JPH08134340A - Thermosetting composition, its production, molding material, method for decomposition treatment of thermosetting composition and apparatus for decomposition treatment of thermosetting composition - Google Patents

Abstract

PURPOSE: To obtain a thermosetting composition capable of readily carrying out the decomposition treatment in disposal and a molding material and provide methods both for producing the composition and for decomposition treatment thereof and an apparatus for the decomposition treatment. CONSTITUTION: This thermosetting composition is constituted so as to uniformly disperse polycaprolactone in an unsaturated polyester resin and a molding material is constituted by using the composition as a substrate. When the composition and the molding material are disposed of, they are immersed in a decomposing solution containing at least a base and a monohydric alcohol to thereby readily carry out the decomposition treatment at normal temperatures. The separating and classifying treatment of the decomposing solution after the decomposition treatment is performed according to a filtering, a distilling away and a dissolving means by using this apparatus for the decomposition treatment.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermosetting composition which is excellent in strength and heat resistance and is widely used in industrial materials, particularly a thermosetting composition which can be easily disposed of after use, and its production. The present invention relates to a method, a molding material using the same as a base material, a decomposition treatment method and a decomposition treatment apparatus for the same.

[0002]

2. Description of the Related Art Thermosetting resins have been produced in the amount of about 2 million tons in one year of 1990.
It has been growing at a rate of several percent per year. As the thermosetting resin, for example, epoxy resin, phenol resin,
Examples include polyurethane resin, unsaturated polyester resin, urea resin, melamine resin, and polyimide resin. These resins may be used alone, but most of them are used as composite materials, and for example, in unsaturated polyester, about 80% of the production amount is used as fiber reinforced plastic (FRP). The unsaturated plastic contains, as main constituent materials used together with it, inorganic materials such as calcium carbonate, talc and silica, and organic materials such as pulp and wood, in addition to glass fiber. As described above, since it is easy to mix fillers and additives such as inorganic substances and to reinforce with fibers, they are used in various fields such as molding materials, laminated boards, adhesives, paints, and other industrial fields and consumer fields.

On the other hand, since these resins are three-dimensionalized by a curing reaction and generally become an insoluble and infusible solid, decomposition treatment has been conventionally difficult, and it is difficult to adapt it to recycling and reuse. There was no choice but to discard. However, as attention has been paid to the waste problem, the development of recycling / recycling technology has become necessary, and the use of pyrolysis as a raw material has begun to be considered, but the hardness and strength of thermosetting resins have The advantages of heat resistance, flame retardancy and chemical resistance, on the contrary, make waste treatment technically difficult.

[0004]

[Problems to be Solved by the Invention] As described above, the waste problem is becoming more and more serious, and there is an urgent need to develop techniques for reducing the volume of discarded resin and treating technology for reuse. . Especially fiber reinforced unsaturated polyester is used for fishing boats,
Since it is often used for manufacturing large products such as tanks and housing equipment, the decomposition and recycling of waste is serious. In addition, many thermosetting resins are often used as structural materials due to their strength and other factors, and thus often include other materials such as metals, such as motor molding materials. Can be seen. 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. In other words, the present situation is that the conventional problems and treatment methods for thermosetting resins cannot solve the waste problem. Therefore, it is an object of the present invention to provide a thermosetting composition that can be easily treated when it is discarded, a method for producing the same, a molding material, and a simple method for decomposing and a device for decomposing.

[0005]

In order to achieve the above object, the thermosetting composition of the present invention contains at least an unsaturated polyester resin and polycaprolactone, and the amount of polyacrylic acid is 100 parts by weight of the unsaturated polyester resin. The amount of caprolactone is 3 parts by weight or more and 10 parts by weight or less.

In the thermosetting composition, polycaprolactone preferably has a molecular weight of 10,000 or more and 70,000 or less.

Further, in one embodiment of the present invention, the thermosetting composition contains at least an unsaturated polyester resin and polycaprolactone, and is further configured to contain polyester fibers or polyamide fibers.

[0008] In another embodiment of the present invention, the thermosetting composition further contains water, and the thermosetting composition is constituted so as to be dispersed and held in a large number of water droplets.

Further, in another embodiment of the present invention, the thermosetting composition further comprises a large number of bubbles, which are dispersed and held in a porous state.

The molding material of the present invention comprises the above-mentioned thermosetting composition containing at least an unsaturated polyester resin and polycaprolactone as a base material.

Further, according to the present invention, a step of dispersing water in a thermosetting composition before curing containing at least an unsaturated polyester resin and polycaprolactone, and a step of curing the dispersion while keeping it dispersed in a large number of water droplets There is also provided a method for producing a thermosetting composition, the method including:

Further, the present invention comprises a step of dispersing water in a thermosetting composition before curing containing at least an unsaturated polyester resin and polycaprolactone, and a step of curing the water while keeping it dispersed in a large number of water droplets. There is also provided a method for producing a thermosetting composition, which comprises the step of: and the step of immediately volatilizing water in a water drop state to form a porous composition.

The method for decomposing a thermosetting composition of the present invention comprises immersing a thermosetting composition containing at least an unsaturated polyester resin and polycaprolactone in a decomposition solution containing at least one base and one monohydric alcohol. It is configured to include a step of performing.

Further, the apparatus for decomposing a thermosetting composition of the present invention is a thermosetting composition containing at least an unsaturated polyester resin and polycaprolactone. Holding means for maintaining the state of being immersed in a decomposition solution containing a polyhydric alcohol, filtration means for filtering solid components insoluble in the decomposition solution, and distillation for distilling a solvent containing at least a monohydric alcohol from the filtrate after the filtration. It is configured to have a removing means and a separating means for dissolving and separating at least a saturated acid from the solid content after the filtration and the solid content after the distillation.

[0015]

According to the above-mentioned constitution of the present invention, since the thermosetting composition is in a state where polycaprolactone is mixed in an amount of 3 parts by weight or more and 10 parts by weight or less with 100 parts by weight of the unsaturated polyester resin, the thermosetting composition is uniformly dispersed. By the method for decomposing a thermosetting composition of the present invention, the decomposition solution rapidly penetrates into the composition due to the presence of the polycaprolactone to be dispersed by immersing it in a decomposition solution containing at least a base and a monohydric alcohol. At the same time, polycaprolactone is solvolytically decomposed. Next, some ester bonds constituting the composition skeleton also undergo solvolysis, and the composition loses its three-dimensional structure and disintegrates, so that the volume can be sufficiently reduced and disposal is easy. To Further, in the above constitution, since the molecular weight of polycaprolactone mixed in the unsaturated polyester resin is 10,000 or more and 70,000 or less, it is possible to exhibit the decomposability by being immersed in a decomposition solution containing at least a base and a monohydric alcohol. of course,
It is easy to mix polycaprolactone, and the effect of preventing shrinkage at the time of molding can be expected.

Further, according to the constitution of the present invention, the thermosetting composition contains at least an unsaturated polyester resin and polycaprolactone, and further contains polyester fibers or polyamide fibers, so that the composition strength is improved. Furthermore,
By dipping in a decomposition solution containing at least a base and a monohydric alcohol, the decomposition solution rapidly penetrates into the composition due to the presence of the polyester fiber or the polyamide fiber as well as the polycaprolactone to be dispersed, and at the same time, the polycaprolactone is dispersed. And the polyester or polyamide fibers that underpin the composition strength also undergo solvolysis.
At this time, some ester bonds constituting the skeleton of the composition undergo solvolysis, so that the composition largely loses its strength and disintegrates, so that the volume can be sufficiently reduced and the disposal process becomes easy.

Further, according to the constitution of the present invention, the thermosetting composition contains at least an unsaturated polyester resin and polycaprolactone, and is cured with water dispersed therein. Therefore, the thermosetting composition is extremely lightweight and low in cost. In addition, by soaking in a decomposition solution containing at least a base and a monohydric alcohol, not only the dispersed polycaprolactone but also the decomposition solution rapidly penetrates into the composition due to the presence of water, and the polycaprolactone and the composition skeleton In addition to the solvolysis of the ester bond constituting the composition, dispersed water droplets also flow out into the decomposition solution, so that the composition largely loses strength and collapses.

Further, according to the constitution of the present invention, the thermosetting composition contains at least an unsaturated polyester resin and polycaprolactone, disperses water, cures the mixture as it is, and immediately evaporates water to form a porous structure. Since it has a shape, it can be used as a foam having a higher strength than ordinary urethane foam. Furthermore, by immersing in a decomposition solution containing at least a base and a monohydric alcohol, the decomposition solution penetrates into the composition very quickly because it is porous and due to the presence of polycaprolactone to be dispersed, Since the polycaprolactone and the ester bond constituting the skeleton of the composition are subjected to solvolysis, the composition largely loses strength and disintegrates in a short time.

On the other hand, according to the constitution of the present invention, the mold material contains at least a base and a monohydric alcohol because the base material is any of the thermosetting compositions containing at least an unsaturated polyester resin and polycaprolactone. By being immersed in the decomposition solution, the decomposition solution rapidly penetrates into the composition due to the presence of at least polycaprolactone, and at least a part of the ester bonds constituting the composition skeleton of the composition undergoes solvolysis. , The mold material loses its three-dimensional structure due to these decompositions,
Since it disintegrates, the volume can be sufficiently reduced and the disposal process becomes easy.

Further, according to the constitution of the present invention, the decomposition treatment device for the thermosetting composition is a holding means for immersing and holding the thermosetting composition containing at least the unsaturated polyester resin and polycaprolactone in the decomposition solution. A filtering means for filtering a solid content insoluble in the decomposition liquid; a distilling means for distilling a solvent containing at least a monohydric alcohol from the filtrate after the filtration; a solid content after the filtration; Since it has a separation means for dissolving and separating at least a saturated acid from the solid content, the decomposition solution after the decomposition treatment is separated and can be reused for each purpose including the decomposition treatment method of the present invention without discarding.

[0021]

The present invention will be described in detail below with reference to its examples. First, a preferred first embodiment of the thermosetting composition of the present invention and a first embodiment of the decomposition treatment method of the thermosetting composition of the present invention will be described. The thermosetting composition according to the present invention is obtained by mixing polycaprolactone into at least the unsaturated polyester resin. Less than,
The method for producing the thermosetting composition and the result of the decomposition treatment will be described with reference to the first example according to the present invention.

Example 1-1 A thermosetting composition was prepared by using 80 parts by weight of an unsaturated polyester resin (manufactured by Nippon Shokubai Co., Ltd., trade name: Epolak) and polycaprolactone (molecular weight: 4).
Manufactured by Daicel Chemical Co., Ltd., trade name: Praxel) 3
It was configured such that the 0 wt% styrene solution was 20 parts by weight. After mixing these two components well, 1 part by weight of a curing agent tertiary butyl peroxybenzoate (manufactured by NOF CORPORATION, trade name: Perbutyl Z) was added to 100 parts by weight of the mixture, and the mixture was added at 120 ° C. Cured for 30 minutes.

Since 30 wt% of styrene is mixed in advance in the unsaturated polyester resin, the thermosetting composition will contain 38 wt% of styrene.

Thus, a thermosetting composition containing 6.4 parts by weight of polycaprolactone based on 100 parts by weight of the unsaturated polyester resin can be obtained.

The unsaturated polyester resin includes unsaturated polybasic acids such as maleic acid and fumaric acid, saturated polybasic acids such as phthalic acid and isophthalic acid, and propylene glycol,
It is a liquid resin in which an unsaturated polyester formed by polycondensation with a polyhydric alcohol such as diethylene glycol or triethylene glycol is dissolved in a polymerizable vinyl monomer such as styrene, vinyltoluene or diallylphthalate.
A curing agent and an accelerator can be added to this liquid resin, and molding can be performed according to each application. The unsaturated polyester used in this example comprises maleic acid, phthalic acid, and propylene glycol, and the molar composition ratio is 1: 1: 2 in order.

In the same procedure as in the above example, the unsaturated polyester resin and the styrene solution of polycaprolactone were mixed and cured at different ratios to thereby cure the thermosetting composition having different amounts of polycaprolactone mixed with the unsaturated polyester. You can get things. In this example, a thermosetting composition was prepared by mixing 1 to 15 parts by weight of polycaprolactone with 100 parts by weight of unsaturated polyester. Further, as a comparative sample, a thermosetting composition composed only of an unsaturated polyester resin containing no polycaprolactone was similarly molded.

In this example, the weight ratio of unsaturated polyester constituting the unsaturated polyester resin and styrene as a cross-linking agent in these thermosetting compositions was 56: 3.
It is fixed at 8.

Each thermosetting composition has a thickness of 1 when cured.
After casting into a plate of mm, the casting plate is 10 mm × 20
It was cut into a rectangle of mm and used as a sample for the decomposition treatment experiment.

However, when the amount of polycaprolactone mixed with 100 parts by weight of the unsaturated polyester resin exceeds 12 parts by weight, it is difficult to uniformly mix it at room temperature. For example, after dissolving and mixing by heating at about 50 ° C., Needs to be cured. However, in this case, since the liquid resin contains a carbon-carbon double bond having a polymerization reactivity, it is necessary to avoid heating more than necessary. However, the storage stability at room temperature is still poor, and it is desirable that the polycaprolactone is dissolved and then rapidly cured.

The basic resin properties of the thermosetting composition containing these polycaprolactones were investigated and compared with the thermosetting composition consisting of the unsaturated polyester resin alone. As a result, the gelling time and curing time showing curability were almost the same. The same is true, and the spiral flow length, which determines the formability during injection molding and transfer molding, is about 10% shorter, and there is no major problem. In the case of a thermosetting composition consisting only of unsaturated polyester resin, about 7% at the time of molding
Although the shrinkage rate of the unsaturated polyester resin 1 was decreased in the thermosetting composition containing polycaprolactone.
In the thermosetting composition in which 3 parts by weight or more of polycaprolactone is mixed with 00 parts by weight, the shrinkage rate is 0.1% or less, and it can be seen that the incorporation of polycaprolactone has the function of preventing shrinkage. Also in the molded product of the composition, a scumming phenomenon in which a mottled pattern was formed on the surface was slightly recognized in the case where the polycaprolactone content was large, but there was no problem in mechanical strength and the like.

Next, a plate-shaped molded sample of each thermosetting composition having a different amount of polycaprolactone mixed was immersed in a decomposition solution of 1 g of sodium hydroxide as a base, 27 g of monohydric alcohol and 3 g of water at room temperature. A decomposition treatment test was performed. Table 1 shows the results.

[0032]

[Table 1]

Each of the samples showed a weight loss due to penetration of the decomposition solution into the interior and solvolysis. The sample without polycaprolactone was about 1% even after 500 hours.
However, in all the samples mixed with polycaprolactone, the weight loss exceeded the amount of the mixture, and the tendency became larger as the amount of the mixture increased, and the weight decreased when the amount of mixture was 10 parts by weight or more. The rate will reach a ceiling.

Further, in the case of the composition containing 3 parts by weight or more of the mixture, the degree of decomposition is large, and the composition is decomposed into several pieces and is in a disintegrated state. I found that it was disassembled. Further, the presence of phthalic acid which constitutes the unsaturated polyester was confirmed by the measurement of nuclear magnetic resonance (NMR) of the decomposition solution after the decomposition treatment experiment.
Therefore, it was found that the thermosetting composition having the above-mentioned constitution is subjected to solvolysis treatment not only with the ester in the mixed polycaprolactone but also with the ester bond portion in the unsaturated polyester by the decomposition solution.

As in this example, the thermosetting composition constituted by polycaprolactone in an amount of 3 parts by weight or more and 10 parts by weight or less based on 100 parts by weight of the unsaturated polyester resin is a conventional unsaturated compound. Compared with polyester resin, it is not inferior in moldability, strength, etc., and has excellent shrinkage prevention properties during molding.
By using a decomposition solution containing ethanol, which is a polyhydric alcohol, decomposition treatment can be performed even at a low temperature of about room temperature.

The thermosetting composition is not limited to the constitution and manufacturing method described in the above experimental example.
For example, the amount of styrene is not limited to the value shown in the present embodiment, and rather, it is preferable that the amount of styrene is smaller than the amount of styrene mixed in the present embodiment, because the permeability of the decomposition solution is improved and the decomposition treatment is made efficient. Further, the molar ratio of the unsaturated acid and the saturated acid constituting the unsaturated polyester is not limited to 1: 1, but rather the saturated acid is decomposed and precipitated as in the present embodiment. As the amount of saturated acid increases, the degree of decomposition of the thermosetting composition increases.

The composition is not limited to these, and may include inorganic materials such as glass fiber, calcium carbonate, talc and silica, and organic materials such as pulp and wood. In addition, what constitutes the decomposition solution in the decomposition treatment method of the thermosetting composition according to the present invention is not limited to the base and the monohydric alcohol described in the above experimental examples, and examples thereof include potassium hydroxide and water. A base such as barium oxide, sodium ethoxide, potassium butoxide, or an alcohol such as methanol or propanol can be used, or these may be mixed.

In addition to the water used in this example, even if a plurality of solvents that are well compatible with the monohydric alcohol and do not hinder the dissolution of the base, such as acetone, methyl ethyl ketone, diethylene glycol, diethyl ether, dioxane, etc., are mixed. good. Further, it is possible to further mix polycaprolactone by increasing the cross-linking agent styrene constituting the unsaturated polyester, but it does not improve the decomposability when the mixed amount exceeds the mixed amount shown in this Experimental Example.

Example 1-2 6 parts by weight of polycaprolactone having a molecular weight of 10,000, 30,000, 40,000, 50,000 and 70,000 were added to a mixture of 56 parts by weight of an unsaturated polyester resin and 38 parts by weight of styrene. To the mixed liquid resin, 1 part by weight of a curing agent dicumyl peroxide (manufactured by NOF CORPORATION, trade name Park Mill D) was mixed and mixed well, then at 3 ° C at 120 ° C.
It was cured for 0 minutes to obtain a thermosetting composition.

When each thermosetting composition was cured, it was cast into a plate having a thickness of 1 mm and then the casting plate was 10 mm × 2.
It was cut into a 0 mm rectangle and used as a sample for a decomposition treatment experiment.
Similar to the thermosetting composition containing polycaprolactone having a molecular weight of 40,000 shown in Example 1, these thermosetting compositions are almost the same as the conventional unsaturated polyester resin cured product in physical properties such as moldability and strength. It was The thermosetting composition containing polycaprolactone having a molecular weight of 10,000 has a slightly lower shrinkage preventive property during molding than the thermosetting composition containing polycaprolactone having another molecular weight, but there is no practical problem.

In Example 1-1, it is sometimes difficult at room temperature to mix 12 parts by weight or more of polycaprolactone having a molecular weight of 40,000 with respect to 100 parts by weight of the unsaturated polyester resin. However, if the molecular weight exceeds 70,000, it may be a little difficult to mix even with the mixed amount in this embodiment, and it is necessary to promote uniform mixing by heating.

The constitution and manufacturing method of these resins are not limited to the above examples, and examples thereof include fillers such as calcium carbonate, calcium silicate, barium sulfate, aluminum hydroxide, talc and mica, and glass fibers. Of course, a reinforcing agent such as carbon fiber, a thickening agent, a release agent, a coloring agent and the like may be mixed.

Next, a decomposed sample of the thermosetting composition mixed with polycaprolactone having different molecular weight was immersed in a decomposition solution containing 1 g of sodium methoxide as a base and 30 g of methanol as a monohydric alcohol at room temperature to obtain the maximum weight. The degree of decomposition was examined by observing changes and appearance changes. The results are shown in Table 2.

[0044]

[Table 2]

As is clear from the results in Table 2, the presence of sodium methoxide as the base and methanol as the monohydric alcohol makes the decomposition solution effective, and the immersed sample undergoes solvolysis to significantly reduce the weight. Indicated. The degree of decomposition was dependent on the molecular weight of the polycaprolactone incorporated, and the largest weight loss was 40,000. Further, even when the weights of the molecular weights of 10,000 and 70,000 were reduced by 10 wt%, the composition was changed into a soft rubber-like state, and it was in a state that it was easy to be crushed and deformed.

As described above, in the thermosetting composition in which polycaprolactone is mixed with unsaturated polyester resin, if the molecular weight of polycaprolactone is 10,000 or more and 70,000 or less, it is easy to mix and the function of preventing shrinkage also works. In addition, it can be decomposed at room temperature with a decomposition solution composed of sodium methoxide which is a base and methanol which is a monohydric alcohol.

The composition of the decomposition solution in the method for decomposing a thermosetting composition according to the present invention is not limited to the bases and monohydric alcohols described in the above examples. A base such as potassium, barium hydroxide, sodium ethoxide, potassium butoxide, or methanol or propanol can be used. Further, not only a single component but also a plurality of these may be mixed.

Further, it is compatible with other solvents such as water, acetone, tetrahydrofuran, dioxane, dimethylformamide, ethylene glycol, propanediol, diethylene glycol diethyl ether, dimethylamine and the like, and is soluble with a base. It may be mixed as long as it does not interfere with the above, but care must be taken not to reduce the decomposition ability.

Although the amount of styrene constituting the skeleton of the thermosetting composition is fixed in the above examples, the amount is not more than the amount used in this example, for example, 40 parts by weight per 100 parts by weight of unsaturated polyester. The thermosetting composition obtained by crosslinking some parts of styrene has a higher permeability of the decomposition solution according to the present invention and can shorten the decomposition treatment time. However, in this case as well, the final degree of decomposition remains almost unchanged, and if the amount of styrene is reduced from 40 parts by weight, the polymerization curability will deteriorate and a large amount of uncured carbon-carbon double bonds will remain, resulting in a thermosetting composition. Will deteriorate the physical properties of.

In the above examples, the molar ratio of saturated acid phthalic acid and unsaturated acid maleic acid constituting the unsaturated polyester was fixed to 1: 1. As described above, the thermosetting composition was used. Since most of the skeletal bonds that undergo solvolysis are ester bonds involving phthalic acid, the content of phthalic acid (saturated acid) in the unsaturated polyester is high. By doing so, the final degree of decomposition of the composition can be improved.
The type of acid is not limited to those described in this embodiment.

In the above examples, the thermosetting composition molded in the form of a plate was subjected to decomposition treatment, but the thermosetting composition capable of decomposition treatment is not limited to this, and at least polycaprolactone is mixed. It may be a paint, putty, adhesive or the like made of the unsaturated polyester resin.

Example 2 A preferred second example of the thermosetting composition of the present invention and its decomposition treatment method will be described. The thermosetting composition according to this example comprises the unsaturated polyester resin of the thermosetting composition of the above-mentioned examples and polycaprolactone, and further contains polyester fibers or polyamide fibers. The method of producing the thermosetting composition and the result of the decomposition treatment will be described below with respect to the second example.

With respect to 38 parts by weight of the unsaturated polyester resin, 2 parts by weight of polycaprolactone (molecular weight 40,000, manufactured by Daicel Chemical Co., Ltd., trade name: Praxel), 10 parts by weight of polyethylene terephthalate fiber, particle diameter of about 5 μm 50 parts by weight of calcium carbonate of tert-butyl peroxybenzoate (manufactured by NOF CORPORATION)
After mixing and kneading perbutyl Z), 150 kg weight / c
A thermosetting composition was obtained by curing at 120 ° C. under a pressure of m ² . As the unsaturated polyester, Epolak manufactured by Nippon Shokubai Co., Ltd. or Rigolac manufactured by Showa High Polymer Co., Ltd. can be used. As the polyethylene terephthalate fiber, a product (trade name COMPET) manufactured by Allied Signal was used.

The present thermosetting composition containing polyester fiber is slightly inferior in strength and elastic modulus as compared with the composition using glass fiber conventionally used as a reinforcing agent, but the impact resistance and the It is excellent in abrasion resistance, electrical insulation, etc., and these are not disturbed even by mixing of polycaprolactone. Moreover, there is an advantage that the price is cheaper than other materials. Further, the moldability is not inferior to the conventional unsaturated polyester FRP.

It is also possible to use other polyester fibers such as polyethylene naphthalate fibers instead of polyethylene terephthalate fibers. Next, a decomposition test was conducted on this thermosetting composition. A thermosetting composition molded into a plate with a thickness of 1 mm and cut into a size of 10 × 20 mm was added to a decomposition solution containing 1 g of potassium ethoxide as a base, 15 g of ethanol as a monohydric alcohol, and 15 g of water at room temperature. Soaked in.

As a result, after 100 hours, many cracks were formed on the surface of the thermosetting composition, and the thermosetting composition was deteriorated to be divided into several pieces, and the weight was reduced by 15%. In this case as well, the amount of polycaprolactone is reduced to more than the mixed amount. In addition, particles of calcium carbonate and polyester fibers were observed in the decomposition solution, and it can be seen that the filler fell into the liquid due to the composition collapse. In addition, it was confirmed by microscopic observation that the polyester fibers, the polyester fibers on the surface of the thermosetting composition and the cracks were significantly deteriorated by corrosion.

As mentioned above, due to the presence of polyethylene terephthalate fibers as well as polycaprolactone,
The decomposition solution rapidly penetrates into the composition, polycaprolactone is solvolytically decomposed, and then the ester bond in the unsaturated polyester resin skeleton and the ester bond in the polyethylene terephthalate fiber supporting the strength of the composition are also formed. Since some appear to undergo solvolysis,
The thermosetting composition largely loses strength and disintegrates.

As described above, the thermosetting composition containing the unsaturated polyester resin and polycaprolactone, and further containing the polyethylene terephthalate fiber which is the polyester fiber, contains potassium ethoxide which is the base and ethanol which is the monohydric alcohol. By immersing in the solution, not only the unsaturated polyester and polycaprolactone but also the polyester fibers undergo solvolysis, so that the penetration of the decomposition solution is accelerated and the strength is greatly reduced, resulting in significant collapse. That is, the polyester fiber has the role of accelerating the decomposition treatment while improving the strength in the composition molded body.

The constitution of the thermosetting composition, the compounding ratio thereof and the manufacturing method are not limited to those shown in this embodiment. In addition, in this example, an example using a polyester fiber was described, but even in the case of using a polyamide fiber (for example, Apiere manufactured by Unitika Ltd., Teijin Ltd., Conex, etc.), a thermosetting composition is also used. The physical properties and degradability of the products are not inferior. Rather, it is superior in strength and the like. Needless to say, the composition and blending ratio of the decomposition solution are not limited to those shown in this embodiment.

Example 3 A preferred third example of the thermosetting composition of the present invention and its decomposition treatment method will be described. The thermosetting composition according to this example is configured such that the thermosetting composition according to the above-mentioned example further contains water, and these are dispersed and held in a state of many water droplets.

This composition comprises the steps of dispersing water in a thermosetting composition before curing containing at least an unsaturated polyester resin and polycaprolactone, and curing the dispersion while maintaining it in the form of many water droplets. It is manufactured by a method for manufacturing a thermosetting composition including a step. The thermosetting composition was manufactured and decomposed in the third example, and the results will be described below.

The thermosetting composition was prepared by adding 3 parts of unsaturated polyester.
4 parts by weight, polycaprolactone 3 parts by weight, styrene 23 parts by weight, and water 40 parts by weight. After vigorously stirring and mixing these, 1 part by weight of a curing accelerator cobalt naphthenate and 1 part by weight of a curing agent, methyl ethyl ketone peroxide, were added to 100 parts by weight of the mixture to give a thickness of 1 m.
It was cast and cured at room temperature into a plate of m.

In the structure of the unsaturated polyester, if the hydrophilic portion such as glycol and the hydrophobic portion such as benzene nucleus are well balanced, and the resin itself has a structure similar to that of one kind of nonionic surfactant, as in this embodiment. Water can be easily dispersed into a water-in-oil type by simply stirring it violently. Even with other structures, a lipophilic surfactant or a tertiary amine (such as triethanolamine) can be dispersed together, and the dispersion can be cured to retain water droplets.

In the thermosetting composition of this example, water has a diameter of 2
It is a very lightweight composition in the form of dispersed droplets of about 5 μm. The thermosetting composition is inferior in physical properties such as bending strength and compressive strength as compared with a composition containing no water, but is within a range that can be sufficiently put to practical use,
It can be used for casting or by being reinforced with a filler such as fiber. There is no problem with respect to moldability and curability. Further, the cost can be reduced.

Next, the casting plate of the thermosetting composition of this example was cut into a rectangle of 10 mm × 20 mm and immersed in a decomposition solution containing 1 g of potassium hydroxide and 30 g of ethanol at room temperature for decomposition. For comparison, a thermosetting composition composed of unsaturated polyester resin containing no water and polycaprolactone (same composition ratio) was similarly decomposed.
Table 3 shows the results.

[0066]

[Table 3]

As can be seen from Table 3, the thermosetting composition that retains water droplets has a greater weight loss and a shorter time to reach the final degree of decomposition. As described above, the presence of water droplets in the thermosetting composition accelerates the solvolysis during the decomposition treatment, and the water droplets themselves fall out due to the decomposition, resulting in a large reduction in weight and a large decrease in strength, resulting in significant collapse.

Moisture can be contained up to about 90% in the thermosetting composition, but only about 60% can be practically used. In this case, the strength decreases linearly with an increase in the water content. Also, in a normal environment, water hardly escapes, but it is more desirable to coat the surface. In this case, the coating is polyethylene, polypropylene, polystyrene,
It can be provided by applying and drying a solution or a suspension in which a resin such as polyvinyl acetal is dissolved.

The thickness of the coat layer is about 0.1 to 0.5 mm.
Therefore, the coated thermosetting composition may be decomposed by shaving the surface with a file or the like and then immersing it in a decomposition solution. When the resin is cured by heating instead of at room temperature as in the present embodiment, it is necessary to select conditions under which water does not dissipate, particularly from the time required for curing and the temperature during curing.

Example 4 A preferred fourth example of the thermosetting composition of the present invention and its decomposition treatment method will be described. The thermosetting composition according to this example is configured such that the thermosetting composition according to the above-described example further contains a large number of bubbles and these are dispersed and held in a porous state.

This composition comprises a step of dispersing water in a thermosetting composition before curing containing at least an unsaturated polyester resin and polycaprolactone, and a step of curing the composition while keeping it dispersed in a large number of water droplets. It is manufactured by a manufacturing method including a step and a step of immediately volatilizing water in a water drop state to form a porous composition. The thermosetting composition was manufactured and decomposed in the fourth example, and the results will be described below.

The thermosetting composition was prepared by adding 3 parts of unsaturated polyester.
4 parts by weight, polycaprolactone 3 parts by weight, styrene 23 parts by weight, and water 40 parts by weight. After vigorously stirring and mixing these, 1 part by weight of a curing accelerator cobalt naphthenate and 1 part by weight of a curing agent, methyl ethyl ketone peroxide, were added to 100 parts by weight of the mixture to give a thickness of 1 m.
It was cast and cured at room temperature into a plate of m.

This plate-shaped thermosetting composition was treated with about 1 mmHg.
When left under reduced pressure, the water was completely evaporated in about 100 hours to obtain a low-expandable foam thermosetting composition. The foam-like thermosetting composition has a higher resin density than normally used urethane foams and has a large compressive strength and bending strength, and can be applied to artificial wood and the like. Further, the material cost can be significantly reduced even when compared with urethane foam having the same resin density.

Next, the thermosetting composition in the form of foam was cut into a rectangle of 10 × 20 mm, and sodium hydroxide 1
g, ethanol 27 g, and water 3 g were immersed in a decomposition solution at room temperature. Since this thermosetting composition is porous, the presence of polycaprolactone also contributes to the extremely rapid penetration of the decomposition solution, and even polycaprolactone and the ester bond constituting the composition skeleton undergo solvolysis. After 80 hours, it was decomposed to a weight loss of about 30 wt% and was in a disintegrated state.

As described above, the thermosetting composition, which is made porous by mixing polycaprolactone into the unsaturated polyester resin, dispersing the water, curing the mixture as it is, and immediately volatilizing the moisture, is a usual urethane. It can be used as a foam having higher strength than foams, etc., and because it is porous by being immersed in a decomposition solution containing sodium hydroxide and ethanol, the decomposition solution is a composition because of the presence of polycaprolactone to be dispersed. Infiltrate very quickly into it, and the polycaprolactone and ester bond constituting the composition skeleton undergo solvolysis,
In a short time the composition loses great strength and disintegrates. In addition,
In this example, the evaporation of water after curing was based on reduced pressure,
The evaporation of water may be promoted by heating.

<Embodiment 5-1> A preferred first embodiment of the molding material of the present invention and its decomposition treatment method will be described. The molding material according to the present invention is based on a thermosetting composition containing at least an unsaturated polyester resin and polycaprolactone. Hereinafter, since the molding material was manufactured, molded, and decomposed, the results will be described.

In this example, an example of a molding material using a thermosetting composition containing the unsaturated polyester resin and polycaprolactone described in Example 1 as a base material will be described. 24 parts by weight of unsaturated polyester resin (manufactured by Nippon Shokubai Co., Ltd., trade name: Epolak), polycaprolactone (molecular weight 40,000, manufactured by Daicel Chemical Industries, Ltd., trade name: Praxel)
6 parts by weight of 30 wt% styrene solution, 0.5 parts by weight of a curing agent tertiary butyl peroxybenzoate (manufactured by Nippon Shokubai Co., Ltd., trade name: Perbutyl Z) were added and mixed well.
A thermosetting composition was obtained in which 6.4 parts by weight of polycaprolactone was mixed with 100 parts by weight of the unsaturated polyester resin as the base material.

Next, calcium carbonate 57 which is a filler
Parts by weight, 2 parts by weight of zinc stearate as a release agent, and 1 part by weight of thickener magnesium oxide were transferred to a kneader and dry mixed. After about 5 minutes, 30 parts by weight of the thermosetting composition previously mixed was gradually added to this uniformly mixed dry mixture and kneaded to obtain a uniform paste.
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).
It is a kind of molding material called as "," and is non-adhesive in spite of containing styrene. This mold material is put in a transpot and the mold temperature is 150 ° C, 150 kg / c
Transfer molding was performed at an injection pressure of m ² to obtain a plate-shaped molded body.

When this molded product is compared with FRP (fiber reinforced plastic) composed of an unsaturated polyester resin which is usually used industrially, the moldability, curability (curing time, gelling time), strength, etc. Have been found to be about the same, and have been found to be better in terms of dimensional stability. However, the spiral flow length is somewhat shorter, but this is not a problem in molding. Therefore, the molding material according to the present invention can be sufficiently applied to applications in which an FRP material is usually used.

Next, a plate-shaped molded body using the molding material according to the present invention was treated with 2 g of sodium hydroxide and 10 parts of ethanol.
and a decomposition solution of 20 g of methanol at room temperature for decomposition. As a result, after 200 hours,
The strength is extremely low and the shape can be easily broken,
The molded state could not be maintained. In other words, the permeation of the decomposition solution into the molded product causes solvolysis of the polycaprolactone, which is the base material of the molding material and the binder, and the unsaturated polyester resin, so that the molded product can no longer maintain its shape and collapses. Only.

As described above, the molding material based on the thermosetting composition containing at least the unsaturated polyester resin and the polycaprolactone is a molding material which can be applied in the same manner as the present FRP material and is at least a base. It can be easily disintegrated even at room temperature by immersing it in a decomposition solution composed of sodium hydroxide and a monohydric alcohol.

In this embodiment, transfer molding is used at the time of molding, but compression molding or injection molding may be used. Further, in the above embodiments, the bulk-shaped molding material has been described, but in addition to the bulk-shaped molding material, sheet-shaped S
MC (sheet molding compound) and granular PMC
(Pelletized type molding compound) may be used.

Example 5-2 In this example, an example of a molding material based on a thermosetting composition containing an unsaturated polyester resin and polycaprolactone and further containing polyester fibers or polyamide fibers will be described. To do. 19 parts by weight of unsaturated polyester resin (manufactured by Showa Highpolymer Co., Ltd., product name: Rigolac), polycaprolactone (molecular weight 4
1 part by weight of Daicel Chemical Co., Ltd., trade name: Praxel, and 0.4 parts by weight of tertiary butyl perbenzoate, which is a curing catalyst, are added and mixed well to form a base thermosetting composition. Got

Next, calcium carbonate 6 having a particle size of 4 to 6 μm
8 parts by weight, 1.2 parts by weight of zinc stearate as a release agent, and 0.4 parts by weight of calcium hydroxide as a thickening agent were dry-mixed in a kneader, and then the above thermosetting composition was added. It was gradually added and kneaded. Further, 10 parts by weight of polyethylene terephthalate fiber was added, and when they were uniformly dispersed, the kneading was terminated to obtain a block-shaped molding material. This mold material is press-fitted into the hopper of a plunger-screw type injection molding machine, the mold surface temperature is 150 ° C., the screw rotation speed is 50 rpm, the injection pressure is 140 kg / cm ² , the injection time is 5
Injection molding was carried out under the conditions of second and pressure holding time of 30 seconds.

The molded product obtained by this molding is lighter in weight than the molded product reinforced with glass fiber, and it is possible to realize further weight reduction in the field where conventional FRP is used such as automobile parts and sports equipment. it can. Further, the surface is smoother than that of the glass-reinforced molded product, which is convenient for a member that is normally handled. Also,
Compared to the glass fiber reinforced product, although the strength and elastic modulus are reduced, it has excellent electrical insulation, impact resistance, and toughness.
It can be sufficiently used for electrical equipment and as a structural material. Further, the workability during molding also exceeds that of the glass fiber reinforced molding material.

Next, using the molding material of the present invention, 20 m
A molded product molded into a cylindrical shape of mφ × 15 mmH was immersed in a decomposition solution composed of 2 g of sodium hydroxide, 20 g of ethanol, and 10 g of water at room temperature for decomposition treatment. At the same time, a molded body made of a molding material having the same compounding ratio but the polyethylene terephthalate fiber replaced by glass fiber was also decomposed.

As a result, after 200 hours, many cracks were formed on the surface of both molded products, and calcium carbonate, polyethylene terephthalate fibers or glass fibers that had fallen out due to the collapse of the molded products were observed in the decomposition liquid. However, after 50 hours or 100 hours, the polyethylene terephthalate fiber-containing molded article obviously has a higher permeability to the decomposition solution, and thus the deterioration progresses faster.

Further, this molded product is a molded product having a little thickness, and it may take time for the decomposed solution to penetrate completely into the interior, but it may not completely collapse after 200 hours. The breaking strength was reduced to about 1/8. The decrease in fracture strength of the glass fiber-containing molded product is about 4
Since the polyethylene terephthalate fiber in the decomposition liquid and the cracked surface of the molded body was corroded and deteriorated, this decomposition treatment also causes the polyethylene terephthalate fiber that supports the strength of the molded body to undergo solvolysis. , It can be seen that the strength has dropped significantly.

As described above, the molding material based on the thermosetting composition containing the unsaturated polyester resin and the polycaprolactone and further containing the polyester fiber is easy to process, and the molded product is the glass fiber. Compared to the inclusions, it is lighter in weight and has superior electrical insulation, impact resistance, and toughness. In addition, not only polycaprolactone and unsaturated polyester resin but also polyester fiber that supports strength undergoes solvolysis by immersing in a decomposition solution containing sodium hydroxide that is a base and ethanol that is a monohydric alcohol. Penetration is promoted and the strength is greatly deteriorated.

In this embodiment, an example using polyester fiber has been described, but the use of polyamide fiber is not inferior to the physical properties of the molding material and the physical properties and decomposability of the molded product. Further, in this embodiment, injection molding is used at the time of molding, but compression molding, transfer molding or the like may be used. In addition, although the bulk-shaped molding material has been described in the present embodiment, in addition to the bulk-shaped molding material, a sheet-shaped SMC (sheet molding compound) is used.
And granular PMC (pelletized type molding compo)
und).

Example 5-3 In this example, a molding material based on a thermosetting composition containing an unsaturated polyester resin and polycaprolactone and holding water dispersed therein is used. An example will be described. The thermosetting composition comprises 28 parts by weight of unsaturated polyester, 2.5 parts by weight of polycaprolactone, 20 parts by weight of styrene, 50 parts by weight of water, 1 part by weight of triethanolamine, and a third curing agent.
0.5 parts by weight of grade butyl peroxy-2-ethylhexanoate (trade name: Perbutyl O, Percure O, manufactured by NOF CORPORATION) was mixed and stirred vigorously to mix water in oil. It was dispersed in a water droplet form.

With respect to 40 parts by weight of this thermosetting composition,
The release agent, 1.5 parts by weight of zinc stearate, 58 parts by weight of calcium carbonate, and 0.5 part by weight of a thickening agent, magnesium oxide, were mixed to give a well kneaded paste. Chopped strands obtained by cutting glass fibers with a cutter were scattered on a polyethylene film and impregnated with the pasty material to obtain a molding material. The required length of the impregnated mold material is rolled up and aged to increase the viscosity to the required consistency. As a result, about 30 parts by weight of glass fiber was added to 100 parts by weight of the paste-like material.

The molding material thus obtained is in the form of a sheet, and is therefore one type of molding material usually called SMC (sheet molding compound), and is in a non-adhesive state despite containing styrene. In addition, water has a diameter of 2-5 μ
It is a molding material that is dispersed in the form of small droplets having a size of m and is light in weight because it contains water.

Next, this molding material was put into a mold, and a pressure of 100 kg / cm ² was applied by closing the mold to perform compression molding at a temperature of 65 ° C. The molded product thus obtained is lighter in weight as compared with a product containing no pure water,
Although it has no problem in terms of moldability and curability, it is slightly inferior in bending strength, compressive strength, etc., but since it contains glass fiber as a reinforcing material, it is a molded product that can withstand practical use.

A plate-shaped molded body molded using the molding material of the present invention was immersed in a decomposition solution consisting of 1 g of sodium hydroxide, 1 g of sodium methoxide, 25 g of methanol and 5 g of water for decomposition at room temperature. As a result, the decomposability of the molded product of the present molding material accelerates the penetration of the decomposing liquid and the solvolysis due to the presence of water droplets, as in the case of the decomposition of the thermosetting composition as the base material described in Example 3. In addition, the water drops are removed by the decomposition, so that the weight is reduced and the strength is decreased, and the porous state is caused, so that further penetration of the decomposition solution is induced. Therefore, it will collapse significantly.

The amount of water is preferably up to 60 wt% in the molding material in order to obtain practical strength. It should be noted that it is desirable to mold as soon as possible after the molding material is manufactured in order to avoid the dissipation of water. Further, even after the molding, in a normal environment, water does not dissipate, but it is more preferable to coat the surface with a thermoplastic resin or the like. In addition, a porous molded body can be obtained by intentionally allowing moisture to dissipate after molding, and can be used as a foam material for artificial wood or the like.

The triethanolamine used in this example is for stabilizing water by dispersing it in oil, and other lipophilic surfactants and tertiary amines can be used, and only stirring is required. If you can stabilize dispersion with, you don't need to use it.

Also a catalyst (and accelerator) for curing
Considering that it contains water, a room temperature curing type ketone peroxide-cobalt organic acid salt system, acyl peroxide-aromatic tertiary amine system is used, or a medium temperature as shown in this experimental example is used. It is desirable to use a curable peroxyester type or peroxycarbonate type. In that case, especially in the case of a room temperature curing system, it is necessary to pay sufficient attention because there is no grace time from the molding material production to the molding. Further, when using a high temperature curing agent, it is necessary to examine conditions such that water does not escape from the curing time and curing temperature.

In this embodiment, the sheet-shaped molding material has been described. However, in addition to the sheet-shaped molding material, bulk-shaped BMC (bulk molding compound) or granular PMC is used.
(Pelletized type molding compound) may be used.

As can be seen from the above examples, the molding material based on a thermosetting composition containing at least an unsaturated polyester resin and polycaprolactone can be immersed in a decomposition solution containing at least a base and a monohydric alcohol. ,
The thermosetting composition has the ability to decompose, undergoes solvolysis, and disintegrates.

The composition of the molding material is not limited to that used in this embodiment, and thickeners such as beryllium oxide, magnesium oxide, magnesium hydroxide, calcium oxide, calcium hydroxide, zinc oxide, etc., Mold release agents such as stearic acid and calcium stearate, curing agents such as benzoyl peroxide and tertiary butyl peroctoate,
Carnauba wax, wax such as paraffin, and coloring agents such as chromium oxide, carbon black, and white titanium can be mixed. Also, the composition ratio is not limited to the values in this embodiment.

Further, in the above-mentioned examples, only the example in which the plate-shaped molded body is molded by using the molding material according to the present invention is shown, but of course the invention is not limited to this, and construction materials, civil engineering materials, housing equipment It can be molded into various shapes for automobile parts. For example, a molded motor can be obtained by integrally molding with a motor,
In this case, the decomposition treatment of the molding material is a very effective application example because it enables not only the collapse of the molding material but also the recovery of metal parts such as coils made of iron and copper and stators.

Further, the values of the respective conditions at the time of molding and decomposition in the above embodiment, the composition of the decomposition solution and the like are not limited to those of this embodiment.

Example 6 A preferred first example of the apparatus for decomposing a thermosetting composition of the present invention will be described. The apparatus for decomposing a thermosetting composition according to the present invention is a holding means for immersing and holding a thermosetting composition containing at least an unsaturated polyester resin and polycaprolactone in a decomposing solution, and a solid content insoluble in the decomposing solution. Filtration means, a distillation means for distilling a solvent containing at least a monohydric alcohol from the filtrate after the filtration, and at least a saturated acid is dissolved and separated from the solid content after the filtration and the solid content after the distillation. It has a separating means. The thermosetting composition was decomposed in the first example, and the results 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 of tertiary butyl peroxy 1 part by weight of benzoate (manufactured by NOF CORPORATION, trade name: Perbutyl Z) is mixed, and further 30 parts by weight of calcium carbonate having a particle diameter of 50 μm, 10 parts by weight of glass fiber having a diameter of 0.5 mm and a length of 20 mm. Weigh and knead these,
The thermosetting composition molded body 1 was obtained by curing at 120 ° C. for about 30 minutes under a pressure of 0 kg / cm ² .

Next, this thermosetting composition was decomposed by a decomposition apparatus. FIG. 1 shows a schematic diagram of the decomposition processing apparatus in the present invention. This decomposition treatment apparatus carries out a work consisting of a combination of filtration, distillation, and dissolution after the thermosetting composition molded body is held by immersion. Of these, a series of process steps performed by the decomposition treatment device on the decomposition solution after the thermosetting composition was held by immersion is shown in FIG.

This thermosetting composition molded body 1 (1000
When g) was immersed at room temperature in the decomposition tank 2 filled with the decomposition solution 2a consisting of 50 g of sodium hydroxide as a base, 2700 g of ethanol and 300 g of water, the weight of the molded body 1 decreased to 600 g within 100 hours. It was observed that the fillers such as calcium carbonate and glass fiber had fallen out into the decomposition solution.

In this apparatus, first, by switching the valve 3 and the three-way cock 4, the decomposition solution 2a after composition decomposition is introduced into a separation tank 5, and a G4 (pore size 5 to 10 μm) glass filter 5a is used. It was filtered. By this filtration, the filtrate 6 and the solid matter on the glass filter 5a were separated. The solids consist of particles, fibers and white precipitate.
After completion of this separation, 30 g of an aqueous sodium hydroxide solution was added from the pouring tank 8 by switching the three-way cock 4, and the white precipitate on the glass filter 5a was dissolved and the solid matter 7 consisting of particles and fibers remained. The dissolved white precipitate is
The filtrate 6 was mixed and precipitated again.

Subsequently, the filtrate 6 was filtered through a glass filter 10 by opening the valve 9 and separated into a filtrate 11 and a white precipitate 12. The white precipitate 12 is isophthalic acid having an unsaturated polyester skeleton, and may be washed with ethanol and dried. Isophthalic acid can be reused as a raw material for polyester such as unsaturated polyester. Further, the solid matter 7 and the residue present in the decomposition tank 2 are the calcium carbonate particles, the glass fiber and the resin component which is not decomposed, and again the thermosetting composition according to the present invention and other thermosetting resin or thermoplastic resin. Can be reused as a filler. The filtrate 11 is
When the valve 13 is opened, it is guided to the heating tank 14, the solution 15 consisting of ethanol and water is distilled off, and the solution 15 is stored in a liquid state in the tank 17 through the cooling pipe 16, and a solid substance remains in the heating tank 14.

Next, by switching the three-way cock 19, about 100 g of water was added to the heating tank 14 from the pouring tank 20, the solid matter was partially dissolved, but the white precipitate 18 remained undissolved. This white precipitate 18 is polycaprolactone,
The molecular weight was reduced by solvolysis with the decomposition solution. The filtrate 23 from which the white precipitate 18 has been removed by opening the valve 21 and filtering with the glass filter 22 is an aqueous sodium hydroxide solution, and can be stored in the injection tank 8 by opening the valve 24. It is also possible to design the device so that it is introduced into the decomposition tank 1 and mixed with the decomposition liquid. On the other hand, the solution 15 stored in the tank 17 is a mixed solution of water and ethanol, and can be reused as a decomposition solution of the thermosetting composition by opening the valve 25.

As described above, the apparatus for decomposing a thermosetting composition according to the present invention, after the thermosetting composition is dipped and held in the decomposing solution, the solid content of the decomposing solution is insoluble in the decomposing solution. A filtration step of filtering the solvent, a distillation step of distilling a solvent containing at least a monohydric alcohol from the filtrate after the filtration,
By subjecting the thermosetting composition to a decomposition treatment by subjecting the solid content after the filtration and the solid content after the distillation to a separation step of dissolving and separating isophthalic acid and polycaprolactone which are saturated acids with an aqueous alkaline solution and water, The decomposed solution after the decomposition treatment is separated into each component.

The separated substances can be reused in the thermosetting composition according to the present invention, the decomposition treatment method thereof and other uses. In this Example, only isophthalic acid was a component of the unsaturated polyester that appeared in the decomposition solution by solvolysis in the decomposition treatment of the thermosetting composition, but further solvolysis proceeded. When propylene glycol other than isophthalic acid falls out in the decomposition solution, it can be separated from ethanol and water by adding a fractionation device in the distillation means of the decomposition device. The propylene glycol thus obtained can be reused as a component of unsaturated polyester resin or other urethane resin.

In addition to the glass filter, the filter used for filtration at each stage may be a unglazed filter, a platinum sea surface layer filter, a porous aluminum oxide filter, a fabric filter made of cloth, etc. The size of can also be changed according to the composition of the thermosetting composition, the filler, and the particle size of calcium carbonate. The filtration operation may be normal filtration, suction filtration, or the like. Further, the equipment of each component of the decomposition apparatus is not limited to that shown in the present embodiment, and for example, an agitator or a heating heater is introduced into the decomposition tank 2 in order to accelerate the decomposition treatment of the thermosetting composition. You can also do it.

Even with this decomposition apparatus, it is practically impossible to completely separate the decomposed solution after decomposition into each component. Therefore, although a very small amount of phthalic acid or polycaprolactone may remain in the filtrate 11 or the filtrate 23, the ability to be reused as it is as a decomposition treatment liquid does not make a big difference in the ability. In addition, after decomposing several thermosetting compositions, all of the decomposing solution may be separated at once, or a system in which a part of the decomposing solution is continuously immersed and held in the thermosetting composition. It may be introduced to the outside and subjected to separation by means of filtration, evaporation, and dissolution to remove phthalic acid, polycaprolactone, calcium carbonate, glass fibers, etc., and then returning the decomposition solution to a system in which the thermosetting composition is immersed and retained. It may be a continuous circulation type.

For the purpose of partially separating the substance existing in the decomposition solution after the decomposition treatment, only a part of the decomposition treatment apparatus according to the present invention may be used. In addition, the composition of the thermosetting composition and its decomposition treatment solution, the compounding ratio, the kind of the solution used for the fractional dissolution, the amount, and the like are not limited to those in this example. For example, in the dissolution / separation in the heating tank 14, sodium hydroxide was dissolved / separated using water in the present embodiment, but polycaprolactone may be dissolved / separated using an organic solvent such as ethyl acetate, methyl acetate, or toluene. it can. However, in that case, it cannot be introduced into the injection tank 8 and reused in the system.

Further, the apparatus diagram in FIG. 1 is merely an outline, and the shape and arrangement or the pipes connecting the respective tanks are not necessarily as shown in this figure.

[0118]

INDUSTRIAL APPLICABILITY As described above, in the present invention, the thermosetting composition is formed so that polycaprolactone is uniformly dispersed in the unsaturated polyester resin, and the molding material is constituted by using them as a base material. When the material and the molding material are discarded after use, the composition is easily decomposed by immersing in a decomposition solution containing at least a base and a monohydric alcohol, and at this time, the composition is a soft rubber-like substance and is crushed. In addition to being able to easily perform processing such as deformation, separation and peeling from other parts, the decomposition solution is also separated by the decomposition processing device and each component can be reused. It can also be reduced.

[Brief description of drawings]

FIG. 1 is a first decomposition treatment apparatus for thermosetting compositions of the present invention.
FIG.

FIG. 2 is a first decomposition treatment apparatus for thermosetting compositions of the present invention.
Of process steps for explaining the embodiment of FIG.

[Explanation of symbols]

 1 Thermosetting Composition Molded Body 2 Decomposition Tank 2a Decomposition Solution 3 Valve 4 Three-way Cock 5 Separation Tank 5a Glass Filter 6 Filtrate 7 Solids 8 Injection Tank 9 Valve 10 Glass Filter 11 Filtrate 12 White Precipitate 13 Valve 14 Heating Tank 15 Solution 16 Cooling Pipe 17 Storage Tank 18 Solids 19 3 Way Cock 20 Injection Tank 21 Valve 22 Glass Filter 23 Filtrate 24 Valve 25 Valve

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display location C08L 67/04 LPG 77/00 LQU

Claims (10)

[Claims] 1. A thermosetting composition containing at least an unsaturated polyester resin and polycaprolactone, and 3 parts by weight or more and 10 parts by weight or less of polycaprolactone relative to 100 parts by weight of the unsaturated polyester resin. 2. The thermosetting composition according to claim 1, wherein the polycaprolactone has a molecular weight of 10,000 or more and 70,000 or less. 3. The thermosetting composition according to claim 1, which further contains polyester fibers or polyamide fibers. 4. The thermosetting composition according to claim 1, further comprising water, which is dispersed and held in a number of water droplets. 5. The thermosetting composition according to claim 1, further comprising a large number of bubbles, which are dispersed and held in a porous state. 6. A molding material comprising the thermosetting composition according to claim 1, as a base material. 7. A thermosetting composition before curing containing at least an unsaturated polyester resin and polycaprolactone,
A method for producing a thermosetting composition, comprising: a step of dispersing water; and a step of curing the dispersion while maintaining it dispersed in a large number of water droplets. 8. A thermosetting composition before curing containing at least an unsaturated polyester resin and polycaprolactone,
A thermosetting composition including a step of dispersing water, a step of curing while maintaining the dispersed state in a large number of water droplets, and a step of immediately volatilizing water in a water droplet state to form a porous composition. Method of manufacturing things. 9. A decomposition treatment of a thermosetting composition, which comprises a step of immersing a thermosetting composition containing at least an unsaturated polyester resin and polycaprolactone in a decomposition solution containing at least one base and one monohydric alcohol. Method. 10. A thermosetting composition containing at least an unsaturated polyester resin and polycaprolactone, which is maintained by immersing the composition in a decomposition solution containing at least one base and one monohydric alcohol. Means, a filtering means for filtering a solid content insoluble in the decomposition liquid, a distilling means for distilling a solvent containing at least a monohydric alcohol from the filtrate after the filtration, a solid content after the filtration and the distilling off A decomposition treatment apparatus for a thermosetting composition, which comprises a separation means for dissolving and separating at least a saturated acid from the subsequent solid content.