JP2000198877A - Method and device for treating to decompose product containing thermosetting resin-cured product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a simple method and device for decomposing products including cured products of thermosetting resins in order to reuse and reutilize resources, the thermosetting resin and other constituent ingredients, from the products including the cured products of thermosetting resins. SOLUTION: This method for treating products including cured products of thermosetting resins comprises (a) a step of contacting products including cured products of thermosetting resins to a decomposition solution containing a solvent capable of breaking main chains and/or cross-linked chains in the cured products of the thermosetting resins in a decomposition tank and (b) a step of heating the decomposition solution at >=250 deg.C to less than the critical point of the solvent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method and an apparatus for decomposing a product using, as a binder, a thermosetting composition which is excellent in strength and heat resistance and widely used for industrial materials. .

[0002]

2. Description of the Related Art Conventionally, thermosetting resins such as unsaturated polyester resins, epoxy resins and phenolic resins are easy to mix with fillers and additives such as inorganic substances, and are easily reinforced by fibers. It is applied to laminates, adhesives and paints. This thermosetting resin is cross-linked into a three-dimensional shape by a curing reaction, and generally becomes an insoluble and infusible solid. For this reason, it is difficult to decompose the cured thermosetting resin, and it has been discarded as unsuitable for regeneration treatment and reuse.

However, as the problem of waste has been attracting attention in recent years, it has become necessary to develop a technique for recycling and recycling thermoset resin cured products, and the use of raw materials by thermal decomposition has begun to be studied. For example, fiber-reinforced unsaturated polyester resins and the like are frequently used in the production of large products such as fishing boats, tanks, and housing equipment, and the waste problem is serious. However, there has been a problem that advantages such as hardness, strength, heat resistance, flame retardancy, and chemical resistance of the cured thermosetting resin have made waste disposal technically difficult.

[0004] Further, thermosetting resins are often used as structural materials due to their strength and the like, but they also often include materials such as metals. Since such metals and the like are more expensive than thermosetting resins, it can be said that their importance in recycling and reuse is great.
However, the copper-clad laminate and the IC mold using an epoxy resin, a phenol resin or the like as a binder contain, in spite of their small size, paper, fibers, and the like, as well as precious metals such as copper, gold, and silver. That is, there is a demand for separation of the metal together with the decomposition treatment of the thermosetting resin. On the other hand, the conventional processing method has a problem that such metal components are not sufficiently reused and recycled.

[0005]

DISCLOSURE OF THE INVENTION In view of the above facts, the present invention aims to recycle and recycle a product containing a cured product of a thermosetting composition, which has been insufficient conventionally. . Specifically, the present invention provides a method for reusing and recycling thermosetting resin and other components from a product containing a cured thermosetting resin. An object of the present invention is to provide a simple decomposition processing method and a simple processing apparatus.

[0006]

According to the present invention, (a) a product containing a cured thermosetting resin is brought into contact with a decomposition solution containing a solvent capable of decomposing the cured thermosetting resin in a decomposition tank. And (b) heating the decomposition solution to a temperature of 250 ° C. or higher and lower than the critical temperature of the solvent.
In this case, the decomposition solution may be vaporized before contacting the product. In this case, after the step (a), the step (b)
Before the step (a ′), it is preferable to include a step of removing oxygen in the decomposition tank. Further, it is preferable that the step (a ′) comprises a step of replacing the gas in the decomposition tank with nitrogen gas and / or a step of evacuating and decompressing the inside of the decomposition tank.
Examples of the solvent in the step (a) include those that decompose the cured thermosetting resin by solvolysis or catalytic action.

Solvents for decomposing the thermosetting resin by solvolysis include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, isoprene glycol, triethylene glycol, tetraethylene glycol, 2-methoxyethanol, -Ethoxyethanol, 2-dimethoxyethanol, 2-isopropoxyethanol, 2-butoxyethanol, 2-isopentyloxyethanol, 2-
Hexyloxyethanol, 2-phenoxyethanol, 2-benzyloxyethanol, 1-methoxy-2
-Propanol, 1-ethoxy-2-propanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether and tripropylene glycol monomethyl ether At least one selected from the group is given.

[0008] Solvents for decomposing the thermosetting resin by a catalytic action include tetralin, biphenyl, naphthalene, 1,4-hydroxynaphthalene, naphthol, 1,4-naphthoquinone, pitch, creosote oil, methyl Examples include at least one selected from the group consisting of isobutyl ketone, isophorone, 2-hexanone, 2-heptanone, 4-heptanone, diisobutyl ketone, acetonylacetone, holon, cyclohexanone, methylcyclohexanone, and acetophenone. Here, the decomposition solution in step (a) preferably contains calcium oxide, and the content in this case is preferably 10 parts by weight or less based on 100 parts by weight of the solvent in the decomposition solution. At this time, the method preferably includes a step (f) of adding carbon dioxide to the solution obtained in the step (a) to neutralize calcium oxide.

Further, the decomposition solution in the step (a) preferably contains an antioxidant or a reducing agent. Examples of such antioxidants or reducing agents include at least one selected from the group consisting of hydroquinone, methoquinone, benzoquinone, naphthoquinone, butylcatechol, butylhydroquinone, sodium hypophosphite, sodium thiosulfate, and ascorbic acid. Can be

The cured thermosetting resin in the step (a) is selected from the group consisting of a cured unsaturated polyester resin, a cured epoxy resin, a cured phenol resin, a cured polyurethane resin and a cured amino resin. At least one selected from them is given.

On the other hand, the product in the step (a) includes a mold motor or a mold transformer including a metal member. In addition, at least one substrate selected from the group consisting of woven or non-woven fabric made of glass fiber, polyester fiber, polyamide fiber, acrylic fiber or aramid fiber, paper such as mica paper and linter paper, cotton cloth and asbestos, Resin laminates obtained by laminating and molding a prepreg impregnated with a curable resin are exemplified. Furthermore, as such a resin laminate,
There is a printed circuit board on which a conductor pattern is formed and electronic components are mounted.

Here, after the step (b), the method comprises:
(C) a step of solid-liquid separation of a mixture containing the heated thermosetting resin cured product and the decomposition solution, (d) a step of dissolving the separated solids to obtain a solution, and (e) subsequently remaining from the solution. It preferably includes a step of separating solids.
At this time, in step (d), acetone, acetylacetone, acetaldehyde, ethyl acetoacetate, methyl acetoacetate, methyl ethyl ketone, diethyl ketone,
Methyl isobutyl ketone, methyl isopropyl ketone,
At least one selected from the group consisting of dimethylsulfoxide, dimethylformamide, ethyl acetate, isopropyl acetate, butyl acetate, tetrahydrofuran, dioxane, diethyl ether, water, ethanol, and methanol
Depending on the species, the separated solids can be dissolved.

According to the present invention, a product containing a cured thermosetting resin and a decomposition solution containing a solvent capable of decomposing the cured thermosetting resin are stored at a temperature of 250 ° C. or higher and lower than the critical temperature of the solvent. A decomposing tank provided with means for heating the mixture, a solid-liquid separating tank for solid-liquid separating the mixture obtained in the decomposing tank, and a thermosetting liquid dissolving and separating tank for dissolving and separating the solids separated in the solid-liquid separating tank. The present invention also relates to an apparatus for decomposing a product containing a cured resin.

The decomposition processing apparatus further comprises a supply unit for supplying a product containing the cured thermosetting resin and a decomposition solution containing a solvent capable of decomposing the cured thermosetting resin. It is preferable to include an extruding means for mixing and continuously extruding the decomposed liquid and a means for heating the product and the decomposed liquid in the extruding means. Preferably, the extruding means is capable of applying a shear stress to the product and the decomposition solution.

[0015]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention provides (a) a step of bringing a product containing a cured thermosetting resin into contact with a decomposition solution containing a solvent capable of decomposing the cured thermosetting resin in a decomposition tank;
And (b) a method for decomposing a product containing a cured thermosetting resin, comprising a step of heating the decomposition solution to a temperature of 250 ° C. or higher and lower than the critical temperature of the solvent.

First, a product containing a cured thermosetting resin which is the object of the decomposition treatment method of the present invention will be described. The product containing the cured thermosetting resin to be subjected to the decomposition treatment method of the present invention uses the thermosetting resin as a binder. That is,
A thermosetting resin is compounded with a filler, a base material, an additive, and the like, and is cured by a curing reaction of the thermosetting resin.

Examples of such a thermosetting resin include unsaturated polyester resin, phenol resin, epoxy resin, polyurethane resin, melamine resin, urea resin and the like. The production method and conditions for these thermosetting resins are not particularly limited. For example, the polymerization ratio of the monomer components is also arbitrary. In addition, as an epoxy resin, a bisphenol A type, a glycidyl ether type, etc. are mentioned, for example. Also, as the unsaturated polyester resin,
It is obtained by a conventional method from dibasic acids such as maleic anhydride and adipic acid, dihydric alcohols such as ethylene glycol, and vinyl monomers such as styrene, hydroxyethyl acrylate and hydroxyethyl methacrylate.

Among the unsaturated polyester resins, at least an unsaturated polyester, a low shrinkage agent, styrene,
Those containing at least one addition-polymerizable monomer selected from the group consisting of hydroxyethyl acrylate and hydroxyethyl methacrylate are preferred. In this case, of course, the concentration and the mixing ratio of the unsaturated polyester and the low shrinkage agent are not particularly limited.

Examples of products using an unsaturated polyester resin as a binder include BMC (bulk molding compo) added with a filler, a thickener, a release agent, a wax, a coloring agent, and the like.
und), molding products such as SMC (Sheet Molding Compound), lining materials including glass and other flakes and fibers, paints including wax, putty including fillers, aggregates, fillers, etc. Resin concrete,
Examples include artificial marble to which fillers and pigments are added, foams to which foaming agents are added, and adhesives to which curing accelerators, stabilizers and the like are added. Further, the thermosetting resin may be used as a bulk molding material, and a sheet-like SMC,
Or PMC (Pelletized type Molding Compou
nd).

As fillers and aggregates for products containing the above-mentioned cured thermosetting resin, there are inorganic materials and organic materials. Examples of the inorganic material include carbonates such as calcium carbonate and magnesium carbonate, (sulfite) salts such as calcium sulfate, barium sulfate and calcium sulfite, clays, mica, glass balloons, montmorillonite, silicic acid, kaolin and talc. Acid salts, silica, siliceous earth, iron oxide, pumice balloon, oxides such as titanium oxide and alumina, and hydroxides such as aluminum hydroxide and magnesium hydroxide. Also, graphite, glass fiber, carbon fiber, asbestos fiber and the like can be mentioned. On the other hand, examples of the organic material include wood flour, rice hull, cotton, paper strip, polyamide (nylon) fiber, polyethylene fiber, wood, pulp, and cellulose.

Examples of the thickener include beryllium oxide,
Examples include magnesium oxide, magnesium hydroxide, calcium oxide, calcium hydroxide, zinc oxide, benzoic acid, phthalic anhydride, tetrahydrophthalic anhydride, and maleic anhydride. Further, examples of the release agent include stearic acid, zinc stearate, calcium stearate and the like. Examples of the wax include Hoechst wax, carnauba wax and paraffin. Examples of the coloring agent include titanium white, chromium oxide and carbon black.

Examples of products using a urea resin or a melamine resin as a binder include moldings, adhesives, and paints to which the same fillers, substrates, and additives as those of the unsaturated polyester resin are added. Also, when a polyurethane resin is used as the binder, foams, paints, adhesives, and the like to which the same additives as the unsaturated polyester resin are added can be used. Examples of the product using a phenolic resin as a binder include, in addition to the same product as the cured resin obtained using the above-described unsaturated polyester resin as a binder, glass fiber, polyamide fiber, acryl fiber or polyester fiber woven fabric or Resin laminates formed by laminating a prepreg obtained by impregnating a non-woven fabric, a cotton cloth, asbestos, or the like with a resol-type phenol resin, and the like are listed.
This resin laminate is further laminated with a copper foil coated with an adhesive to form a copper-clad laminate. Further, a printed circuit board on which a conductive pattern is formed and electronic components are mounted may be used. For example, the product may be a printed wiring board manufactured from a copper-clad laminate through steps such as circuit printing and etching. In this case, the resist is similarly decomposed by the decomposition processing method of the present invention.

Products using an epoxy resin as a binder are also similar to the case of the unsaturated polyester resin in the same manner as in the case of the phenol, such as woven or nonwoven fabric of glass fiber, polyester fiber or aramid fiber, mica paper and linter paper. Resin laminates obtained by laminating a prepreg obtained by impregnating an epoxy resin with paper or the like as a base material, and the like can be given. In this case as well, a copper-clad laminate is obtained by laminating and forming a copper foil coated with an adhesive. Further, a product using a thermosetting resin such as a polyimide resin as a binder is also an object of the method for decomposing a cured resin of the present invention.
In addition, a mold motor or a mold transformer including a metal member such as a winding and a core made of copper and iron is also an object of the method of the present invention.

The products to be subjected to the decomposition treatment of the present invention include, for example, construction materials such as bathtubs, toilet tubs, water tanks and wash basins, household goods such as chairs, desks and furniture, tiles, artificial marble and pipes. Civil engineering materials, ships, automobiles,
Examples include bodies and parts of transportation equipment such as railways and aircraft, housing equipment, decorative boards, and decorative articles. Also,
The form and shape of the thermosetting resin in these products are not limited, and may be used as paints, putties, adhesives and the like. The product to be subjected to the decomposition treatment method of the present invention can be manufactured by a conventionally known curing molding method such as compression molding, transfer molding or injection molding.

Hereinafter, the present invention will be described along each step for easy understanding. First, in step (a), a product containing a cured thermosetting resin to be subjected to the decomposition treatment of the present invention described above is converted into a decomposition solution containing a solvent capable of decomposing the cured thermosetting resin in a decomposition tank. Contact.

The decomposing liquid mainly comprises a solvent capable of decomposing the cured thermosetting resin. That is, as a result of intensive studies, the present inventors have found that if the solvent heated to a predetermined temperature is brought into contact with a cured thermosetting resin, the main chain and / or cross-linked chain of the thermosetting thermosetting resin will be reduced. They found that they could be cut and completed the present invention. Examples of the solvent capable of decomposing the cured thermosetting resin include those which break the main chain and / or the crosslinked chain by solvolysis or catalytic action.

Here, the solvolysis means that the solvent molecule cuts the main chain and / or the cross-linked chain of the cured thermosetting resin,
And it means to bond to the cut part of the thermosetting resin chain,
It has a significance equivalent to hydrolysis. On the other hand, in the decomposition by the catalytic action, only the solvent molecule exerts the catalytic function to cut the main chain and / or the crosslinked chain, and does not bond to the cut portion of the thermosetting resin chain.

Examples of the solvent for decomposing the cured thermosetting resin by solvolysis include ethylene glycol,
Propylene glycol, diethylene glycol, dipropylene glycol, isoprene glycol, triethylene glycol, tetraethylene glycol, 2-methoxyethanol, 2-ethoxyethanol, 2-dimethoxyethanol, 2-isopropoxyethanol, 2-butoxyethanol, 2-isopentyl Oxyethanol, 2-hexyloxyethanol, 2-phenoxyethanol, 2-benzyloxyethanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, dipropylene Glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene At least one can be cited is selected from glycol monomethyl ether and the group consisting of tripropylene glycol monomethyl ether. Among these, ethylene glycol and propylene glycol are preferred from the viewpoints of solvolysis ability, availability, and low cost.

On the other hand, examples of the solvent which decomposes the thermosetting resin cured product by the catalytic action include tetralin, biphenyl, naphthalene, 1,4-hydroxynaphthalene, naphthol, 1,4-naphthoquinone, pitch, creosote oil, methyl Examples include at least one selected from the group consisting of isobutyl ketone, isophorone, 2-hexanone, 2-heptanone, 4-heptanone, diisobutyl ketone, acetonylacetone, holon, cyclohexanone, methylcyclohexanone, and acetophenone. Among these, tetralin and isophorone are preferred from the viewpoint of low pressure during treatment. Further, tetralin is more preferable because it has a reducing action and can prevent oxidation of metals and the like contained in the product.

In addition, the decomposition solution preferably contains an antioxidant or a reducing agent in addition to the solvent in order to more reliably prevent oxidative deterioration of the solvent and metals contained in the product. As such an antioxidant or a reducing agent, for example, hydroquinone, methoquinone, benzoquinone, and the like are preferable because they have good solubility in the solvent and a high effect of preventing oxidation (deterioration) of the solvent and metal. Examples include at least one selected from the group consisting of naphthoquinone, butylcatechol, butylhydroquinone, sodium hypophosphite, sodium thiosulfate, and ascorbic acid.

Of these, hydroquinone and methoquinone are preferred because of their excellent antioxidant ability. These antioxidants or reducing agents may be used in an amount of 0.2 to 10 parts by weight based on 100 parts by weight of the solvent in the decomposition solution, from the viewpoint of exhibiting an antioxidant function and a reducing function. From the point of solution stability of the liquid, 1
It is preferably from 5 to 5 parts by weight.

When the solvent in the decomposition solution is a solvent that decomposes the main chain and / or crosslinked chain of the cured thermosetting resin by solvolysis, calcium oxide is added to the decomposition solution. Is preferred. In this case, when the solvent cuts the main chain and / or cross-linked chain of the thermosetting resin, the calcium oxide acts as a catalyst that promotes the solvolysis of bonds such as esters and ethers of the thermosetting resin. . Calcium oxide may be added in an amount of 10 parts by weight or less based on 100 parts by weight of the solvent so that each decomposition reaction is efficiently accelerated and does not become an impurity of the thermosetting resin to be recycled. Further, from the viewpoint of solubility in a decomposition solution and ease of neutralization treatment in the step (f) described below, 0.5 to 0.5%
It is preferable to add 5 parts by weight.

When calcium oxide is added,
In consideration of the quality of the thermosetting resin and metal to be reused, it is preferable to neutralize calcium oxide by adding carbon dioxide to the decomposition solution in step (f) described below.

As the decomposition tank, a conventionally known decomposition tank may be used. In the step (a), the product containing the cured thermosetting resin in the decomposition tank may be in contact with the decomposition liquid containing the solvent. From the viewpoint of enabling efficient decomposition treatment, it is preferable to immerse the entire product including the cured thermosetting resin in a decomposition solution containing the solvent.

Next, in the step (b), the decomposition solution in contact with the product containing the cured thermosetting resin is heated at 250 ° C.
Heat to a temperature above and below the critical temperature of the solvent.
This is to obtain a large decomposition reaction rate. Among them, it is preferable that the temperature of the decomposition solution is high.
If it is 0 ° C. or higher, the reaction rate is greatly accelerated. However, if the temperature is too high, the pressure will be too high to require high pressure resistance of the decomposition tank, the amount of gas generated by decomposition will be large, and its recovery will be difficult, and the solvent in the decomposition liquid will be difficult. The temperature of the decomposition solution is preferably lower than the critical temperature of the solvent, since decomposition itself may occur. For example, in the case of propylene glycol, the critical temperature is 351
° C.

The decomposition solution may be heated and vaporized before contacting the product, and the vaporized decomposition solution may be brought into contact with the product.

Here, the solvent has high stability at high temperatures, and rarely generates oxygen by its own decomposition and induces oxidation of metals and the like contained in the cured resin. However, a pretreatment step such as oxygen elimination is not necessarily required. However, in the case where slight oxidation of metal or the like contained in the cured resin becomes a problem, or in order to prolong the life of the decomposition solution, a pretreatment step such as oxygen exclusion may be provided. That is, after the step (a) and before the step (b), as the step (a ′), it is preferable to exclude oxygen in the decomposition tank.

This step can be carried out by a conventional method. For example, a gas introduction pipe and an exhaust valve may be provided in a decomposition tank charged with the product and the decomposition solution, and gas may be directly sent from a nitrogen gas cylinder. Further, the gas in the decomposition tank may be exhausted by reducing the pressure. To reduce the pressure, for example, an exhaust valve may be provided in a decomposition tank charged with the product and the decomposition solution, and a vacuum pump may be connected. The degree of pressure reduction at this time is preferably as close to vacuum as possible. Preferably it is 10 mmHg or less. Furthermore, in any of the methods, the efficiency of oxygen exclusion can be increased by stirring the decomposition solution or heating it appropriately.

Preferably, both of these methods are adopted and any method may be used as long as oxygen in the decomposition tank can be exhausted. For example, the gas in the decomposition tank is replaced with nitrogen gas. Then, it is preferable to exhaust the nitrogen gas to reduce the pressure inside the decomposition tank. As described above, by performing the decomposition treatment after the pretreatment for removing oxygen, oxidation, which is the main cause of degradation of the decomposition liquid during the high-temperature reaction treatment, is prevented, the life of the decomposition liquid is extended, and the reusability is improved. Further, it is possible to prevent the deterioration of metals contained in the product by oxidation and the like, and to improve the quality of materials separated and recovered.

Further, in the method of the present invention, after the step (b), a step (c) of solid-liquid separation of a mixture containing the heated thermosetting resin cured product and the decomposition solution, and a step of dissolving the separated solids Preferably, the method includes a step (d) of obtaining a solution by the reaction, and a step (e) of separating a residual solid content from the solution.

In the step (c), the mixture containing the heated thermosetting resin cured product and the decomposed liquid is insoluble in the decomposed liquid of the metal parts, the inorganic filler, and the thermosetting resin decomposed product of the product. The solid-liquid separation of a solid such as a product and a liquid such as a solvent (decomposed liquid) containing a cured product of a cured thermosetting resin soluble in the decomposition liquid.

Then, in the step (d), the separated solid (a thermosetting resin decomposition product, for example, bisphenol A-epichlorohydrin resin in the case of an epoxy resin) is dissolved to obtain a solution. Here, acetone, acetylacetone, acetaldehyde, ethyl acetoacetate, methyl acetoacetate, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, methyl isopropyl ketone, dimethyl sulfoxide, dimethylformamide, ethyl acetate, isopropyl acetate, butyl acetate, tetrahydrofuran, dioxane, diethyl Ether, water, ethanol,
The separated solid can be dissolved by at least one selected from the group consisting of methanol. Next, in the step (e), residual solids such as a metal component, an inorganic filler, and a substrate such as glass fiber are separated from the solution.

As described above, by bringing the product containing the cured thermosetting resin into contact with the decomposition solution containing the solvent,
The main chain and / or the three-dimensional crosslinked chain of the cured thermosetting resin can be cut. When the cured thermosetting resin is decomposed, the function of the thermosetting resin as a binder decreases and collapses. That is, the cured thermosetting resin is
The filler, base material, additives, and the like bound by the curing cannot be retained, and the thermosetting resin component can be easily separated from other components. Since the thermosetting resin component itself is decomposed, it can be recovered as a monomer. In that case,
Each component is obtained as a solid content, oil, or a solute in a solution, depending on the solubility in the decomposition solution. According to the method for decomposing a cured resin of the present invention, a product having a thermosetting resin as a binder, which has been difficult to decompose, can be easily decomposed. After further decomposition, a resin component, a filler, a substrate, an additive, and these constituent components can be obtained.

Next, the present invention also relates to a decomposition processing apparatus which can be used in the above-mentioned method for decomposing a cured thermosetting resin. The decomposition treatment apparatus for a product containing a cured thermosetting resin of the present invention comprises a decomposition product containing a product capable of cutting a main chain and / or a cross-linked chain of the product containing a cured thermosetting resin and the cured thermosetting resin. A decomposition tank provided with means for containing a liquid and heating to a temperature of 250 ° C. or higher and lower than the critical temperature of the solvent, a solid-liquid separation tank for solid-liquid separation of a mixture obtained in the decomposition tank, and the solid-liquid separation tank. It comprises a dissolution separation tank for dissolving and separating the solids separated in the separation tank.

Supply means for supplying a product containing the cured thermosetting resin and a decomposition solution containing a solvent capable of cutting the main chain and / or crosslinked chain of the cured thermosetting resin;
It is preferable to include an extruding means for mixing and continuously extruding the supplied product and solvent, and a means for heating the product and solvent in an extruder. Particularly, from the viewpoint of improving the efficiency of the decomposition treatment, it is preferable that the extruding means can apply shear stress to the product and the solvent. Further, the extruding means may also serve as a decomposition tank.

Further, in a decomposition tank having an extruding function, it is assumed that it is difficult to extrude a mixture of the product and the decomposition liquid by a gas component generated by heating. Therefore, it is preferable to provide a gas vent in the decomposition tank. Further, a gas component can be recovered by installing a condenser in the degassing section.

Specifically, the decomposition treatment apparatus of the present invention supplies the product and a decomposition solution containing a solvent, and then kneads and extrudes the mixture while heating them. That is, it is possible to continuously perform a decomposition process of a product using a thermosetting resin as a binder. The heating temperature in this apparatus is desirably 250 ° C. or higher and lower than the critical temperature, as in the decomposition treatment method of the present invention described above.

Extrusion can be carried out by rotating a single-screw or twin-screw, transferring by a pump, or the like. In particular, when the extrusion is performed by a single-screw or twin-screw rotation, it can be expected that the extrusion efficiency is high and that the decomposition reaction is more efficient by mixing and stirring the product and the decomposition solution while applying a shearing force. Furthermore, by attaching a plurality of disks to the screw rotating shaft perpendicularly to the screw, for example, by extruding the mixture of the cured resin and the decomposition solution by screw rotation, and further applying a shearing force by passing through the gap between the disks. And the reaction efficiency can be increased. The pressure, speed, distance, and the like for extruding the product and the decomposition solution can be determined by the time required for the decomposition reaction. Therefore, an in-line injection molding machine or the like can be used.

By providing a means for supplying an additional decomposed liquid to the kneaded product of the product and the decomposed liquid being heated and extruded, the decomposed liquid can be supplemented and the decomposition reaction can be made more efficient. It is desirable that the product to be charged into the present apparatus has a large surface area in order to increase the efficiency of the reaction by the decomposition solution. For example, it is preferable that the product has a pulverizing means as a pre-process before being charged into the present apparatus.

In the decomposition treatment apparatus of the present invention, the product is brought into contact with a decomposition solution containing the solvent, heated at a temperature in the range of 250 ° C. or more and less than the critical temperature, and then the insoluble component is separated from the decomposition solution ( Solid-liquid separation). Then, the solid-liquid separated insoluble component is further dissolved and separated into a soluble component and an insoluble component.
This apparatus enables the decomposition of the cured resin and the separation of the components of the cured resin after the decomposition. By immersing the cured resin in a decomposition solution, the main chain and / or the three-dimensional crosslinked chain of the thermosetting resin is decomposed. When the thermosetting resin is decomposed, the function of the thermosetting resin as a binder decreases, and the cured resin collapses. The cured resin cannot retain the filler, the base material, the additives, and the like bound by the curing of the thermosetting resin as the binder.

Then, by separating the insoluble components by solid-liquid separation, the components other than those soluble in the decomposed liquid among the decomposed components, such as most of the fillers, base materials, additives, and binders, are recovered. be able to. The insolubles can then be further dissolved and separated into components of the binder, which is a thermosetting resin, and other components such as fillers, base materials, and additives, which can be reused. Becomes

As the solid-liquid separation means, filtration with a filter or the like, centrifugal separation, or the like can be used. For centrifugation, for example, a centrifugal separator such as a cylindrical type, a separation plate type, and a decanter type can be used.

For dissolving and separating the solid, acetone,
Acetylacetone, acetaldehyde, ethyl acetoacetate, methyl acetoacetate, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, methyl isopropyl ketone, dimethyl sulfoxide, dimethylformamide, ethyl acetate, isopropyl acetate, butyl acetate, tetrahydrofuran, dioxane, diethyl ether, water ,
At least one solvent selected from the group consisting of ethanol and methanol can be used.

These exhibit high solubility in a thermosetting resin as a binder. Further, when calcium oxide is added to the decomposition solution to improve reactivity, calcium oxide not consumed by the reaction is, as described above,
It can be neutralized by carbon dioxide. For example, calcium oxide can be easily neutralized as calcium carbonate by injecting insolubles into a solvent and blowing carbon dioxide with stirring. The generated calcium carbonate can be reused as an inorganic filler after dissolution separation. For neutralization, at least carbon dioxide may be present, and a gas containing carbon dioxide, an exhaust gas from air or a boiler may be blown, or dry ice may be directly injected.

In the decomposition method or the decomposition apparatus according to the present invention, of the components generated by the decomposition reaction, components soluble in the decomposition liquid are separated by a step such as extraction, and the solvent is reused as the decomposition liquid again. Can also. Further, when polyester resin fiber or the like is used as the base material and the filler, the product is decomposed together with the thermosetting resin by the decomposition treatment method and the decomposition treatment device of the present invention, so that the decomposability of the product is enhanced. In this case, the decomposition component can also be separated and recovered by the decomposition treatment device of the present invention, and can be reused as a raw material again.

Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited to only these.

[0057]

Examples << Examples 1-3 and Comparative Examples 1 and 2 >>
35 parts by weight of styrene were mixed with 65 parts by weight of an unsaturated alkyd composed of phthalic anhydride, fumaric anhydride and propylene glycol. Then, 0.01 parts by weight of a polymerization inhibitor, methoxyhydroquinone, was added and dissolved by stirring at room temperature to obtain an unsaturated polyester resin. On the other hand, at room temperature, 36 parts by weight of polydipropylene adipate was added to methacrylic acid 2-
It was mixed with 64 parts by weight of hydroxyethyl and dissolved by stirring to obtain a low-shrinking agent.

To 74 parts by weight of the unsaturated polyester resin, 26 parts by weight of a low-shrinking agent, and 1,1-
One part by weight of (t-butylperoxy) 3,3,5-trimethylcyclohexane was added and mixed with stirring to obtain a liquid resin composition. Next, calcium carbonate 1 as a filler
7.8 parts by weight, 48.5 parts by weight of aluminum hydroxide, 1.5 parts by weight of zinc stearate as a release agent, and 0.4 parts by weight of carbon powder as a colorant were transferred to a kneader and dried for about 5 minutes. Mixing was performed. This uniformly mixed dry mixture was obtained, and 22 parts by weight of the previously prepared resin composition was gradually added and kneaded to obtain a uniform paste-like mixture. And
To this paste-like mixture, 9.8 parts by weight of glass fiber was added as quickly as possible while uniformly dispersing the glass fiber. When the glass fiber was wet and uniformly dispersed, kneading was completed, and the thermosetting resin was combined with the binder. Molding material was obtained.

The molding material thus obtained is usually BMC
Is a type of bulk molding material called non-adhesive despite containing a solvent. This molding material was subjected to compression molding at a mold temperature of 150 ° C. and a pressure of 35 kgf / cm ² to obtain a product containing a 20-mm-diameter cylindrical thermosetting resin cured product.

Next, this product was immersed in a decomposition solution consisting only of propylene glycol, and was immersed at 200 ° C. (Comparative Example 1).
200 ° C. (Comparative Example 2), 250 ° C. (Example 1), 300
C. (Example 2) or 350.degree. C. (Example 3) for 5 hours to carry out the decomposition treatment method of the present invention. At this time, the rate of penetration of the decomposition solution and the surface hardness of the cured thermosetting resin after the decomposition treatment were measured. The hardness was measured using a rubber hardness meter. Table 1 shows the results.

[0061]

[Table 1]

As can be seen from Table 1, when a product containing a cured thermosetting resin is treated with a decomposition solution of propylene glycol at 250 to 350 ° C. according to the method of the present invention,
The decomposed liquid penetrated into the inside of the cured thermosetting resin, and the hardness was reduced until it could not be measured with a rubber hardness meter. That is, it was recognized that the product could not maintain its structure and collapsed because the cured unsaturated polyester resin was chemically decomposed. As described above, a product containing a cured unsaturated polyester resin as a binder can be promptly decomposed by a decomposing liquid composed of propylene glycol.

The comparative examples 150 and 200 ° C.
In the treatment at 250 to 350 ° C., the permeation rate of the decomposition solution is large, and the hardness is significantly reduced as compared with the treatment in the above. In the decomposition treatment at 150 or 200 ° C., which is a comparative example, the penetration of the decomposition liquid into the cured thermosetting resin is slow, and almost no decrease in hardness is observed. That is, in the treatment at a temperature of 250 ° C. or higher, the thermosetting resin cured product is disintegrated by the decomposition solution, whereas at a temperature lower than 250 ° C., the disintegration effect is small.

In this embodiment, a bulk molding material has been described. However, as described above, a sheet-like SMC or a granular PMC (Petletized type Molding Compound) may be used. This applies to all the embodiments described later.

Embodiment 4 In this embodiment, the mold motor was disassembled. First, a molded motor was manufactured using the molding material prepared in Example 1. That is, the electromagnetic laminated steel sheet provided with the electromagnetic winding was set in a mold, injection molding of the molding material was performed at a molding temperature of 150 ° C., and a molded motor was obtained as a product containing a cured thermosetting resin. . The thickness of the molded part in this molded motor is at most 10
mm. Next, this mold motor was immersed at 300 ° C. in a decomposition solution composed of ethylene glycol to which calcium oxide was added. The calcium oxide content of this decomposition solution was 1 part by weight based on 100 parts by weight of ethylene glycol. After immersion for 5 hours, the mold motor was taken out of the decomposition solution. As a result, the cured portion of the thermosetting resin in the mold motor was in a collapsed state and could be easily peeled off. That is, the electromagnetic members such as the electromagnetic winding and the electromagnetic laminated steel plate could be easily separated and collected from the molded motor.

<< Examples 5 to 7 and Comparative Example 3 >> Example 4
The molded motor used in
0.5 parts by weight of calcium oxide with respect to parts by weight (Example 5), 5 parts by weight (Example 6), 10 parts by weight (Example 7)
And 15 parts by weight (Comparative Example 3), and immersed in four kinds of decomposed liquids, and heated at 300 ° C. for 5 hours. As a result, when the addition amount of calcium oxide was 10 parts by weight or less, the electromagnetic members such as the electromagnetic winding and the electromagnetic laminated steel sheet could be easily separated and collected from the molded motor. In addition, since calcium oxide becomes an impurity when the peeled resin cured portion is reused, it is not preferable that calcium oxide is present in a large excess. When 15 parts by weight of calcium oxide is added to 100 parts by weight of ethylene glycol,
A large amount of unconsumed calcium oxide adhered to the periphery of the cured thermosetting resin, and it was difficult to peel off the cured thermosetting resin.

As can be seen from the results of Examples 5 to 7 and Comparative Example 3, the unsaturated polyester resin hardened in the mold motor by the decomposition solution composed of ethylene glycol containing calcium oxide had a hardness large enough to be peeled off with bare hands. Indicates a decline. Therefore, valuable metals such as copper and iron in the electromagnetic members of the electromagnetic winding and the electromagnetic laminated steel sheet can be easily separated and collected.

In the present embodiment, the mold motor is subjected to the disassembling process as it is. However, the disassembling process may be performed after pre-processing such as coarse crushing and cutting. By doing so, the thickness from the outer surface of the cured thermosetting resin portion is reduced, and the time for contact with the decomposition solution can be reduced. Further, if a crack or the like occurs in the mold motor, the crack surface becomes a new outer surface, and the thickness of the cured thermosetting resin portion from the outer surface is reduced. Therefore, even if only the product is scratched by flea or the like, the decomposition process is made easier. In order to separate and separate the cured thermosetting resin after the mold motor is disassembled, a bare hand wearing chemical resistant gloves or a jig such as a spatula or a press die may be used. Alternatively, the separation may be performed by irradiation with high-pressure water.
These are true in all of the following examples.

Example 8 In this example, a laminate, which is a product using an epoxy resin and a phenol resin as a binder, was decomposed. After impregnating kraft paper with the phenolic resin varnish, the solvent was evaporated by heating to produce a prepreg. Next, the prepregs were cut, overlapped, inserted into a press, and heated and pressurized to cure the phenol resin to obtain a laminate. On the other hand, a glass fiber woven fabric was impregnated with an epoxy resin and then heated to evaporate the solvent, thereby producing a prepreg. The prepreg was cut and overlapped, and a copper foil coated with a modified epoxy resin adhesive was placed thereon, inserted into a press, and cured by heating and pressing to obtain a copper-clad laminate.

Next, these laminates were immersed in a decomposition solution obtained by adding 2 parts by weight of calcium oxide to 100 parts by weight of ethylene glycol, and heated at 250 ° C. for 5 hours. As a result, the resin as the binder was decomposed and dissolved or dispersed in the decomposition solution, leaving kraft paper, glass fiber woven fabric, and copper foil as the base material of the laminate. Glass fiber woven fabric
It was in a state where it could be easily separated into the number of sheets stacked in the laminate manufacturing process. As described above, the laminate, which is a cured resin obtained by using the epoxy resin and the phenol resin, which are thermosetting resins, as binders, can be rapidly decomposed by the decomposition solution composed of ethylene glycol containing calcium oxide. .

Embodiment 9 A first embodiment of the apparatus for decomposing a product containing a cured thermosetting resin according to the present invention will be described with reference to FIG. The apparatus comprises a hopper 1 for supplying a cured thermosetting resin, a hopper 2 for supplying a decomposition liquid, and a decomposition tank 3 for mixing and extruding the decomposition product and the product supplied from these hoppers. The decomposition tank 3 has a cylindrical shape with one end opened as a nozzle 4, has a single-screw 5 for extrusion inside, and a winding heater 6 for heating outside.

First, the product using the unsaturated polyester resin used in Example 1 as a binder was coarsely pulverized to a particle size of 1 mm or less and filled in the hopper 1. Ethylene glycol was injected into the hopper 2. Next, after the inside of the decomposition tank 3 was heated to 300 ° C. by the winding heater 6, the screw 5 was rotated, and the product and the decomposition liquid were continuously supplied to the decomposition tank from the hopper 1 and the hopper 2, respectively. The supply amount of the decomposition liquid was such that the thermosetting resin cured product portion of the product became wet. By the rotation of the screw, the product and the decomposition liquid are kneaded and simultaneously subjected to a shearing force, and then continuously discharged from the nozzle 4 which is an opening of the decomposition tank. At this time, the product was in a collapsed state, and the particle components or glass fibers appeared to be exposed. When the released product was analyzed, it was confirmed that the ester bond or the cross-linked chain of the unsaturated polyester resin as the binder was chemically decomposed. Since the binder was decomposed, it was easy to separate and recover the filler, and it was also possible to recover the components of the binder.

As described above, according to the decomposition apparatus of the present invention, an apparatus for continuously decomposing a cured resin using a thermosetting resin as a binder to facilitate recovery and reuse of each component. be able to. In the present embodiment, aluminum hydroxide as a filler in the cured resin material subjected to the decomposition treatment,
Even by heating during the decomposition treatment, it was not dehydrated to aluminum oxide, but could be recovered as aluminum hydroxide. Therefore, it could be reused as a flame-retardant filler.

In order to replenish the kneaded product of the product and the decomposition solution during heating and extrusion with the decomposition solution, an opening 7 is provided in the middle of the decomposition tank 3 as shown in FIG. Can be provided. The configurations of the extruding device, the heating device, and the replenisher for the decomposition solution are not limited to the configuration of the present embodiment as described above.

Embodiment 10 A second embodiment of the apparatus for decomposing a product containing a cured thermosetting resin according to the present invention will be described with reference to FIG. In this apparatus, a product using a thermosetting resin as a binder is immersed in a decomposition liquid, and a decomposition tank 11 for heating, a decomposition liquid in which a soluble component generated by thermal decomposition in the decomposition tank is dissolved, and a decomposition liquid insoluble component are dissolved. And a dissolution separation tank 13 for dissolving and separating the separated solid components with a solvent. In addition, the first distillation column 1 that separates the solution separated by the solid-liquid separation tank 12 into a decomposition liquid solvent component and a dissolved component derived from a cured product of a cured thermosetting resin by distillation.
4. a drying tank 15 for distilling off residual solvent components from the insoluble solids generated by the dissolution / separation tank 13; a second distillation column 16 for distilling off the solvent from the solution generated by the dissolution / separation tank 13 to separate from the dissolved resin component; And a third distillation column 17 for separating a solvent component. Further, the decomposition tank 11 is provided with a heater 18 for heating the cured thermosetting resin and the decomposition liquid in a temperature range of 250 ° C. or more and less than the critical temperature.

100 g of the columnar product of Example 1 is immersed in a decomposition tank 11 filled with a decomposition liquid composed of 500 g of ethylene glycol, and the decomposition liquid is heated at 300 ° C. by a heater 18.
The product was completely disintegrated within 10 hours, and it was confirmed that fillers such as calcium carbonate and glass fibers and a part of resin components were precipitated in the decomposition solution. Next, the content of the decomposition tank 11 was transferred to a solid-liquid separation tank 12, and separated into a filtrate and insoluble solids. This solid content is composed of glass fiber, calcium carbonate and a decomposed resin component. The filtrate obtained by centrifugation in the solid-liquid separation tank 12 was transferred to the first distillation column 14 and separated into ethylene glycol and the dissolved resin-decomposed component by decomposition. Ethylene glycol is used again as a decomposition solution in the decomposition tank 11. The dissolved resin-decomposed component was propylene glycol or the like constituting the unsaturated polyester, and could be reused as a raw material for the unsaturated polyester resin.

On the other hand, the solid content separated by the solid-liquid separation tank 12 is dissolved in a dissolution separation tank 13 filled with acetone as a solvent.
The solid content insoluble in acetone was recovered as a precipitate in the dissolution separation tank 13. The sediment is deposited in the drying tank 1
After drying in 5, the resin was recovered and found to contain almost no resin and almost all fillers of the product, such as calcium carbonate, aluminum hydroxide and glass fibers. The solvent distilled off by drying is transferred to the second distillation column 16. Further, the solvent in the dissolution / separation tank 13 is also transferred to the second distillation column 16.

Here, the solvent and the dissolved resin component derived from the decomposition product of the cured thermosetting resin are separated. Then, the recovered dissolved resin component is reused as a raw material of the thermosetting resin. The solvent is further transferred to the third distillation column 17, where it is separated into acetone and residual ethylene glycol. Acetone is again injected into the dissolution / separation tank 13 and used as a solvent, and ethylene glycol is transferred to the decomposition tank 11 and used again as a decomposition solution.

As described above, according to the decomposition treatment apparatus of the present invention, the product is decomposed, the cured thermosetting resin after the decomposition treatment is further separated into each component, and the decomposition liquid is recovered. You. Each of the separated substances can be reused again for the cured resin, its decomposition treatment method, and other uses. The aluminum hydroxide as a filler in the product subjected to the decomposition treatment in this example was not dehydrated into aluminum oxide by heating by the decomposition treatment method of the present invention, and could be recovered as aluminum hydroxide. . Therefore, it could be reused as a filler having flame retardancy.

The equipment of each component used in the decomposition processing apparatus is not limited to that shown in this embodiment. For example, a stirrer or the like may be introduced into the decomposition tank 11 to accelerate the decomposition processing. it can. Further, after decomposing several cured resin products, all of the decomposed liquid may be separated at a time. A part of the decomposition solution is continuously introduced outside the decomposition tank,
A continuous circulation type may be used in which the solid content is separated and the solvent is removed from the decomposition solution by distillation to remove the separated material, and then the decomposition solution is returned to the decomposition treatment tank by a high-pressure pump. Further, if the purpose is to separate a part of the substances present in the decomposition solution, only a part of the decomposition treatment apparatus according to the present invention may be used. The number of dissolution / separation tanks can be increased in accordance with the number of constituent components of the cured thermosetting resin, and the dissolution / separation can be repeatedly performed to finely separate components.

Further, it is also possible to separate the thermosetting resin cured product which is continuously decomposed by the combination with the decomposition apparatus according to the first embodiment of the present invention. It may be combined with other means such as specific gravity separation. An apparatus for performing another process may be added before the decomposition processing apparatus of the present invention. For example, by adding a pretreatment step of roughly crushing a product containing a thermosetting resin cured product, the decomposition treatment time in the decomposition tank can be shortened.

<< Comparative Example 4 >> Diameter 20 used in Example 1
mm columnar product is immersed in water instead of the decomposition solution,
Heated at 300 ° C. for 5 hours. Thereafter, the rate of water penetration and the surface hardness of the cured thermosetting resin part of the product after the treatment were measured. As a result, a large crack was formed in the cured product, but water hardly penetrated into the cured product portion, and almost no decrease in hardness was observed. That is, the effect of the decomposition treatment cannot be expected with water.

<< Comparative Example 5 >> Diameter 20 used in Example 1
mm cylindrical product was heated to 300 ° C. in air for 5 hours. As a result, some small cracks occurred in the cured product portion, and very small crater-like holes were observed on the surface, but the columnar shape was maintained as it was, and hardly any decrease in hardness was observed. That is, the effect of the decomposition treatment cannot be expected only by heating to 300 ° C.

<< Examples 11 and 12 >> 35 parts by weight of styrene were mixed with 65 parts by weight of an unsaturated polyester comprising phthalic anhydride, fumaric anhydride and propylene glycol, and the polymerization inhibitor methoxyhydroquinone was added in an amount of 0.1 part.
After adding 01 parts by weight, the mixture was stirred and dissolved at room temperature to obtain an unsaturated polyester resin. Further, 36 parts by weight of polydipropylene adipate was stirred and dissolved at room temperature in 64 parts by weight of 2-hydroxyethyl methacrylate to obtain a low-shrinking agent. 26 parts by weight of a low-shrinking agent and 1 part by weight of a polymerization initiator 1,1- (t-butylperoxy) 3,3,5-trimethylcyclohexane are added to 74 parts by weight of the unsaturated polyester resin, and the mixture is stirred and mixed. Thus, a resin composition was obtained.

Next, the filler calcium carbonate 1
7.8 parts by weight, 48.5 parts by weight of aluminum hydroxide, 1.5 parts by weight of zinc stearate as a release agent, and 0.4 parts by weight of carbon powder as a colorant were transferred to a kneader, and dry-mixed. . After about 5 minutes, 22 parts by weight of the previously mixed resin composition was gradually added to the uniformly mixed dry mixture,
The mixture was kneaded to obtain a uniform paste-like mixture. Further, 9.8 parts by weight of glass fibers were added to this paste-like mixture in an extremely short time while being uniformly dispersed, and when the glass fibers were wet and uniformly dispersed, kneading was completed to produce a molding material. .

Next, the electromagnetic laminated steel sheet provided with the electromagnetic winding is supplied into a mold, and the resin-cured material is subjected to injection molding at a molding temperature of 150 ° C. to obtain a product containing a cured thermosetting resin. A certain mold motor was obtained. The thickness of the molded portion of this molded motor was 10 mm at the maximum.

Next, this mold motor was immersed in a decomposition solution composed of ethylene glycol and charged in a decomposition tank.
Thereafter, nitrogen gas was supplied to the decomposition tank from a nitrogen gas cylinder through a nozzle, and the gas in the decomposition tank was replaced with nitrogen gas. Then, the mixture was heated to 300 ° C. and kept for 5 hours (Example 11). The same procedure was followed except that nitrogen gas was not replaced (Example 12).

After 5 hours, the mold motor was taken out of the decomposition solution. In both cases, the cured portion of the thermosetting resin in the mold motor collapsed and swelled in a gel state, so that it could be easily peeled off. That is, the electromagnetic members such as the electromagnetic winding and the electromagnetic laminated steel plate could be easily separated and collected from the molded motor.

In the case of Example 11 in which the pretreatment for nitrogen substitution was performed, the maximum pressure in the decomposition tank during the decomposition treatment was 10 kg / cm.
² became the pressure at approximately 300 ° C. of ethylene glycol. The decomposition solution after the treatment was slightly brownish except for a precipitate derived from the decomposition of the thermosetting resin.
On the other hand, in the case of Example 12 in which nitrogen substitution was not performed, the maximum pressure in the decomposition tank during the decomposition treatment was 20 kg / cm.
More than ² , more decomposed gas was generated, and the decomposed liquid after the treatment was also dark brown. That is, the degradation of the decomposition solution was slightly observed. Further, components derived from the oxidation of ethylene glycol, such as aldehydes, were also detected from the analysis of the generated gas, and it was confirmed that the oxidation was progressing.

Also, on the surface of copper or iron, which is the material of the electromagnetic member of the electromagnetic winding and the electromagnetic laminated steel sheet separated and recovered,
Example 11 in which the nitrogen substitution pretreatment was performed had a clearly lower degree of oxidative deterioration. Thus, the quality of metals and the like to be recovered can be improved.

As shown in this embodiment, the decomposition liquid of ethylene glycol causes the cured portion of the cured thermosetting resin in the mold motor using the unsaturated polyester resin as the binder to have a large decrease in hardness to such an extent that it can be peeled off with bare hands. Show. Further, by performing the pretreatment of nitrogen substitution, the pressure during the decomposition treatment can be suppressed, and the degradation of the decomposition liquid and the generation of the decomposition gas can be suppressed. Moreover,
Oxidation of copper and iron to be separated and recovered can be suppressed, and higher-grade metals and the like can be recovered. In the present embodiment, the mold motor is subjected to the disassembling process as it is. However, the disassembling process may be performed after performing a pretreatment such as coarse crushing and cutting. By doing so, the thickness of the cured resin portion from the outer surface is reduced, so that the time for immersion in the decomposition solution can be shortened.

<< Examples 13 to 16 and Comparative Examples 6 to 8 >>
In the present example, a laminate, which is a product using an epoxy resin as a binder, was disassembled. After impregnating the glass fiber woven fabric with the epoxy resin, the solvent was evaporated by heating to prepare a prepreg. Next, the prepregs were cut and overlapped, and a copper foil on which an adhesive was coated with a modified epoxy resin was placed on the upper surface, inserted into a press, and cured by heating and pressing to obtain a copper-clad laminate.

In this example, a decomposition solution composed of ethylene glycol was used. After the laminate was immersed in the decomposition solution and charged in the decomposition tank, the decomposition tank was sealed, a vacuum pump was connected to a nozzle provided in the decomposition tank, and the gas in the decomposition tank was evacuated and depressurized. Thereafter, the entire decomposition tank was heated at 270 ° C. for 5 hours.
(Example 13) Further, the processing temperatures were set to 200 (Comparative Example 6), 230 (Comparative Example 7), 240 (Comparative Example 8), 250 (Example 14), and 3
00 (Example 15) The same process was carried out except that the temperature was changed to 00 ° C. Further, the same procedure was performed at 270 ° C. except that the pressure was not reduced by the vacuum pump (Example 16).

As a result, when the treatment temperature was 200, 230 or 240 ° C., although traces of discoloration were observed in the cured portion of the thermosetting resin, the shape of the copper-clad laminate remained and the strength was almost changed. Did not. On the other hand, in the case of 250, 270 and 300 ° C., which is 250 ° C. or higher, the resin as the binder is completely decomposed and dissolved or dispersed in the decomposition solution, and the laminate is made of glass fiber woven fabric, copper Only the foil was left. The glass fiber woven fabric was in a state where it could be easily separated into the number of sheets laminated in the laminate manufacturing process. Similarly, when the treatment was carried out at 270 ° C. without performing the evacuation and decompression by the vacuum pump, the laminate only left the glass fiber woven fabric and the copper foil as the base material.

However, in the case of performing the pretreatment of the exhaust pressure reduction,
The maximum pressure in the decomposition tank during the decomposition treatment is 10 kg / cm ^{2, which} is almost the pressure of ethylene glycol at 300 ° C.
The decomposition solution after the treatment was slightly brownish except for the precipitate derived from the decomposition of the cured thermosetting resin. On the other hand, when nitrogen substitution was not performed, the maximum pressure in the decomposition tank during the decomposition treatment exceeded 20 kg / cm ² , more decomposition gas was generated, and the decomposition liquid after the treatment was also thick. It was brownish, and it was recognized that the decomposition solution was further deteriorated.

The degree of oxidative deterioration of the copper foil recovered after the separation was clearly reduced when the copper foil was degassed under reduced pressure. Also, in the case of glass fiber woven fabrics, degassing under reduced pressure is less likely to cause deterioration of the liquid, so that dirt due to the decomposition liquid is less, and washing is easier.

As described above, according to the present invention, it is possible to rapidly decompose a laminated board which is a cured resin using an epoxy resin which is a thermosetting resin as a binder. Further, by evacuating under reduced pressure, the pressure at the time of the decomposition treatment can be suppressed, and the deterioration of the decomposition liquid and the generation of the decomposition gas can be suppressed. Further, it is possible to suppress oxidation of copper and a base material such as a glass woven fabric to be recovered after separation, and to recover higher quality metals and the like. Therefore, this treatment method in which the gas in the decomposition tank is evacuated and decompressed and heated to 250 ° C. or higher can easily separate and separate the cured thermosetting resin, and can be used for metal such as copper foil or glass woven fabric. This is a processing method that separates and collects materials easily and with good quality, and causes less degradation of the decomposition solution used. The degree of pressure reduction is preferably as close to vacuum as possible. Preferably 10 mmHg
It is as follows. In this case, the base material made of polyester, nylon, acrylic, or the like can be decomposed in the same manner as the epoxy resin.

Embodiments 17 to 19 In this embodiment, a case will be described in which a printed circuit board, which is a product using a phenol resin as a binder, is disassembled. After impregnating kraft paper with the phenolic resin varnish, the solvent was evaporated by heating to produce a prepreg. Next, the prepregs were cut, overlapped, inserted into a press, and heated and pressed to harden the phenol resin to obtain a laminate. Furthermore, through the process of circuit printing, etching, etc. on this copper clad laminate,
A printed circuit board was obtained by forming a conductor pattern and mounting electronic components.

In this embodiment, hydroquinone was added as an antioxidant to propylene glycol to prepare a decomposition solution. Hydroquinone 1 per 100 parts by weight of propylene glycol
Parts by weight were added. The printed circuit board is immersed in this decomposition solution, and the gas in the decomposition tank is evacuated and decompressed with a vacuum pump.
Heated at 270 ° C. for 5 hours (Example 17). The same conditions were used when a decomposition solution consisting of propylene glycol alone without the addition of hydroquinone was used (Example 18), and when the decomposition solution was propylene glycol only and the exhaust pressure was not reduced (Example 19).

As a result, under any processing conditions, the cured thermosetting resin as a binder is decomposed and dissolved or dispersed in a decomposition solution, and the kraft paper as a base material is partially decomposed and deformed to a carbonized state. And the laminate was partially peeled off. The copper foil and the electronic component were separated from the laminate and existed in the decomposition solution due to the force due to the deformation. Further, a thermoplastic resin such as polybutylene terephthalate constituting an electronic component has fallen into the liquid.

However, the pressure at the time of the decomposition reaction differs under three conditions. The pressure in the case of not decompressing and decompressing with a decomposition solution containing only propylene glycol is 60 kg / cm ² , but the decompression and decompression is 30 kg / cm ^2. / Cm ² , and 20 kg by adding hydroquinone.
/ Cm ² . This indicates that the gas generated during decomposition can be reduced by reducing the pressure of the exhaust gas and further adding hydroquinone. That is, generation of gas due to decomposition and degradation of the decomposition liquid propylene glycol and generation of gas due to secondary decomposition of the cured thermosetting resin can be suppressed. Therefore, the decomposition liquid is less deteriorated, and the decomposition product derived from the cured thermosetting resin is also a solid or liquid, so that it can be easily collected and reused.

When the decomposition solution after decomposition was observed, it was found that when the decomposition solution was decomposed only with propylene glycol without exhausting under reduced pressure, the stain was most intensely blackened and an odor was felt. In comparison, when the exhaust pressure was reduced or hydroquinone was further added, the degree of dirt was small and the odor was not felt much.

When the recovered and separated copper foils were compared under the three conditions, the copper gloss remained well when the exhaust pressure was reduced or when hydroquinone was further added. On the other hand, when decomposed with propylene glycol alone without evacuation under reduced pressure, the surface was oxidized, and much dirt was found due to deterioration of the decomposition solution.

As described above, a printed circuit board, which is a product using a phenol resin, which is a thermosetting resin, as a binder,
The resin component or the base material could be rapidly decomposed by the decomposition liquid containing propylene glycol, and the copper foil and the electronic component could be separated and collected. Further, the present invention is a method that enables recovery of valuable resources and volume reduction of a printed circuit board, and a phenol substrate is a suitable object. Further, in the present invention, the degradation of the decomposition solution can be suppressed by reducing the pressure of the exhaust gas or adding hydroquinone, and the metal or the like can be recovered with high quality. Further, since the amount of generated gas is small, the pressure does not increase significantly, and a high pressure resistance is not required for the decomposition tank.

Example 20 In this example, a cured resin obtained by further coating a printed circuit board using an epoxy resin as a binder with a urethane resin was decomposed. After impregnating the glass nonwoven fabric and the glass woven fabric with the epoxy resin varnish, the solvent was evaporated by heating to produce a prepreg. Next, the prepreg was cut, superposed together with a copper foil, inserted into a press, and heated and pressed to cure the epoxy resin to obtain a copper-clad laminate. Further, a printed circuit board was obtained by forming a conductor pattern on the copper-clad laminate through steps such as circuit printing and etching, and mounting electronic components thereon. Next, the printed circuit board was coated with a urethane resin having a thickness of about 2 cm and cured.

This printed circuit board was immersed in a decomposition solution of tetralin as a decomposition solution and heated at 280 ° C. for 5 hours. As a result, first, the urethane resin was completely decomposed and dissolved in the solvent, and the epoxy resin was also decomposed and dissolved or dispersed in the decomposition solution. In addition, the laminate of the woven fabric and the nonwoven fabric was peeled off as the base material. In addition, due to the decomposition of the binder, the copper foil and the electronic component were separated from the laminate and existed in the decomposition solution. In addition, a thermoplastic resin such as polybutylene terephthalate constituting an electronic component has fallen into the liquid. The solder for mounting electronic components was collected while remaining attached to the copper foil.

As described above, according to the present invention, a printed circuit board, which is a cured resin obtained by using an epoxy resin, which is a thermosetting resin, as a binder and further coating with a urethane resin,
By immersion in the tetralin decomposition solution, the resin component could be rapidly decomposed, and the electronic component, glass woven fabric, and nonwoven fabric could be recovered. In the present invention, the decomposition tank was not subjected to the pretreatment before the decomposition treatment. However, as described above, when a slight oxidation of the contained metals or the like becomes a problem, the pressure is reduced by the exhaust or the chip is removed. A deaeration treatment by nitrogen substitution can be used, and a treatment with less oxidation deterioration can be performed by evacuating and reducing the pressure after the nitrogen substitution. Also, as described above, after the decomposition solution is repeatedly used, the dissolved substance can be separated and reused,
It can be used as fuel as it is as fuel.

Comparative Examples 9 and 10 As a comparative example of the decomposition treatment method of the present invention, a laminate using the epoxy resin as the binder used in Example 9 was immersed in a decomposition solution composed of n-tetradecane or liquid paraffin. Then, it was heated at 300 ° C. for 5 hours. The rate of decomposition solution penetration and the surface hardness of the thermosetting resin portion after the decomposition solution immersion treatment were measured. as a result,
There was no change in the appearance of the cured product, and there was almost no decrease in the hardness of the decomposed liquid permeated into the cured product. That is, the effect of the decomposition treatment cannot be expected with a decomposition solution composed of n-tetradecane or liquid paraffin.

[0109]

As described above, by using the decomposition treatment method according to the present invention, a product containing a cured thermosetting resin can be easily decomposed. In addition, since the resin cured product is continuously decomposed or separated by the decomposition treatment apparatus of the present invention, and each component can be reused, the amount of waste treatment can be reduced by efficient decomposition treatment.

[Brief description of the drawings]

FIG. 1 is a schematic longitudinal sectional view showing the configuration of an apparatus for decomposing a product containing a thermosetting resin cured product of the present invention.

FIG. 2 is a schematic longitudinal sectional view showing another configuration of a device for decomposing a product containing a cured thermosetting resin of the present invention. It is a longitudinal section showing the schematic structure of the decomposition processing equipment of other examples.

FIG. 3 is a flowchart for explaining each step of a method for decomposing a product containing a cured thermosetting resin according to the present invention.

[Explanation of symbols]

 1, 2 hopper 3 decomposition tank 4 nozzle 5 screw 6 heater 7 opening 8 decomposition liquid replenisher 11 decomposition tank 12 solid-liquid separation tank 13 dissolution separation tank 14 first distillation column 15 drying tank 16 second distillation column 17 third distillation column 18 heater

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 61/06 C08L 61/06 61/20 61/20 63/00 63/00 Z 67/06 67/06 75/04 75/04 H02K 5/02 H02K 5/02 F term (reference) 4F301 AA21 AA22 AA23 AA24 AA25 AA29 CA02 CA04 CA09 CA12 CA23 CA24 CA32 CA41 CA53 CA64 CA71 CA72 4J002 CC031 CC131 CD001 CF211 CK021 DE019 DE087 DG048 DH048 ED026 EE058 FD078 4J027 AB02 AB06 AB07 AB16 AB24 AB36 BA05 BA08 CA11 CA19 CA36 CA38 CD01 5H605 BB05 CC03 FF06 FF11

Claims (21)

[Claims] 1. A step of (a) bringing a product containing a cured thermosetting resin into contact with a decomposition solution containing a solvent capable of decomposing the cured thermosetting resin in a decomposition tank; and (b) the decomposition solution. Is heated to a temperature of at least 250 ° C. and less than the critical temperature of the solvent. 2. The method for decomposing a product containing a cured thermosetting resin according to claim 1, wherein the decomposition solution is vaporized and then brought into contact with the product. 3. After the step (a) and before the step (b),
3. The method for decomposing a product containing a cured thermosetting resin according to claim 1, further comprising: (a ′) a step of removing oxygen from the decomposition tank. 4. The thermosetting resin curing according to claim 3, wherein the step (a ′) comprises a step of replacing gas in the decomposition tank with nitrogen gas and / or a step of evacuating the decomposition tank. Method of decomposing a product containing a substance. 5. The thermosetting resin according to claim 1, wherein the solvent in the step (a) decomposes the thermosetting resin by solvolysis or catalytic action. How to disassemble the product. 6. The method according to claim 1, wherein the solvent in the step (a) is ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, isoprene glycol, triethylene glycol, tetraethylene glycol, 2-methoxyethanol, 2-ethoxyethanol, or 2-dimethoxy. Ethanol, 2-isopropoxyethanol, 2-butoxyethanol, 2-isopentyloxyethanol, 2-hexyloxyethanol,
-Phenoxyethanol, 2-benzyloxyethanol, 1-methoxy-2-propanol, 1-ethoxy-
At least one selected from the group consisting of 2-propanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether and tripropylene glycol monomethyl ether A method for decomposing a product containing the cured thermosetting resin according to claim 1, which is a seed. 7. The pre-solvent in step (a) is tetralin, biphenyl, naphthalene, 1,4-hydroxynaphthalene, naphthol, 1,4-naphthoquinone, pitch, creosote oil, methyl isobutyl ketone, isophorone, At least one selected from the group consisting of hexanone, 2-heptanone, 4-heptanone, diisobutyl ketone, acetonylacetone, holon, cyclohexanone, methylcyclohexanone and acetophenone
A method for decomposing a product containing the cured thermosetting resin according to claim 1, which is a seed. 8. The method for decomposing a product containing a cured thermosetting resin according to claim 6, wherein the decomposition solution in step (a) contains calcium oxide. 9. The method according to claim 8, wherein the content of the calcium oxide is 10 parts by weight or less with respect to 100 parts by weight of the solvent in the decomposition solution. 10. The decomposition treatment of a product containing a cured thermosetting resin according to claim 8 or 9, further comprising the step of (f) adding carbon dioxide to the solution obtained in step (a) to neutralize calcium oxide. Method. 11. The method for decomposing a product containing a cured thermosetting resin according to claim 1, wherein the decomposition solution in step (a) contains an antioxidant or a reducing agent. 12. The method according to claim 12, wherein the antioxidant or the reducing agent is hydroquinone, methoquinone, benzoquinone, naphthoquinone,
2. The at least one member selected from the group consisting of butylcatechol, butylhydroquinone, sodium hypophosphite, sodium thiosulfate, and ascorbic acid.
A method for decomposing a product containing the cured thermosetting resin according to claim 1. 13. The thermosetting resin cured product in the step (a) is selected from the group consisting of a cured unsaturated polyester resin, a cured epoxy resin, a cured phenol resin, a cured polyurethane resin, and a cured amino resin. A method for decomposing a product containing a cured thermosetting resin according to any one of claims 1 to 12, which is at least one of the following. 14. The method for decomposing a product containing a cured thermosetting resin according to claim 1, wherein the product in the step (a) is a mold motor or a mold transformer containing a metal member. 15. The woven or non-woven fabric comprising glass fiber, polyester fiber, polyamide fiber, acrylic fiber or aramid fiber, wherein the product in step (a) is:
2. A resin laminate obtained by laminating a prepreg obtained by impregnating a thermosetting resin on at least one kind of substrate selected from the group consisting of paper, cotton cloth and asbestos.
A method for decomposing a product containing the thermosetting resin cured product according to any one of claims 14 to 14. 16. The printed circuit board according to claim 1, wherein the resin laminate is a printed circuit board on which a conductive pattern is formed and an electronic component is mounted.
A method for decomposing a cured thermosetting resin according to claim 5. 17. After the step (b), (c) a step of solid-liquid separation of a mixture containing the heated thermosetting resin cured product and the decomposition liquid, and (d) a step of dissolving the separated solid to form a solution. The method for decomposing a product containing a cured thermosetting resin according to any one of claims 1 to 16, further comprising: a step of obtaining; and (e) subsequently separating a residual solid content from the solution. 18. In the step (d), acetone, acetylacetone, acetaldehyde, ethyl acetoacetate,
Selected from the group consisting of methyl acetoacetate, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, methyl isopropyl ketone, dimethyl sulfoxide, dimethylformamide, ethyl acetate, isopropyl acetate, butyl acetate, tetrahydrofuran, dioxane, diethyl ether, water, ethanol, and methanol The method for decomposing a product containing a cured thermosetting resin according to claim 17, wherein the separated solids are dissolved by at least one of the following. 19. A product containing a cured thermosetting resin and a decomposition solution containing a solvent capable of decomposing the cured thermosetting resin are accommodated, and heated to a temperature of 250 ° C. or higher and lower than the critical temperature of the solvent. Thermosetting resin curing device comprising a decomposition tank provided with a means for performing Decomposition equipment for products containing waste. 20. A supply means for supplying a product containing the cured thermosetting resin and a decomposition solution containing a solvent capable of decomposing the cured thermosetting resin, wherein the supplied product and the decomposition solution are supplied. 20. The apparatus for decomposing a product containing a cured thermosetting resin according to claim 19, comprising an extruding means for mixing and continuously extruding, and a means for heating the product and the decomposition liquid in the extruding means. 21. The apparatus for decomposing a product containing a cured thermosetting resin according to claim 20, wherein the extruding means can apply a shear stress to the product and the decomposition solution.