. It hardens and becomes useless.
In addition, if a catalyst or the like is added to accelerate the curing, the pot life will be shortened more rapidly than the shortening of the opening time during curing, and the remainder will be wasted more and more. As described above, in multi-component reaction curable resins, the separated and stored components are weighed and compounded immediately before use, but there are many accidents such as a mistake in the compounding ratio and forgetting of the compound, and it is necessary to meter and mix each time. There is a strong demand for a single container that does not have one component.

To meet this demand, a one-component urethane resin has been developed and used, but this is a prepolymer having a terminal isocyanate group, which is applied to painting, adhesion, etc. in the air or in an applied product. Although it is polymerized and cured by the water content of the one-component type, it is called a one-part moisture curing type, but the water content acts as a curing agent, and it is effectively a two-part type and is stored completely isolated from the moisture before application. Since the curing is left to the reaction with moisture, the curing rate is slow, and it is difficult to accelerate this, and it is necessary to take a so-called aging period. Also, from the viewpoint of molecular design, there are many restrictions due to the viscosity of the prepolymer, the physical properties of the cured product, and the like, and the application is naturally limited.

Also, since the reaction does not occur at room temperature or the reaction is very slow, the type in which this is mixed in advance and heat-cured if necessary is described above, but this is the whole amount required for molding in the mold. It is then set in a hot press or hot press and put under heating for a certain period of time to promote the reaction and molding. The curing time is relatively long due to its inherently low reactivity. For example, when it is used as an adhesive, it must be fixed with a fixture for a considerable period of time until it is cured and fixed so that it will not flow and slip or fall off. Fixing and holding at high temperature is not preferable in terms of work, it takes time to move to the next step, and workability is greatly impaired, such as the time and effort to attach and detach the fixtures. In addition, those that can be premixed and mixed at room temperature with such reactive components have low reactivity.
The compounding ratio is also limited, and there is a wide variety of compounding types and compounding ratios, which are characteristics of multi-component reaction type resins, and the advantage that a wide range can be obtained is lost.

[0009] A combination of highly reactive compounds, such as those having an isocyanate component and a hydroxyl component, is selected in view of release from these drawbacks, and if the mixture is stored in advance, the reaction proceeds even during storage, and the viscosity changes or solidifies. Or or,
For example, in the case of a combination of an isocyanate component and a component containing an aliphatic primary amino group, the reaction is almost instantaneous and it is difficult to evenly mix the two liquids. In such a case, it is necessary to use a compound having a low reactivity such as an aromatic amine having chlorine attached to the position adjacent to the amino group, resulting in a very limited combination. Even if one is a solid component and one is a liquid and a different phase combination, one is permeated and diffused into the solid, and in the case of a highly active combination, the reaction proceeds during storage. That is, it cannot be uniformly dissolved or dispersed in advance for storage. In any case, in the conventional curing by the ordinary heating method, the combination having high reactivity cannot be mixed and stored as one component, and if the storage property is secured, the curing becomes slow.

[0010]

The invention of the present application solves the above-mentioned problems and has advantages of multi-component type, that is, abundant combinations of blends, stable storage in separate containers, etc. Even if you choose a combination with a fast curing rate, you can store it as a one-component type in a single container, the resin handling is simple and easy, and the work efficiency is improved by the rapid curing. It provides a method that can be achieved. That is, the invention of the present application is a method in which a curable resin composition in which each reaction component is substantially isolated and which is finely dispersed and mixed is subjected to a high-speed electromagnetic field, a laser, or the like having a high transparency or a high-speed heating method capable of easily adding energy concentration. It is a one-pack storage and curing method of a new resin that is cured by heating, diffusion and reaction. .

The ultrasonic heating method is also effective in point and line applications, and when one of the reaction components is microencapsulated, it is effective for destruction and integration, and high-speed heating. Therefore, the present invention can be applied to the present invention. In this case, the resin composition may be preliminarily molded into a film sheet to improve workability.

In the present invention, the necessary amount is heated and melted in a short time, and the heating can be stopped instantaneously.
Waste can be reduced. In other words, the energy addition is directly applied to the resin, and unlike the conventional method that uses heat from the outside, such as hot air, electric heat, or a mold, it is possible to turn the energy addition on and off with a single switch. it can. The high-frequency electromagnetic field, laser, etc. are different from the method by conduction in which heat is gradually transferred from the surface to the inside, such as the heating method of hot air, electric heat, infrared lamp, etc., which is generally used in the past. It is a method of rapidly heating without distinction between the inside and the outside, and the temperature is raised uniformly and in a short time. A substance placed under a high-frequency electromagnetic field undergoes intense molecular vibration due to the high-frequency electromagnetic field due to the polarity of the substance, and as a result, the temperature rises from the inside of the substance. That is, the surface layer and the inside are simultaneously heated at the same time. So-called high frequency induction heating is a familiar example of a household microwave oven.

Ultrasonic heating is also a heating method by internal friction of a substance, and is known in the field of plastic processing as a dotted-line heating method such as film welding sealing and metal tack welding. The laser is a new energy concentration adding method that has already been applied to metal cutting and the like, and energy concentration to a minute area is unique. As the laser, a ruby laser, neodymium YAG laser, argon laser, carbon dioxide laser, excimer laser, Hooker hydrogen laser, or the like can be used. The output of these lasers may be either a pulsed beam or a continuous beam and may be selected according to the application conditions. In terms of output, this depends on the amount and type of the composition to be melted, the beam convergence density, or the conditions of application and construction such as point irradiation, line irradiation, etc., but generally, several watts to 100 kilowatts and the purpose and work. Set according to the speed. A carbon dioxide laser with an output of several hundreds of Watts is one of the suitable ones. The irradiation time also depends largely on the output, the application situation, the intensity wavelength distribution, etc., but is generally 1/1000.
0 to several tens of seconds. Is.

The present invention utilizes these rapid energy addition methods for a short time to instantaneously melt a multi-component reaction composition which is substantially phase-separated and finely mixed and mixed, and is blended by integration and diffusion mixing. , Solving and improving the application constraints and drawbacks of conventional multi-component resins.
Substantially phase separation, as a multi-component mixed finely dispersed, each component is mixed in a solid powder, at least one component is a liquid, other powdery components are dispersed in the liquid, A solid powder-like component with another solid powder-like component adhered and adhered by the third component to form a new powder, that is, a sugar-like powder, one component forming a layer around the other component There may be many forms such as powder particles with overlapping structure, one component powder surrounded by many other components, etc., but it is substantially separated and mixed with minute dispersion If it is a state, the form does not matter. For example, the shape may be a multi-layered needle shape or a spider web shape.

If the fine dispersion is expressed in terms of dimensions, the component resin,
There are many factors such as the melt viscosity and molecular weight of a compound, the violence and graduality of the molecular motion of its component resin, and these are not strictly determined, but the particle size of one component or the distance from the other component is It is 1000 microns or less, preferably 100 microns or less. More preferably 50
It is less than micron.

Next, regarding the method of use and the method of curing, as described above, a high-frequency electromagnetic field is added while the composition in which minute dispersions are mixed is being sent to an object to be processed by an air flow such as a spray while flowing. . In the high frequency dielectric method, the resin is heated by passing it between two electrodes facing each other, and the temperature is instantly raised so that the resin is melted when it reaches an object. When a laser is used, various application methods can be adopted by controlling the focus to one point or scanning the focus, for example, by melting the string-shaped solder in sequence from the thread-like composition that is continuously supplied in the form of a thread. Moreover, the dissolution reaction can be performed at a high speed.

Resins usable in the present invention include epoxy resin, urethane resin, urea resin, melamine resin,
Guanamine resin, dup resin, vinyl ester resin, phenol resin, furan resin, unsaturated polyester resin,
Any reaction-curable type can be applied, such as silicone resin, polyimide resin, xylene / formaldehyde resin, rosin-modified maleic acid resin, etc., as long as they have multiple reactive groups that react with each other. HCO -, - CO-O- CO -, - Si (R) 2 Cl,
-Si- (OR) ₃ , -CO-, -CO-NH-CO
-, Epoxy ring, imine ring, lactam ring, lactone ring,
Between the same or different groups, such as oxazoline ring,
Polymerization, condensation, addition, ring-opening polyaddition, ring-opening condensation, etc.
Any combination that cures can be applied.
Although they contain reactive groups, the combination of them has the same groups but different skeletons, different active groups that react with each other, H ₂ O, O ₂ , various catalysts, etc. react to react. , There are many combinations, and any combination can be used as long as it has reactivity within a wide range from low temperature to high temperature and within a range where decomposition does not occur in the reactive group itself or other parts in the molecule. Good. The particularly advantageous combination is a highly reactive combination in which, when the reaction components are mixed as a uniform single phase, gelation occurs in several hours or less, preferably 30 minutes or less, more preferably 5 minutes or less. Is the case. Isocyanate groups, acid chloride groups and amines have high activity and are examples to which the present method can be advantageously applied.

For example, a solid raw material of a resin having a plurality of active groups that react with each other is made into a fine powder, and both reaction components are stored in the presence or absence of the third non-reactive component. ·use. Here, the solid state also includes a powdery body in which a reaction component originally in a liquid state is formed in a solid state by impregnation with a third component in a solid state, encapsulation and the like. For example, a powder obtained by uniformly mixing and dissolving a curing-accelerating catalyst in a solid component and then solidifying and pulverizing it, or one in which one component is impregnated in porous silica is used. A third component C 3, which is involved in the direct reaction, may be included. When A and C are used as one component and B is used as another reaction partner, or a composition in which three components A, B, C, and three components react with each other may be a composition in which three types of components are separated and mixed.

FIG. 1 is a schematic representation of the state of polymerization and curing. A and B represent a reactive group, and both react to bond two molecules to form a polymer. The two components are substantially separated and mixed in a finely dispersed manner, and a necessary amount is transported to an application site or installed at the time of use to add energy as described above.

[0020]

In the method of the present invention, since the reaction composition which is substantially separated and mixed in a dispersed state is stored, for example, as a mixture of powders of the respective components, no reaction occurs during storage, Even when stored for a long period of time, there is no increase in viscosity, no change in curing, etc., and the state ready for use can be maintained at any time. When using,
For example, a required amount of the mixed powder may be sent to a required place by means such as gravity flow or pneumatic transportation. On the way to the heating, immediately before the application of the object by the above-mentioned heating method,
Alternatively, after reaching the object to be applied, energy is added to melt, integrate, and react. Since heating and melting can be performed continuously and instantly, no excess is produced and only a necessary amount can be melted, thus eliminating waste.

Since the composition is a combination of multiple components, it does not leave it to the other party as in the case of leaving one component to natural moisture as in the moisture-curing type, and it is a combination of the types of components and reactivity. The degree of freedom of is large. Therefore, the selection range of the physical properties of the cured product is very wide, and the application is unlikely to be restricted.
That is, the workability can be greatly improved while maintaining the advantages of the multi-liquid curing type.

Since melting, diffusion and mixing are carried out in a minute area in a short time, a highly reactive combination, which was difficult even in the conventional method, can be easily incorporated, and the curing time can be greatly shortened. In addition, for example, dissolution / reaction at a separated place like a composition supplied to the other side of glass or a resin plate,
Curing can also be done without damaging these isolation materials.

EXAMPLES Examples of the present invention will be given below.

[0023]

Example 1 A urethane resin powder containing an amino group was prepared as follows. 20 g of polyurethane prepolymer (Takenate L-1031 manufactured by Takeda Pharmaceutical Co., Ltd., solid content 100%, isocyanate group content 2.15%)
12 g of polyisocyanate solution (Duranate E405-80T manufactured by Asahi Kasei Kogyo Co., Ltd., solid content 80%, isocyanate content 7.0%) and 15 cc of toluene were mixed, and 0.4 g of a surfactant (NOF Corporation) Manufactured by Pronone 204), 300 cc of deionized water
The mixture was injected and dispersed at 50 ° C under high speed stirring. Dissolve 2.25 g of hexamethylenediamine in 10 cc of water and gradually add it under high-speed stirring, and continue stirring for about 2 hours, and then the prepolymer particles were separated by filtration and dried. The powder obtained contains terminal amino groups. On the other hand, Takenate D-1
03 (manufactured by Takeda Pharmaceutical Co., Ltd.) was washed and precipitated with N-hexane, filtered and dried to prepare a powder having an isocyanate group,
A mixture of this and powdered silica gel at a ratio of 1: 1 was prepared. The above powders were mixed at a ratio of 2: 1 to obtain the composition A of the present invention. A was stored in a glass bottle with a rubber packing, and its storability was confirmed. Even after storage for 3 months, there was no aggregation or solidification of the powder, and a dry powder state could be confirmed.

The above composition A was sandwiched between two FRP plates (glass fiber reinforced polyester resin plate, thickness 2 mm), and a copper plate electrode was placed on the outside of the two plates for high frequency dielectric heating. Maximum output of high frequency oscillator 3kW, oscillation frequency 40MHz, application time 50 seconds, anode current 0.9Am
The melting of the composition A was confirmed by p. The melting can be easily confirmed by a slight shrinkage of the gap between the electrodes and the flow of the composition A due to the melting. The adhesive strength between the obtained FRP plates was measured and a result of 20 Kg / cm ² was obtained. Further, when the test piece was put in a dryer at 70 ° C. for 10 minutes and sheared and pulled immediately after being taken out, the strength was 15 Kg / cm ^2, which was a low decrease, and the effect of reaction curing could be confirmed.

[0025]

Example 2 Powdery 2,2 ′ (1,3-phenylene)
10 g of bis (2-oxazoline) and methylenebisP,
A powder of 8 g of P'dianiline was mixed well. Powder 2 obtained by grinding 0.5 g of octyl bromide and silica gel into this mixture.
g was added and mixed and stored. After 2 months, the state of the mixed powder was observed, but there was no change such as aggregation and solidification, and the fluidity of the powder was almost the same as that at the time of adjustment. One week after the preparation of the mixed powder, a part thereof was taken out and the curability was examined. 0.5 g of mixed powder
A high-frequency oscillator sandwiched between polyethylene sheets with a thickness of mm, placed in a high-frequency electromagnetic field and melted and cured had a maximum output of 10 kW and a frequency of 6.7 MHz, and an anode current of 2.0 Amp. In 3
It was applied for 0 seconds. The melt-cured sample was in close contact with polyethylene.

[0026]

Example 3 The same powder as the sample cured in Examples 1 and 2 was made to flow through a 2 mm hole between two electrodes facing each other in parallel at an interval of 10 mm. Maximum output of 5 kW for electrodes
A high frequency electromagnetic field was applied by connecting an oscillation frequency of 13.56 MHz. Maximum current 0.5 Amp. Met. The powder that had flowed down could be melted and fluidized to form a cured coating layer. The cured product 1 (Example 1) had a Shore A hardness of 50, and the cured product 2 (Example 2) had a Rockwell hardness M100.

[0027]

[Embodiment 4] Carbon dioxide laser light (5 W, 0.01 sec) was applied while flowing the same sample as in Embodiments 1 and 2 through a 2 mm hole.
c. The luminous flux diameter was 5 mm). It radiated downward from the top at a tilt angle of 10 degrees with respect to the falling line. The down-flowing line of the powder and the light beam meet at the down-flow reaching point with an inclination of 10 degrees. The falling powder could be melted and integrated to form a film. The surrounding non-irradiated part other than the irradiated part could be easily separated from the cured part without any change.

[0028]

Example 5 The NH ₂ -terminated prepolymer powder obtained in Example 1 was mixed with phthalic acid- (2,3-epoxypropane) diester powder (Denacol EX-711, manufactured by Nagase Kasei Kogyo Co., Ltd.). Stored in glass bottles for 6 months. No change such as aggregation or solidification was observed, and it was stable. When this mixture was placed on a ground iron plate and exposed to an excimer laser, the mixture was instantly melted and integrated and fixed to the iron plate.
Beam irradiation is performed at an energy density of about 0.03 J / cm ² ,
Irradiation diameter 1 mm, 1 sec. Irradiation with x 2 shots was sufficient.

[0029]

Example 6 The amine-terminated prepolymer powder obtained in Example 1 and calcium oxide powder were mixed in a weight ratio of 1/3. This powder was dispersed in a solution of an epoxy resin (Epicoat 828) dissolved in 10 times the volume of toluene at a ratio of amino groups to epoxy groups in an equimolar ratio. This was spray-granulated by a continuous fluidized granulation dryer Mixgrad (manufactured by Okawara Seisakusho). The obtained particles have an average particle size of about 200 microns, and have a structure in which fine particles of calcium oxide particles are surrounded by a urethane prepolymer by microscopic observation. It is also seen that epoxy is coated between the particles and on both particle surfaces. Was observed. The particle powder did not change its state even after 3 months, and maintained its fluidity. Immediately after the granulation and one month later, a carbon dioxide laser under the same conditions as in Example 4 was irradiated to examine the film-forming property, and a slightly elastic film was obtained in both cases.

[0030]

Example 7 A mixture of 8 g of powdered isophthalic acid and 20 g of silica gel powder was placed in a fluidized bed granulator, and while being fluidized, oxazoline group-holding polymer K-1020.
E (manufactured by Nippon Shokubai Co., Ltd., solid content 40% emulsion) 110
g was sprayed and granulated. The particles obtained had an average particle size of about 30 microns. It was in the form of composite particles in which isophthalic acid and silica gel were coated with a polymer. The obtained particles were placed in a high-frequency electromagnetic field under the same conditions as in Example 1, and dissolution and curing could be confirmed. The obtained cured product had a Shore hardness A of 90.

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[Procedure amendment]

[Submission date] June 27, 1994

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] Brief description of the drawing

[Correction method] Change

[Correction content]

[Brief description of drawings]

FIG. 1 shows an example of the curing mechanism of a multi-component reactive resin of the present application, in which the molecular structures before and after the reaction of one component and the other component dispersed and mixed are expressed as A and B by generalizing the active groups. Schematic diagram shown

[Explanation of symbols] is an active group having reactivity in the resin molecule, such as a hydroxyl group, an amino group and a carboxyl group. B is an active group that reacts with A, such as an isocyanate group, an epoxy group, or an oxazoline ring. Excluding the active moiety, such as - _{(CH 2} -CH 2 -
O) n-CH ₂ CH _2- (n is an integer and indicates that the same chemical structure is repeated to form a large molecule),-
_{CH 2 -CH 2 OCO-C 6} H 4 CO (OCH 2 -CH
_{2 -OCO-C 6 H 4 CO} ) n-OCH 2 -CH 2 -,
_{-CH 2 (OC 6 H 4 CC} (H 3) 2 -C 6 H 4 -O-
_{CH 2 -CH (OH) -CH 2} ) n-O-C 6 H 4 -C
_{(CH 3) 2 -C 6 H} 4 -O-CH 2 -, - C 6 H 4 -
_{C (CH 3) 2 -C 6} H 4 -, - C 6 H 4 - polymer chain or molecule residues, and the like. -AB- and -BA- represent that the active groups A and B have reacted and bonded. -This is added for the purpose of showing the state of separation, dispersion and mixing before the reaction.

[Procedure Amendment 2]

[Document name to be corrected] Drawing

[Correction target item name] All drawings

[Correction method] Change

[Correction content]

[Figure 1]

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Claims (4)

[Claims] 1. A reactive resin composition in which components that react with each other are dispersed and mixed in a substantially separated state by heating by an energy addition method such as a high frequency electromagnetic field or various laser beams to carry out reaction curing. One-pack storage and curing method of reactive resin composition characterized by 2. The storage and curing method according to claim 1, wherein the composition in which the reactive components are substantially separated and dispersed and mixed is a powder mixture of the respective components. 3. The substantially isolated phase is one in which at least one of the reaction components is microencapsulated.
The storage and curing method according to claim 1, wherein the energy is applied by ultrasonic waves. 4. A high-frequency electromagnetic field, a laser, etc., is applied to a predetermined application or molding place during the transportation of a reactive resin composition in which it is dispersed and mixed, for example, in a transportation pipe or in a flight away from a spray gun to reach an application. The method for preserving and curing according to claim 1, wherein concentrated addition is performed immediately before application or when the object is reached.