JPH093184A - Thermosetting composition, mold material, and method for decomposition of molded mold material - Google Patents

Abstract

PURPOSE: To obtain a thermosetting composition which rapidly decomposes to a great extent when subjected to, e.g. pyrolysis or solvolysis by blending an unsaturated polyester, an addition-polymerizable monomer and a specified monomer undergoing ring-opening polymerization. CONSTITUTION: This composition contains at least an unsaturated polyester, an addition-polymerizable monomer and a monomer undergoing ring-opening polymerization, wherein the monomer undergoing ring-opening polymerization comprises at least one selected from a group consisting of cyclic ketene acetals and methylenedioxolane derivatives. It is desirable that this composition further contains an aliphatic polyester. The composition forms a three-dimensional crosslinked structure having an ester linkage not only in the main chain but also in the crosslinking chain after curing and molding. Therefore, it rapidly decomposes to a great extent when subjected to, e.g. pyrolysis or solvolysis. The mold material containing the composition can be very readily decomposed by a prescribed decomposition treatment when the molded material thereof is discarded.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermosetting composition, a molding material using the composition, and a method for decomposing a molded product.

[0002]

2. Description of the Related Art A thermosetting composition having an unsaturated polyester and an addition polymerizable monomer as a skeleton is sometimes used alone, but most of them are used as a composite material, and about 80% of the production amount is fiber. Used as a reinforced plastic (FRP). This thermosetting composition is easily applied to fillers such as inorganic substances, additives, and reinforcement by fibers, and is therefore applied to molding materials, laminates, adhesives, paints and the like. On the other hand, since these resins are three-dimensionalized by a curing reaction and generally become an insoluble and infusible solid, it has been difficult to decompose them from the past, and it is said that they are difficult to adapt to regeneration treatment and reuse. I had no choice but to discard it. The molding material is a molding material in which a resin as a binder is filled with an inorganic material such as glass fiber, calcium carbonate, talc, or silica, or an organic material such as pulp or wood. The addition of the above-mentioned filler makes it a material having a large specific strength and specific rigidity, and is thus applied to various fields in the industrial field and consumer field.

Since this molding material is a composite material,
Generally, it is difficult to process for recycling after use. Further, if the binder resin is a thermosetting resin, it becomes three-dimensional by the curing reaction and generally becomes an insoluble and infusible solid, so that it has been difficult to decompose it from the past, and it is difficult to recycle or reuse it. It had to be discarded because it was difficult to fit. However, recently, as the problem of waste has received attention,
Reusable / recycling technology development was required, and consideration was given to using raw materials by thermal decomposition. However, these thermosetting resins or molding materials have the advantages such as hardness, strength, heat resistance, flame retardancy, and chemical resistance that make waste treatment technically difficult. There is.

[0004]

The problem of waste is becoming more and more serious, and the development of technologies for reducing the volume of discarded thermosetting compositions or molded moldings, and processing technologies for reuse, etc. Is in a hurry. In particular, unsaturated polyester resins reinforced with fibers are frequently used in the production of large products such as fishing boats, tanks, and housing equipment, so that the decomposition and regeneration of wastes are serious. In addition, many molding materials using a thermosetting resin as a binder are often used as structural materials due to their strength and the like, and often include other materials such as metals. The fact that metals and the like are valuable materials more expensive than resin materials and hinders the possibility of recycling and reuse thereof has become a bigger problem. That is, at present, the problem of waste cannot be solved by the conventional configuration and processing method for the molding material. It is an object of the present invention to provide a thermosetting composition and a molding material that can be easily treated when discarded. Another object of the present invention is to provide a simple method for disassembling a molded body of molding material.

[0005]

The thermosetting composition of the present invention contains at least an unsaturated polyester, an addition polymerizable monomer, and a ring-opening polymerizable monomer, and the ring-opening polymerizable monomer is a cyclic ketene acetal or At least one selected from the group consisting of methylenedioxolane derivatives
It is a seed. This thermosetting composition preferably further contains an aliphatic polyester. The molding material of the present invention contains a thermosetting composition composed of at least an unsaturated polyester, an addition polymerizable monomer, a ring-opening polymerizable monomer, and an aliphatic polyester as a binder, and the ring-opening polymerizable monomer is a cyclic ketene acetal. And at least one selected from the group consisting of methylenedioxolane derivatives.

Further, the molding material of the present invention contains an unsaturated polyester, an addition polymerizable monomer, and an aliphatic polyester as a binder, and further contains aluminum hydroxide, aluminum nitrate hydrate, calcium sulfate hydrate,
Calcium phosphonate hydrate, calcium dihydrogen phosphate hydrate, calcium oxalate hydrate, magnesium hydroxide, magnesium hydrogen phosphate hydrate, magnesium phosphate hydrate, magnesium oxalate hydrate, and zinc phosphate water It contains at least one selected from the group consisting of Japanese products. It is desirable that this mold material further contains a base.

As the above-mentioned aliphatic polyester, polycaprolactone, polypropiolactone, polylactic acid, polyglycolic acid, polyethylene adipate, polybutylene adipate, polytetramethylene adipate, polyethylene succinate, polybutylene succinate, polycaprolactone diol, It is preferably at least one selected from the group consisting of polycaprolactone triol and a copolymer of 3-hydroxyalkanoate.

The method for decomposing a molded molding of the present invention comprises a molded molding containing at least an unsaturated polyester, an addition-polymerizable monomer and an aliphatic polyester as a binder, at least a base, a monohydric alcohol and dimethyl sulfoxide. And a step of immersing in a decomposition solution containing. The mixing ratio of the monohydric alcohol and dimethyl sulfoxide in the decomposition solution is preferably 40/60 or less in volume ratio.

Further, in the method for decomposing a molded molding of the present invention, a molded molding containing at least an unsaturated polyester, an addition-polymerizable monomer, and an aliphatic polyester as a binder is used at least with a base and a monohydric alcohol. A holding step of maintaining the state of being immersed in a decomposition solution containing dimethylsulfoxide, a filtration step of filtering solid components insoluble in the decomposition solution, an injection step of injecting water or a monohydric alcohol into the filtrate after the filtration, and after the injection It has a second filtration step of filtering solids, and a distillation step of distilling water or monohydric alcohol from the solution content after the injection.

[0010]

The thermosetting composition of the present invention contains an unsaturated polyester, an addition polymerizable monomer, and a ring-opening polymerizable monomer, and the ring-opening polymerizable monomer is a cyclic ketene acetal and / or methylenedioxolane. After curing and molding, a three-dimensional crosslinked structure having an ester bond not only in the main chain but also in the crosslinked chain is formed by the copolymerization of the unsaturated polyester, the addition polymerizable monomer, and the ring-opening polymerizable monomer. For this reason, when the thermal decomposition treatment, the solvolysis treatment or the like is performed, the decomposition is rapid and the degree of decomposition is large.

If the above thermosetting composition further contains an aliphatic polyester, the aliphatic polyester is dispersed in the three-dimensional structure after the curing and molding. Therefore, by immersing the thermosetting composition after curing and molding in a decomposition solution containing at least a base and a solvolytic solvent, the decomposition solution is rapidly added to the composition even at room temperature due to the presence of the aliphatic polyester. And the aliphatic polyester undergoes solvolysis. Also,
Among the ester bonds in the unsaturated polyester resin constituting the composition skeleton, and among the ester bonds in the crosslinked chain formed by the ring-opening polymerization of cyclic ketene acetal or methylenedioxolane, those which undergo solvolysis appear,
It loses its three-dimensional structure and the thermosetting composition collapses.

A molding material containing an unsaturated polyester, an addition-polymerizable monomer, an aliphatic polyester, and a ring-opening polymerizable monomer as a binder, and the ring-opening polymerizable monomer is a cyclic ketene acetal and / or methylenedioxolane is a cured material thereof. After that, a three-dimensional crosslinked structure having an ester bond in both the main chain and the crosslinked chain is formed by the copolymerization of the unsaturated polyester, the addition-polymerizable monomer, and the ring-opening polymerizable monomer, and the fat in the three-dimensional structure is formed. The group polyester is in a dispersed state. Therefore, the mold material after curing and molding is immersed in a decomposition solution containing at least a base and a solvolytic solvent, so that the decomposition solution rapidly penetrates into the composition due to the presence of the aliphatic polyester, Among the ester bonds in the unsaturated polyester resin which constitutes the composition skeleton after the aliphatic polyester is subjected to solvolysis, and in the ester bonds in the crosslinked chain formed by the ring-opening polymerization of cyclic ketene acetal or methylenedioxolane. Some appear to undergo solvolysis, the binder resin loses its three-dimensional structure, and the molded body collapses.

In the above constitution, the aliphatic polyester is polycaprolactone, polypropiolactone,
Selected from the group consisting of copolymers of polylactic acid, polyglycolic acid, polyethylene adipate, polybutylene adipate, polytetramethylene adipate, polyethylene succinate, polybutylene succinate, polycaprolactone diol, polycaprolactone triol, 3-hydroxyalkanoate By having at least one of the above, the affinity for the decomposition solution containing at least the base and the solvolytic solvent is high, and the solvolysis is high. Therefore, the molding material containing these contains at least the base and the hydrophilic solvent. Penetration of decomposition solution when immersed in decomposition solution,
The solvolysis of the unsaturated polyester resin crosslinked structure as the binder proceeds more efficiently and effectively.

Further, it contains an unsaturated polyester, an addition-polymerizable monomer, and an aliphatic polyester as a binder, and further contains aluminum hydroxide, aluminum nitrate hydrate, calcium sulfate hydrate, calcium phosphonate hydrate, and phosphoric acid dihydrate. A composition containing at least one of calcium hydrogen hydrate, calcium oxalate hydrate, magnesium hydroxide, magnesium hydrogen phosphate hydrate, magnesium phosphate hydrate, magnesium oxalate hydrate, and zinc phosphate hydrate. After curing and molding, the molding material is such that the aliphatic polyester is dispersed in the three-dimensional crosslinked structure formed by the copolymerization of the unsaturated polyester and the addition polymerizable monomer, and the above-mentioned metal compound is filled therein. Is in a state. For this reason, by heating the mold material after curing and molding to the decomposition point of at least the filled inorganic compound, these metal compounds decompose and release water at the same time. Then, some of the ester bonds of the ester bonds in the unsaturated polyester resin constituting the composition skeleton are also hydrolyzed, the binder resin loses its three-dimensional structure, and the molded body collapses. Further, in the above-mentioned constitution, if the mold material further contains a base, it becomes a catalyst in the hydrolysis reaction of the binder resin by heating after curing and molding, and the release of water from the metal compound, so that the decomposition treatment is promoted. Can be done more quickly.

Further, in the above constitution, the aliphatic polyester is polycaprolactone, polypropiolactone, polylactic acid, polyglycolic acid, polyethylene adipate, polybutylene adipate, polytetramethylene adipate, polyethylene succinate, polybutylene succinate, polybutylene succinate, At least one selected from the group consisting of copolymers of caprolactone diol, polycaprolactone triol, and 3-hydroxyalkanoate
The seed has a high affinity for water and a high hydrolyzability when heated, and is easily decomposed by water released by the inorganic compound, and promotes water penetration into the binder resin phase, resulting in unsaturated. The hydrolysis of the polyester resin crosslinked structure proceeds more efficiently and effectively.

Further, the decomposition solution used in the decomposition treatment method of the molded molding material of the present invention contains at least a base, a monohydric alcohol and dimethyl sulfoxide. This decomposition solution has a high affinity for aliphatic polyester and a high solvent-solving ability, and quickly penetrates into the molding material,
Since dimethylsulfoxide accelerates the solvolysis reaction due to the action of the base and the monohydric alcohol, the three-dimensional structure of the molding material is rapidly eliminated and destroyed. Further, in the above-mentioned constitution, when the mixing volume ratio of the monohydric alcohol and dimethyl sulfoxide is 40/60 or less, the decomposition solution permeates into the molding material molded body, and the solvolysis of the binder is carried out most quickly. The green compact collapses efficiently and effectively.

Further, according to the method for decomposing a molded molding material of the present invention, the molded molding material and the decomposing solution after the decomposing processing are separated, and the molding material and the decomposing method of the present invention are not discarded. It can be reused for each purpose including.

[0018]

EXAMPLES The unsaturated polyester used in the present invention is
It can be obtained by polycondensing unsaturated polybasic acid or saturated polybasic acid with glycols by a known method. Examples of the unsaturated polybasic acid include maleic anhydride, fumaric acid, itaconic acid, citraconic acid and the like. Examples of the saturated polybasic acids include phthalic anhydride, isophthalic acid, terephthalic acid, adipic acid, sebacic acid, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, endmethylenetetrahydrophthalic anhydride, heptic acid, and tetrabromophthalic anhydride. No. Examples of glycols include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, neopentyl glycol, 1-3 butanediol, 1-6 hexanediol, hydrogenated bisphenol A, bisphenol A propylene oxide compound, and dibromoneopentyl glycol. Is mentioned.

Preferred unsaturated polyesters include copolymers of isophthalic acid and fumaric acid with neopentyl glycol as represented by (Formula 1), phthalic anhydride as represented by (Formula 2), and Examples thereof include a copolymer of maleic anhydride and propylene glycol, an isophthalic acid represented by (Chemical Formula 3), and a copolymer of maleic anhydride and propylene glycol.

[0020]

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[0021]

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[0022]

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In the above formula, n ^{1 to} n ³ are each independently 1 to 30. The unsaturated polyester is practically provided as a solution product dissolved in a polymerizable monomer. Examples of the addition-polymerizable monomer used in the present invention include styrene, vinyltoluene, α-methylstyrene,
Methyl methacrylate, vinyl acetate, diallyl phthalate, diallyl isophthalate, diallyl tetrabromophthalate, phenoxyethyl acrylate, 2-hydroxyethyl acrylate, 1-6 hexanediol diacrylate and the like can be mentioned. In addition, aliphatic polyesters having addition polymerizable ends can also be used. Curability,
Styrene is preferred in consideration of the viscosity control simplicity, cost, and the like. The addition polymerizable monomer is preferably 25 to 15 with respect to 100 parts by weight of the unsaturated polyester.
It is contained in an amount of 0 parts by weight, more preferably 40 to 100 parts by weight.

The aliphatic polyester used in the present invention is a thermoplastic saturated polyester. Among aliphatic polyesters, polymers obtained by ring-opening polymerization of lactones such as polycaprolactone and polypropiolactone represented by the following formula (4); polylactic acid represented by formula (5), and formula (6) A) a polymer of a hydroxy acid such as polyglycolic acid; a glycol represented by the formula (7) such as polyethylene adipate, polybutylene adipate, polytetramethylene adipate, polyethylene succinate, and polybutylene succinate. Copolymer comprising aliphatic dicarboxylic acid; polycaprolactone diol represented by formula (8), polycaprolactone triol represented by formula (9), a polymer having a functional group at the terminal; formula (10) Acrylic-terminated polycaprolactone represented by: 3-hydroxypropionate, 3-
Hydroxybutyrate, 3-hydroxyvalerate, 3
-It is desirable to use polyesters obtained by fermentation of microorganisms such as hydroxyoctanoate.
These polyesters have extremely excellent decomposability with respect to the decomposition solution described below.

[0025]

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[0026]

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Here, n ^{4 to} n ¹⁰ , l ^{1 to} l ² , and m ¹
To m ³ are each independently 10 to 2000, and R ¹ and R ² are each independently a hydrocarbon group having 1 to 20 carbon atoms. The aliphatic polyester is used in an amount of preferably 1 to 100 parts by weight, more preferably 2 to 50 parts by weight, based on 100 parts by weight of the unsaturated polyester. The molding material of the present invention preferably contains a curing agent.
Examples of the curing agent include benzoyl peroxide, t-butylperbenzoate, t-butylperoxybenzoate, t-butylperoxylaurate, t-butylperoxy-
2-ethylhexanoate, t-butyl peroctoate and the like can be mentioned. The curing agent is used in an amount of preferably 0.1 to 5 parts by weight, more preferably 0.2 to 4 parts by weight, based on 100 parts by weight of the unsaturated polyester.

Example 1 A preferred first example of the thermosetting composition of the present invention will be described. The thermosetting composition of the present invention is an unsaturated polyester, an addition polymerizable monomer,
And a ring-opening polymerizable monomer, wherein the ring-opening polymerizable monomer is at least one selected from the group consisting of cyclic ketene acetal and methylene dioxolane. The ring-opening polymerizable monomer used in the present invention is a cyclic ketene acetal represented by the formula (12) in which an exomethylene group is introduced at the 2-position and 4-position of the cyclic acetal represented by the formula (11), and a methylene represented by the formula (13). It is a dioxolane derivative. The cyclic acetal is called 2-methylene-1,3-dioxane or 2-methylene-1,3-dioxepane depending on the number of ring members. These monomers can be ring-opened by radicals to introduce an ester bond on a straight chain. The ring-opening polymerizable monomer is used in an amount of preferably 1 to 150 parts by weight, more preferably 1 to 100 parts by weight, based on 100 parts by weight of the unsaturated polyester.

[0029]

[Chemical 6]

Here, n ^{11 to} n ¹² are each independently 1 to
It is 10. Note that these monomers are not limited to the structures shown here, and may have a structure in which a radical stabilizing group such as an alkyl group or a phenyl group is introduced into each carbon. Next, an example in which the thermosetting composition of the present invention was actually manufactured as a trial is shown.

[Trial Production Example 1] Unsaturated polyester represented by Chemical formula 3 (manufactured by Nippon Shokubai Co., Ltd., trade name: Epolak)
With respect to 55 parts by weight, 35 parts by weight of styrene which is an addition-polymerizable monomer, 9 parts by weight of 2-methylene-1,3-dioxepane which is a cyclic ketene acetal, and a curing agent of tertiary butyl peroxybenzoate (NOF Corporation) (stock)
Product name: Perbutyl Z), 1 part by weight, was added and mixed well to obtain a thermosetting composition. 1 of this composition
It was molded into a plate having a thickness of 1 mm by curing at 30 ° C. for 1 hour.

[Comparative Example 1] 44 parts by weight of styrene which is an addition-polymerizable monomer and 1 part by weight of a tertiary butyl peroxybenzoate curing agent are added to 55 parts by weight of the unsaturated polyester represented by the chemical formula (3). In addition, the mixture was thoroughly mixed to obtain a thermosetting composition. This composition was molded into a plate having a thickness of 1 mm by curing at 130 ° C. for 1 hour.

The molded articles of the prototype 1 and the comparative example 1 had almost no change in basic physical properties such as moldability and strength. Next, a decomposition treatment by glycolysis was performed using these two types of thermosetting composition molded bodies.
Glycolysis was carried out by immersing the thermosetting composition molded articles of Prototype Example 1 and Comparative Example 1 in an ethylene glycol solvent mixed with zinc acetate, which is a catalyst, at 200 ° C. based on a conventional method.
It was conducted under the conditions of 30 atm. As a result of the decomposition treatment, the plate-shaped molded article of the thermosetting composition of Comparative Example 1 maintained its shape although deterioration was observed. On the other hand, it was observed that the thermosetting composition molded article of Prototype Example 1 had a severe degree of disintegration, was divided into several pieces, and no longer maintained its shape.

Further, from the analysis of the dissolved substance and the precipitate in the ethylene glycol liquid after the thermosetting composition molded body of Prototype Example 1 was decomposed, phthalic acid and propylene glycol, which are saturated acids constituting the unsaturated polyester, were analyzed. , And addition reaction products of styrene and maleic acid were detected. On the other hand, in the same analysis of the thermosetting composition molded article of Comparative Example 1, only phthalic acid was detected and propylene glycol could not be confirmed. In the case of Comparative Example 1, out of the two kinds of ester bonds, only the ester bond involving phthalic acid and propylene glycol was decomposed, and the ester bond composed of maleic acid and propylene glycol close to the crosslinked chain could not be decomposed. there were. On the other hand, in Prototype Example 1, due to the presence of 2-methylene-1,3-dioxepane, which is a cyclic ketene acetal, an ester bond is formed not only in the main chain but also in the crosslinked chain in the cured composition. Therefore, it was possible to decompose the cross-linked chain by glycol cis, and the decomposition of the cross-linked chain also made it possible to decompose the ester bond between maleic acid and propylene glycol near the cross-linked portion. As a result, glycol was also detected. As described above, the molded product of the thermosetting composition containing the unsaturated polyester, the addition polymerizable monomer, and the ring-opening polymerizable monomer,
It is a thermosetting composition that can be easily decomposed in glycolysis.

In the present embodiment, an example of the decomposition treatment by glycolysis was described, but the decomposition treatment can also be performed more easily by the solvolysis method and the thermal decomposition method than the conventional products. In addition, in the present embodiment, the example of 2-methylene-1,3-dioxepane which is a cyclic ketene acetal has been described, but the same effect can be obtained by using other cyclic ketene acetals or methylene dioxolane. Further, the configuration and manufacturing method of the thermosetting composition is not limited to this example, for example,
Even if fillers such as calcium carbonate, calcium silicate, barium sulfate, aluminum hydroxide, talc, mica, etc., reinforcing agents such as glass fiber, carbon fiber, etc., thickeners, release agents, colorants, etc. are mixed Of course good. In addition, in the present embodiment, an example of forming a plate shape was used, but the present invention is not limited to this, and a molded body having another shape,
It may be paint, putty, adhesive or the like.

Example 2 A preferred second example of the thermosetting composition of the present invention will be described. To 51 parts by weight of unsaturated polyester (manufactured by Nippon Shokubai Co., Ltd., trade name: Epolak), 32 parts by weight of styrene which is an addition polymerizable monomer, polycaprolactone which is an aliphatic polyester (molecular weight 40,000, Daicel Chemical Industries ( Ltd., trade name: Praxel) 6 parts by weight, cyclic ketene acetal 2-
10 parts by weight of methylene-1,3-dioxepane and 1 part by weight of a curing agent tertiary butyl peroxybenzoate (manufactured by NOF CORPORATION, trade name: Perbutyl Z) were added and mixed well to form a thermosetting composition. Obtained.

This composition was molded into a plate having a thickness of 1 mm by curing at 130 ° C. for 1 hour. Next, this plate-shaped compact was immersed at room temperature in a solution containing 1 part by weight of sodium hydroxide, 15 parts by weight of water, and 15 parts by weight of ethanol. After 50 hours of immersion, this molded body has 50 wt%
Showed a decrease in weight. At this time, the molded body completely lost its shape, the strength of each fragment was extremely reduced, and the shape could be easily broken, so that the molded state could not be maintained. Furthermore, in the thermosetting composition of the present example in which the cyclic ketene acetal was mixed, the ester bond was introduced into the crosslinked chain in the three-dimensional crosslinked structure of the unsaturated polyester resin by the curing molding, and the three-dimensional crosslinked structure was formed. The polycaprolactone is dispersed in it. Therefore, the permeability of the solution containing the base and the monohydric alcohol is improved, and the polycaprolactone and the unsaturated polyester resin, as well as the crosslinked chain, undergo solvolysis by the solution containing the base and the monohydric alcohol, and have a three-dimensional structure. Was cut into smaller pieces and the thermosetting composition completely decomposed. As described above, the thermosetting composition molded product having a cyclic ketene acetal is a thermosetting composition which can be easily decomposed even at room temperature by being immersed in a solution containing a base, methanol and water. Is.

The thermosetting composition of the present invention is
The composition and the compounding ratio of this example are not limited. In addition, in the present embodiment, the example of 2-methylene-1,3-dioxepane which is a cyclic ketene acetal has been described, but the same effect can be obtained by using other cyclic ketene acetals or methylene dioxolane. Further, the thermosetting composition molded body of the present invention is immersed, the solution subjected to decomposition is not limited to the composition of the present example, the compounding ratio, as long as it contains at least a base and a solvolytic solvent. Good. As the base, in addition to the sodium hydroxide shown in this example, metal hydroxides such as calcium hydroxide and potassium hydroxide, metal oxides such as sodium oxide and calcium oxide, sodium ethoxide and potassium t.
-Metal alkoxides such as butoxide. These can be used alone or in combination of two or more. Further, as the solvolysis solvent, methanol, ethylene glycol, ammonia, acetic acid, hydrazine, etc. can be used in addition to ethanol and water used in this example.

Further, in the solution used in this example, in addition to the solvolytic solvent, diethyl ether, dioxane,
Hydrophilic organic solvents such as tetrahydrofuran, acetone, dimethylformamide and dimethylamine may be used alone or in combination of two or more. In addition, in the present embodiment, an example in which it is formed in a plate shape is used, but the present invention is not limited to this, and a molded body having another shape, a paint, a putty, an adhesive, or the like may be used.

<Embodiment 3> A preferred first embodiment of the molding material of the present invention will be described. The molding material of the present invention is a molding material containing an unsaturated polyester, an addition polymerizable monomer, an aliphatic polyester, and a ring-opening polymerizable monomer as a binder, wherein the ring-opening polymerizable monomer is a cyclic ketene acetal and methylenedioxolane. It is at least one selected from the group consisting of The ring-opening polymerizable monomer used in the present invention is a cyclic ketene acetal represented by the formula (12) or a methylenedioxolane derivative represented by the formula (13). These monomers can be ring-opened by radicals to introduce an ester bond on a straight chain. The ring-opening polymerizable monomer is used in an amount of preferably 1 to 150 parts by weight, more preferably 1 to 100 parts by weight, based on 100 parts by weight of the unsaturated polyester. The mold material of the present invention, if necessary, a filler,
Thickeners, mold release agents, waxes, colorants and the like may be added.

As the filler, calcium carbonate, carbonates such as magnesium carbonate, calcium sulfate, barium sulfate, (sulfite) salts such as calcium sulfite, clay, mica, glass balloon, montmorillonite, silicic acid, kaolin, Silicates such as talc, silica, siliceous earth, iron oxide, pumice balloon, titanium oxide, oxides such as alumina, aluminum hydroxide, hydroxides such as magnesium hydroxide, graphite, glass fiber, carbon Inorganic fillers such as fibers and asbestos fibers; as well as organic fillers such as wood flour, chaff, cotton, paper flakes, nylon fibers, polyethylene fibers, wood, pulp and cellulose. The filler is a thermosetting composition 100.
It is preferably added in an amount of 5 to 600 parts by weight, more preferably 20 to 500 parts by weight, based on parts by weight. By adding the filler in such a range, the mechanical strength of the mold material is improved.

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

Next, an example in which the first embodiment of the molding material of the present invention is actually prototyped and molded will be described. [Prototype Example 2] Unsaturated polyester (manufactured by Nippon Shokubai Co., Ltd.,
10.5 parts by weight of styrene which is an addition polymerizable monomer, and polycaprolactone which is an aliphatic polyester (molecular weight 40,000,
1.8 parts by weight of Daicel Chemical Industries, Ltd., trade name: Praxel, 2.1 parts by weight of cyclic ketene acetal 2-methylene-1,3-dioxepane, and a curing agent tertiary butyl peroxybenzoate 0.3 part by weight of (trade name: Perbutyl Z manufactured by Nippon Oil & Fats Co., Ltd.) was added and mixed well to obtain a composition serving as a binder. Next, 57 parts by weight of calcium carbonate as a filler, 2 parts by weight of zinc stearate as a release agent, and 1 part by weight of magnesium oxide as a thickener were transferred to a kneader and mixed by dry mixing. After mixing for about 5 minutes, the binder composition previously mixed is gradually added to this uniformly mixed dry mixture and kneaded.
A uniform paste was obtained. Further, 10 parts by weight of glass fibers were evenly dispersed in this paste-like material, and added in a short time as much as possible. When the glass fibers became wet and were uniformly dispersed, kneading was terminated to obtain a molding material.

Since the molding material thus obtained is in a bulk form, it is usually BMC (Bulk Molding Compound).
And a non-adhesive state despite containing styrene. This mold material is put into a transpot, the mold temperature is 150 ° C., the injection pressure is 150
Transfer molding was performed at kg / cm ² to obtain a plate-shaped molded body. When this molded product is compared with FRP (fiber reinforced plastic) made of unsaturated polyester resin that is commonly used in industry, moldability, curability (curing time, gelling time), strength, etc. are almost the same. It was found that the dimensional stability was superior. However, the spiral flow length is somewhat shortened, but this is not a problem in molding. Therefore, the molding material according to the present invention can be sufficiently applied to applications where FRP materials are usually used.

[Comparative Example 2] Unsaturated polyester 15.6
12.6 parts by weight of styrene, 1.8 parts by weight of polycaprolactone (molecular weight 40,000), and 0.3 part by weight of a tertiary butyl peroxybenzoate curing agent as a binder composition Got To this composition, 57 parts by weight of calcium carbonate, 2 parts by weight of zinc stearate, 1 part by weight of magnesium oxide, and further 10 parts by weight of glass fiber were added to obtain a molding material. The manufacturing method is the same as that of the second prototype. This molding material was put in a transpot, and transfer molding was carried out at a mold temperature of 150 ° C. and an injection pressure of 150 kg / cm ² to obtain a plate-shaped molded body.

Comparative Example 3 Unsaturated polyester 15.6
To 1 part by weight of styrene, 12.6 parts by weight of styrene and 0.3 part by weight of a tertiary butyl peroxybenzoate curing agent were added, and 57 parts by weight of calcium carbonate and 2 parts by weight of zinc stearate were added to the composition as a binder. Parts by weight, magnesium oxide 1 part by weight, and glass fiber 10 parts by weight,
A molding material was obtained. The manufacturing method is the same as that of the second prototype. This molding material was put in a transpot, and transfer molding was carried out at a mold temperature of 150 ° C. and an injection pressure of 150 kg / cm ² to obtain a plate-shaped molded body.

The compositions of these three types of molding materials are shown in Table 1.

[0048]

[Table 1]

Next, a plate-shaped molded body using the molding materials of Prototype Example 2 and Comparative Examples 2 and 3 was added to a solution of 1 part by weight of sodium hydroxide, 3 parts by weight of water, and 21 parts by weight of methanol at room temperature. Soaked in. Table 2 shows the weight change rate of the molded body after the solution immersion times of 25, 50 and 100 hours. The molded body made of the molding material of Comparative Example 2 is
After 100 hours, a weight loss of 15 wt% was exhibited. At this time, the strength was extremely reduced, and the shape could be easily broken, and the molded state could not be maintained.

[0050]

[Table 2]

The molded body of the mold material of Prototype Example 2 had a greater degree of decomposition, and after 100 hours, it was about 40.
It showed a wt% weight loss, and it was confirmed that the binder resin had completely lost its shape, and the packing such as particles was precipitated in the decomposition solution. On the other hand, in the molded product of the molding material of Comparative Example 3, no change in shape could be observed even after 100 hours, and no change in weight or deterioration in strength was observed. The mold material of Comparative Example 3 is a mold material having a conventionally used composition and cannot be treated with a solution containing a base and a monohydric alcohol as used here.

However, in the molding material of Comparative Example 2 having a composition in which polycaprolactone, which is an aliphatic polyester, is mixed, the polycaprolactone is dispersed in the three-dimensional crosslinked structure of the unsaturated polyester resin by curing molding. , The permeability of a solution containing a base and a monohydric alcohol is improved, and polycaprolactone and an unsaturated polyester resin, which are binders of the molding material, undergo solvolysis, so that the molded body can no longer maintain its shape and collapses. did. Furthermore, in the molding material of Prototype Example 2 in which the cyclic ketene acetal was mixed, an ester bond was introduced into the crosslinked chain in the three-dimensional crosslinked structure of the unsaturated polyester resin by curing and molding, so that the base material and the monohydric alcohol were included. The solution also caused the solvolysis of the cross-linked chains, the three-dimensional structure of the binder resin was finely cut, and the molded body decomposed while releasing the filling substance. As described above, the molding material having the cyclic ketene acetal in the binder is a molding material that can be applied similarly to the current FRP material, and can be decomposed even at room temperature by immersing it in a solution containing a base and methanol. A mold material that is easy to process.

The molding material in the present invention is not limited to the composition and the compounding ratio of this embodiment. Also,
The solution obtained by immersing the molded product of the present invention in the mold and subjecting it to decomposition treatment is not limited to the composition and the compounding ratio in this example, and may be any solution containing at least a base and a solvolytic solvent.
As the base, in addition to the sodium hydroxide shown in this example, metal hydroxides such as calcium hydroxide and potassium hydroxide, metal oxides such as sodium oxide and calcium oxide, sodium ethoxide and potassium t. -Metal alkoxides such as butoxide. These can be used alone or in combination of two or more. As the solvolysis solvent, ethanol, ethylene glycol, ammonia, acetic acid, hydrazine, or the like can be used in addition to methanol and water used in this example.

In addition, in the solution used in this example, in addition to the solvolytic solvent, diethyl ether, dioxane,
Hydrophilic organic solvents such as tetrahydrofuran, acetone, dimethylformamide and dimethylamine may be used alone or in combination of two or more. In this embodiment, transfer molding is used when molding the molding material, but compression molding, injection molding or the like may be used. Also,
In this embodiment, the bulk-shaped molding material is described, but in addition to the bulk-shaped molding material, sheet-shaped SMC (sheet mol
ding compound) or granular PMC (petletized type)
molding compound). In addition, although a plate-shaped molded product has been described in the present embodiment, the final molded product obtained from this molding material is, in addition to this, a construction material such as a bathtub, a toilet tank, a water tank, and a washbasin; a chair and a desk. , Household goods such as furniture; civil engineering materials such as tiles, artificial marble and pipes; bodies and parts of transportation equipment such as ships, automobiles, railroads and aircraft; housing equipment; decorative sheets; Can be used in.

<Embodiment 4> A preferred second embodiment of the molding material of the present invention will be described. The molding material of the present invention contains an unsaturated polyester, an addition polymerizable monomer, and an aliphatic polyester as a binder, and contains aluminum hydroxide, aluminum nitrate hydrate, calcium sulfate hydrate, calcium phosphonate hydrate, and phosphoric acid. At least one of calcium dihydrogen hydrate, calcium oxalate hydrate, magnesium hydroxide, magnesium hydrogen phosphate hydrate, magnesium phosphate hydrate, magnesium oxalate hydrate, and zinc phosphate hydrate is included. Each of these metal compounds has a decomposition point at a specific temperature, and at the same time as being decomposed at the decomposition point, it has the property of releasing water of crystallization. The decomposition points of each metal compound are shown in Table 3.

[0056]

[Table 3]

Next, an example in which the second embodiment of the molding material of the present invention is actually prototyped and molded will be described. [Prototype Example 3] Styrene 16.6 parts by weight, polycaprolactone (molecular weight 40,000) 2.4 parts by weight, and curing agent tertiary butyl peroxybenzoate 0.1. 4 parts by weight was added to obtain a binder composition. To this composition, 1.5 parts by weight of a release agent of zinc stearate, 58 parts by weight of calcium phosphonate hydrate, and 0.5 parts by weight of a thickening agent of magnesium oxide were mixed to obtain a well kneaded paste. It was The chopped strands obtained by cutting the glass fibers with a cutter were scattered on a polyethylene film, and the glass fibers were impregnated with the pasty material to obtain a molding material.
After the impregnation, the mold material was wound up to a required length and aged to be thickened to a required consistency. As a result, about 30 parts by weight of glass fiber was added to 100 parts by weight of the paste. The molding material thus obtained is in the form of a sheet, and is therefore one type of molding material usually called SMC, and is in a non-adhesive state despite containing styrene.

[Prototype Example 4] Unsaturated polyester 20.6
A composition which becomes a binder by adding 16.6 parts by weight of styrene, 2.4 parts by weight of polycaprolactone (molecular weight 40,000), and 0.4 parts by weight of a tertiary butyl peroxybenzoate curing agent to parts by weight. Got Based on this composition, the release agent was 1.5 parts by weight of zinc stearate, 58 parts by weight of calcium phosphonate hydrate, 0.5 part by weight of magnesium oxide thickener, and 2 parts by weight of calcium hydroxide as a base. Was mixed well and a paste-like material was obtained. Chopped strands obtained by cutting glass fibers with a cutter were sprinkled on a polyethylene film, and the glass fibers were impregnated with the pasty material to obtain a molding material.
After the impregnation, the mold material was wound up to a required length and aged to be thickened to a required consistency. As a result, about 30 parts by weight of glass fiber was added to 100 parts by weight of the paste.

[Comparative Example 4] Unsaturated polyester 20.6
A composition which becomes a binder by adding 16.6 parts by weight of styrene, 2.4 parts by weight of polycaprolactone (molecular weight 40,000), and 0.4 parts by weight of a tertiary butyl peroxybenzoate curing agent to parts by weight. I got it. For this composition, the release agent zinc stearate. 5 parts by weight, 58 parts by weight of calcium carbonate, and 0.5 parts by weight of a thickener magnesium oxide were mixed to obtain a well kneaded paste. The chopped strands obtained by cutting glass fibers with a cutter were scattered on a polyethylene film, and the glass fiber was impregnated with the pasty material to obtain a molding material 6. After the impregnation, the mold material was wound up to a required length and aged to be thickened to a required consistency. As a result, about 30 parts by weight of glass fiber was added to 100 parts by weight of the paste.

Table 4 shows the compositions of these three kinds of molding materials.

[0061]

[Table 4]

Next, the molding materials of Prototype Example 3, Prototype Example 4 and Comparative Example 4 were respectively put into a flat plate type mold, and a pressure of 100 kg / cm ² was applied by closing the mold to perform compression molding at a temperature of 150 ° C. Then, a plate-shaped molded body was obtained. When the molded articles of the molding materials of Prototype Example 3 and Prototype Example 4 were compared with FRP made of an unsaturated polyester resin which is usually used industrially, moldability and curability (curing time, curing time,
Since the gelling time) and the strength are almost the same, it can be sufficiently applied to applications where FRP is usually used.

Next, the plate-shaped molded body made of these three types of molding materials was heated to 200.degree. The molded body of the molding material of Comparative Example 4 tended to show a slight decrease in strength due to the decomposition of the binder resin due to oxidation.
On the other hand, regarding the molded body of the mold material of Prototype Example 3, the water of crystallization released by the filled calcium phosphonate hydrate due to the decomposition behavior is the three-dimensional skeleton of the unsaturated polyester resin as the binder and the aliphatic polyester. To hydrolyze the ester bond of polycaprolactone,
The shape retained by the binder can no longer be maintained, and the molded molding material collapses. Prototype example 4
The molded body of the molding material of No. 2 was used as a catalyst for the hydrolysis reaction of the binder resin by the water of crystallization released by the decomposition of calcium phosphonate hydrate by the calcium hydroxide contained in addition to the constitution of the molding material of Prototype Example 3. Therefore, the collapse of the molded body of the molding material was completed more quickly.

As described above, a molded body of a molding material containing unsaturated polyester, styrene, and polycaprolactone as a binder and filled with calcium phosphonate hydrate can be heated to 200 ° C. to give calcium phosphonate hydrate. It is a mold material that is easily decomposed because it decomposes due to the hydrolysis of the binder resin by the water of crystallization released by the decomposition of the product. Furthermore, the molding material mixed with calcium hydroxide is a molding material that can be decomposed more quickly in order to accelerate the hydrolysis of the binder resin by the water of crystallization released by the decomposition of calcium phosphonate hydrate. is there.

In this example, only the molding material using calcium phosphonate hydrate was described.
In addition, aluminum hydroxide, aluminum nitrate hydrate, calcium sulfate hydrate, calcium dihydrogen phosphate hydrate, calcium oxalate hydrate, magnesium hydroxide,
The molding material filled with magnesium hydrogen phosphate hydrate, magnesium phosphate hydrate, magnesium oxalate hydrate, or zinc phosphate hydrate was heated to the respective decomposition temperatures shown in Table 3 to carry out the present embodiment. The same effect as the example can be obtained. However, it is necessary to take care so that the temperature during molding does not exceed the decomposition point of each metal compound. In addition to the calcium hydroxide used in this example, the base mixed in the molding material is sodium hydroxide,
A metal hydroxide such as potassium hydroxide, a metal oxide such as sodium oxide and calcium oxide, a sodium ethoxide, a metal alkoxide such as potassium t-butoxide, and the like can be used.

The molding material of the present invention is not limited to the composition of this embodiment. Filler, if necessary,
Thickeners, mold release agents, waxes, colorants and the like may be further added. In addition, although the sheet-shaped molding material is described in the present embodiment, a bulk-shaped BMC other than the sheet-shaped molding material is used.
Alternatively, granular PMC may be used. In addition, although a plate-shaped molded product has been described in the present embodiment, the final molded product obtained from this molding material is, in addition to this, a construction material such as a bathtub, a toilet tank, a water tank, and a washbasin; a chair and a desk. , Household goods such as furniture; civil engineering materials such as tiles, artificial marble and pipes; bodies and parts of transportation equipment such as ships, automobiles, railroads and aircraft; housing equipment; decorative sheets; Can be used in.

<Embodiment 5> A preferred first embodiment of the method for disassembling a molding material according to the present invention will be described. A method for decomposing a molding material according to the present invention is a decomposition solution containing at least a base, a monohydric alcohol and dimethyl sulfoxide, which is a molded material of a molding material containing at least an unsaturated polyester, an addition polymerizable monomer, and an aliphatic polyester as a binder. It is immersed in. First, a molding material containing an unsaturated polyester, an addition-polymerizable monomer, and an aliphatic polyester as a binder was constructed as follows. That is, unsaturated polyester 14.7
5.0 parts by weight of styrene and 0.3 part by weight of a tertiary butyl peroxybenzoate curing agent were added to parts by weight to obtain a composition serving as a binder. 68 parts by weight of calcium carbonate, 1 part by weight of zinc stearate, 1 part by weight of magnesium oxide, and 10 parts by weight of glass fiber were added to this composition to obtain a molding material. The manufacturing method is the same as that of the second prototype of the third embodiment.

This mold material is put in a tonspot,
Transfer molding was performed at a mold temperature of 150 ° C. and an injection pressure of 150 kg / cm ² to obtain a plate-shaped molded body having a thickness of 1 mm. 1 g of the potassium hydroxide which is a base, 1
When immersed in a decomposition solution consisting of 20 g of methanol, which is a polyhydric alcohol, and 55 g of dimethyl sulfoxide, at 80 ° C., the three-dimensional structure of the resin, which is a binder, is almost completely decomposed after 20 hours, and calcium carbonate, which is a filler, etc. Was observed to precipitate in the decomposition solution. That is, the molded body made of the molding material of this example was completely decomposed. As described above, the molded body of the molding material containing unsaturated polyester, styrene, and polycaprolactone as a binder has potassium hydroxide as a base, methanol as a monohydric alcohol, and
By immersing it in a solution of dimethyl sulfoxide, the decomposition treatment can be carried out easily and completely.

The mold material targeted by the decomposition treatment method of the present invention is not limited to the composition used in the examples, and if necessary, a filler, a thickener, a release agent,
It may be filled with wax, a coloring agent or the like. Further, the composition of the decomposition solution is not limited to the composition and the compounding ratio of this embodiment,
For example, as the base, in addition to potassium hydroxide shown in this example, calcium hydroxide, metal hydroxides such as sodium hydroxide, sodium oxide, metal oxides such as calcium oxide, sodium ethoxide, Potassium t
-Metal alkoxides such as butoxide. These can be used alone or in combination of two or more. As the monohydric alcohol, ethanol, propanol or the like can be used in addition to the methanol used in this example. Further, a part of the decomposed resin component is precipitated, and the filler component and the resin component can be recovered by filtering the decomposition solution.

<Embodiment 6> A second preferred embodiment of the method for disassembling a molding material according to the present invention will be described. The molding material of Example 5 was used as an example of the molding material containing the unsaturated polyester, the addition-polymerizable monomer, and the aliphatic polyester as a binder. This mold material was put into a transpot, the mold temperature was 150 ° C, and the injection pressure was 15
Transfer molding was performed at 0 kg / cm ² to obtain a plate-shaped molded body having a thickness of 1 mm. Next, seven kinds of decomposition solutions were prepared by dissolving 1 g of potassium hydroxide as a base in 100 ml of a solvent in which methanol as a monohydric alcohol and dimethyl sulfoxide were mixed at different volume ratios. The composition ratio of each is shown in Table 5.

[0071]

[Table 5]

The plate-shaped molded body of the molding material was dipped in these seven kinds of decomposition solutions at 80 ° C., and the weight change after 5, 10 and 15 hours was measured. Table 6 shows the results.

[0073]

[Table 6]

When the mixing volume ratio of methanol and dimethylsulfoxide is 40/60, the resolution of the decomposition solution is largely different, and when the mixing volume ratio is 40/60 or less, the weight change of the molded molding material is large, and the decomposition reaction occurs more quickly. There is. That is, it can be said that a decomposition treatment method using a decomposition solution containing a solvent having a mixing ratio in this range is preferable. As mentioned above,
Unsaturated polyester, styrene, and a molded body of a molding material containing a polycaprolactone as a binder, potassium hydroxide, methanol, in the decomposition method of immersing in a decomposition solution containing dimethylsulfoxide, the volume mixing ratio of methanol and dimethylsulfoxide, 40/6
It is desirably 0 or less.

The molding material molded body to which the method for decomposing a molding material molded body of the present invention is applied is not limited to the composition of this embodiment. Further, the composition of the decomposition solution is not limited to the composition and blending ratio of this embodiment, and examples of the base include, in addition to potassium hydroxide shown in this embodiment, metals such as calcium hydroxide and sodium hydroxide. Examples thereof include metal oxides such as hydroxide, sodium oxide and calcium oxide, and metal alkoxides such as sodium ethoxide and potassium t-butoxide. These can be used alone or in combination of two or more. The monohydric alcohol is ethanol, in addition to the methanol used in this example.
Propanol and the like can be used. The temperature at the time of the decomposition process is not limited to the value of the present embodiment.

<Embodiment 7> A preferred embodiment of the step of disassembling the molding material of the present invention will be described with reference to FIG. The decomposition tank 1 is a holding means for containing a decomposition solution containing at least a base, a monohydric alcohol and dimethylsulfoxide, and holding a molded body of a molding material in a state of being immersed in the decomposition solution. The decomposition solution and the molded body of the molding material immersed in the decomposition solution are then transferred to the filtration tank 2. In this filtration tank, the solid content insoluble in the decomposition solution is filtered and separated. On the other hand, the filtrate is moved to the injection tank 3, where water or a monohydric alcohol is injected, and then the filtrate is transferred to the second filtration tank 4. Here, the solid content produced by injecting water or monohydric alcohol is filtered. The filtrate is collected in the distillation tank 5,
Water or monohydric alcohol is distilled off from the solution.

The results of the disassembling process of the molded molding material according to this embodiment will be described below. 23 parts by weight of styrene, 3 parts by weight of polycaprolactone (molecular weight 40,000) and 34 parts by weight of unsaturated polyester formed by polycondensation of maleic acid, isophthalic acid, and propylene glycol, and a curing agent tertiary butyl peroxybenzoate 1 part by weight was mixed, and further 30 parts by weight of calcium carbonate having a particle size of 50 μm and 10 parts by weight of glass fiber having a diameter of 0.5 mm and a length of 20 mm were kneaded to obtain a molding material. Next, this molding material was cured under a pressure of 150 kg / cm ² at 120 ° C. for about 30 minutes to obtain a molding material molded body. Next, the decomposition treatment of this molded body was performed by the decomposition treatment apparatus of this embodiment. As described above, this decomposition processing apparatus performs a work consisting of a combination of filtration, injection, and distillation after the molded molding material is immersed and held.

100 g of this molded molding material was dipped and held at 80 ° C. in a decomposition tank 1 filled with a decomposition solution consisting of 50 g of potassium hydroxide as a base, 200 ml of methanol, and 800 ml of dimethyl sulfoxide.
It was confirmed that the molded body was completely disintegrated within 00 hours, and filler such as calcium carbonate and glass fiber and a part of the resin component were precipitated in the decomposition solution. Next, the contents of the decomposition tank 1 were transferred to the filtration tank 2 and separated into a filtrate and a solid content. This solid content is composed of glass fiber, calcium carbonate,
And the residual residue of decomposed resin. If these are separated into each component by a separation method utilizing the difference in specific gravity, they can be reused for each purpose including the filler.

The filtrate obtained by filtering with the filtration layer 2 was moved to the injection layer 3 and 300 ml of methanol was injected. After this injection procedure, the filtrate became cloudy and a precipitate formed. Then, the contents of the injection tank were transferred to the second filtration tank 4 and separated into a filtrate and a precipitate. This precipitate was a decomposition product of the binder resin in the molding material, and was dissolved in the decomposition solution, but it became insoluble due to the injection of an excessive amount of methanol and was precipitated. This precipitate is an ester of phthalic acid that constitutes the unsaturated polyester, propylene glycol, or the like, and can be reused as a raw material for the unsaturated polyester resin or the like. The filtrate obtained in the second filtration tank was moved to the distillation tank 5 to distill off methanol. As a result, sodium hydroxide dissolved in methanol was deposited, and the filtrate was only dimethyl sulfoxide. Potassium hydroxide, methanol, and dimethyl sulfoxide are substances that make up the decomposition solution in the present decomposition method, and can be used again as a decomposition solution by adjusting the composition to the optimum.

As described above, the apparatus for disassembling a molded body of a molding material is designed so that the molded body of the molding material contains at least one base.
A holding step of maintaining the state of being immersed in a decomposition solution containing a polyhydric alcohol and dimethylsulfoxide, a filtration step of filtering a solid content insoluble in the decomposition solution, and an injection of injecting water or a monohydric alcohol into the filtrate after the filtration. By performing a step, a second filtering step of filtering the solid content after the injection, and a distilling step of distilling water or a monohydric alcohol from the solution content after the injection, the molding material molded body is decomposed and , The mold material molded body after the decomposition treatment, and the decomposition solution are separated into each component. Further, the separated substances can be reused for the molding material according to the present invention, the decomposition treatment method thereof, and other uses. The components and equipment of the disassembling device are not limited to those shown in this embodiment,
For example, a stirrer or the like may be introduced into the decomposition tank 1 in order to accelerate the decomposition process of the molded molding material. In addition, after decomposing some molding material molded bodies, the whole decomposition treatment liquid may be separated at a time, or a part of the decomposition treatment liquid may be continuously immersed in the molding material molding body and held outside the system. A continuous circulation system may be used in which the decomposition solution is introduced, filtered, injected, and distilled to remove the separated material, and then the decomposition solution is returned to the system for holding the molded body of the molding material.

The disassembling apparatus may have not only the means shown in this embodiment but other means. For example, before the filtrate in the filtration tank 2 is introduced into the injection tank 3, a distillation means may be installed to distill off methanol. In this case, since potassium hydroxide precipitates, if a filtration means is also provided, potassium hydroxide can be separated and a filtrate containing only dimethylsulfoxide as a solvent can be obtained.
The binder resin decomposition product can be precipitated and separated by introducing this filtrate into an injection tank and adding water. Further, for the purpose of partially separating the substances existing in the decomposition solution, only a part of the above decomposition treatment device may be used. The composition, blending ratio, quantity, etc. of the molded molding material and its decomposition treatment solution are not limited to those in this embodiment.

[0082]

As described above, since the thermosetting composition of the present invention is constituted so that the unsaturated polyester resin cross-linked chain also contains an ester bond, it is disposed of by thermal decomposition treatment, solvolysis treatment or the like. Decomposition is rapid and the degree of decomposition is large. When the molded product of the present invention is discarded after use, the molding material is immersed in a decomposition solution containing at least a base and a monohydric alcohol or water, or is heated to the decomposition temperature of the filling compound to form a binder. Since the resin can be easily decomposed, it can be easily disintegrated. According to the decomposition treatment method of the present invention, the molding material can be easily disintegrated, and further, the molding material molded body and the decomposition solution can be separated and the respective components can be reused.

[Brief description of drawings]

FIG. 1 is a diagram showing a process of disassembling a molding material according to an embodiment of the present invention.

[Explanation of symbols]

 1 Decomposition tank 2 Filtration tank 3 Injection tank 4 Second filtration tank 5 Distillation tank

Claims (9)

[Claims] 1. At least an unsaturated polyester, an addition polymerizable monomer, and a ring-opening polymerizable monomer, wherein the ring-opening polymerizable monomer is at least one selected from the group consisting of a cyclic ketene acetal and a methylenedioxolane derivative. A thermosetting composition. 2. The thermosetting composition according to claim 1, further comprising an aliphatic polyester. 3. The aliphatic polyester is polycaprolactone, polypropiolactone, polylactic acid, polyglycolic acid, polyethylene adipate, polybutylene adipate, polytetramethylene adipate, polyethylene succinate, polybutylene succinate, polycaprolactone diol, polycaprolactone diol. The thermosetting composition according to claim 2, which is at least one selected from the group consisting of a copolymer of caprolactone triol and 3-hydroxyalkanoate. 4. A binder comprising a thermosetting composition comprising at least an unsaturated polyester, an addition polymerizable monomer, a ring-opening polymerizable monomer, and an aliphatic polyester, wherein the ring-opening polymerizable monomer is a cyclic ketene acetal or methylene. A molding material which is at least one selected from the group consisting of dioxolane derivatives. 5. An unsaturated polyester, an addition-polymerizable monomer, and an aliphatic polyester as binders, and further aluminum hydroxide, aluminum nitrate hydrate, calcium sulfate hydrate, calcium phosphonate hydrate, dihydrogen phosphate. At least selected from the group consisting of calcium hydrate, calcium oxalate hydrate, magnesium hydroxide, magnesium hydrogen phosphate hydrate, magnesium phosphate hydrate, magnesium oxalate hydrate, and zinc phosphate hydrate. A molding material containing one kind. 6. The molding material according to claim 5, further comprising a base. 7. A molded body of a molding material containing at least an unsaturated polyester, an addition polymerizable monomer, and an aliphatic polyester as a binder, and at least a base and 1
A method for decomposing a molded molding material, which comprises a step of immersing in a decomposition solution containing a dihydric alcohol and dimethyl sulfoxide. 8. The mixing ratio of the monohydric alcohol and dimethyl sulfoxide in the decomposition solution is 40/60 by volume.
The method for decomposing a molding material molding according to claim 7, which is as follows. 9. A molded body of a molding material containing at least an unsaturated polyester, an addition polymerizable monomer, and an aliphatic polyester as a binder, and at least a base and 1
A holding step of holding in a state of being immersed in a decomposition solution containing a polyhydric alcohol and dimethyl sulfoxide, a filtration step of filtering a solid content insoluble in the decomposition solution, an injection step of injecting water or a monohydric alcohol into the filtrate after the filtration, A method for decomposing a molded molding material, comprising a second filtration step of filtering solids after the injection, and a distillation step of distilling water or monohydric alcohol from the solution content after the injection.