JP2005126669A - Method for recycling plastic, treated and recovered plastic, thermosetting resin-forming material and recycled plastic - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for recycling plastic by performing a decomposition and/or solubilization treatment of the plastic including thermosetting resins contained in industrial waste materials or general waste materials by a large amount in a high speed and a large amount, separating and recovering the obtained product or recovering as a mixture and reusing as the raw material of the plastic. <P>SOLUTION: The method for recycling the plastic comprises (a) a process of decomposing and/or solubilizing the plastic to resin components by treating the plastic including the thermosetting resin in a solvent containing a phenolic compound as an indispensable component in a supercritical or sub-supercritical state, and (b) a process of separating the resin components and residue formed by the above treatment, and further having (c) a process of reusing the resin components and/or the residue as the raw material of the plastic. Also, the resin components and residue as a mixture can be reused as the raw material of the plastic. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a plastic recycling method, a plastic processing recovery product, a thermosetting resin molding material, and a recycled plastic.

  Among plastics, thermosetting resins are widely used as materials for electric / electronic parts, automobile parts, and the like because they exhibit excellent electrical insulation, heat resistance, and mechanical strength. However, once the thermosetting resin is cured, it is not softened or melted by heat and does not dissolve in a solvent, and it is technically difficult to regenerate the cured product as a plastic raw material.

  In recent years, in order to overcome these problems, a method for solubilizing a thermosetting resin using a supercritical fluid or a subcritical fluid has been studied. For example, in the case of supercritical water alone, in order to solubilize and recycle a hardly-decomposable thermosetting resin, a method of solubilizing a phenol compound or a water / phenol compound solution in a supercritical or subcritical state. (For example, refer to Patent Document 1 and Non-Patent Document 1). In this method, a cured product of a thermosetting resin such as a phenol resin is solubilized in a short reaction time of about 10 minutes without adding an acid catalyst or an alkali catalyst, and an oligomer component having a molecular weight of 200 to 10,000. The oligomer component can be reused as a raw material for the thermosetting resin.

  In the recycling method, when the thermosetting resin contains a filler, a decomposition residue mainly composed of the filler is generated. Further, when the decomposition reaction of the resin component of the thermosetting resin is not completed or when a polymerization carbonization reaction occurs, a decomposition residue composed of an undecomposed component or a polymerization carbonization product is generated. However, the recycling method does not describe how to reuse these decomposition residues. Further, there is no description regarding a specific recycling method when the oligomer component is reused as a raw material for the thermosetting resin.

JP 2001-151933 A (page 3-4) Proceedings of the 52nd Network Polymer Conference, 56-59 (2002)

  The present invention has been made as a result of various studies in order to solve the above problems. The purpose is mainly to use plastics containing thermosetting resins that have been included in industrial waste and general waste discharged from factories in large quantities but have not been recyclable so far at high speed. Recycling method that recycles the processed recovered material obtained as a raw material of plastic after processing in large quantities, processed recovered material, and thermosetting resin molding material and recycled plastic that reuse processed recovered material as raw materials It is to provide.

  The present inventors produce a resin component obtained by treating a plastic containing a thermosetting resin in a supercritical or subcritical solvent containing a phenol compound as an essential component and / or the aforementioned treatment. It has been found that the residue, or a mixture of the resin component and the residue, can be reused as a raw material for plastics, and the present invention has been completed.

That is, the present invention
(1) (a) A process of decomposing and / or solubilizing a plastic into a resin component by treating the plastic containing a thermosetting resin in a supercritical or subcritical solvent containing a phenol compound as an essential component. And (b) a method for recycling plastic, including a step of separating the resin component and the residue generated by the treatment,
(2) (c) The plastic recycling method according to item (1), including a step of reusing the resin component and / or the residue as a raw material for plastic,
(3) The method for recycling plastic according to (2), wherein the resin component and the residue are reused as a raw material of plastic as a mixture,
(4) The thermosetting resin according to any one of (1) to (3), wherein the thermosetting resin is one or more selected from a phenol resin, an epoxy resin, a melamine resin, and a urea resin. How to recycle plastic. ,
(5) The phenol compound according to any one of (1) to (4), wherein the phenol compound is one or more selected from phenol, cresol, xylenol, resorcin, alkyl-substituted phenol, and naphthol. Plastic recycling methods,
(6) The method for recycling plastic according to any one of Items (1) to (5), wherein the phenol compound is separated and recovered from a resin component obtained from the plastic.
(7) The plastic recycling method according to any one of (1) to (6), wherein the step (a) is performed at a temperature in the range of 200 to 500 ° C.
(8) The plastic recycling method according to any one of (1) to (7), wherein the step (a) is performed at a pressure of 1 to 60 MPa.
(9) Plastic processed and recovered product comprising a resin component and / or residue, obtained by the plastic recycling method according to any one of items (1) to (8),
(10) The plastic recovery product according to (9), wherein the resin component is a compound mainly composed of a resin component having a molecular weight of 200 to 10,000.
(11) The item (9), wherein the residue is selected from an undecomposed resin component of a plastic containing the thermosetting resin, a polymerized carbonized product of the plastic, and a filler contained in the plastic. Plastic processing recovered material,
(12) Recycled plastic obtained by reusing the plastic processing and recovery product of any one of items (9) to (11) as a raw material,
(13) Recycled plastics containing 2 to 80% by weight of the processed and recovered plastics of any one of items (9) to (11), and recycled as raw materials,
(14) A thermosetting resin molding material obtained by reusing the plastic processing / recovery material of any one of items (9) to (11) as a raw material,
Is to provide.

  According to the present invention, a plastic containing a thermosetting resin contained in a large amount in industrial waste and general waste discharged from a factory or the like is obtained by decomposing and / or solubilizing a large amount at high speed. By separating and recovering the treated recovered product or recovering it as a mixture, it can be reused as a plastic raw material.

The present invention includes (a) a step of decomposing and / or solubilizing a plastic into a resin component by treating the plastic containing a curable resin in a supercritical or subcritical solvent containing a phenol compound as an essential component. And (b) a plastic recycling method comprising a step of separating the resin component and the residue produced by the treatment, and (c) reusing the resin component and / or the residue as a raw material for plastic. It has a process.
In the plastic recycling method of the present invention, the resin component and the residue can be reused as a raw material for the plastic as a mixture. The present invention is achieved by these recycling methods and can be reused as a raw material for plastics.
In addition, the process of the plastic in this invention includes the process by chemical decomposition and / or the process by physical solubilization.

  The plastic containing the thermosetting resin recycled by the method of the present invention includes a cured resin, a semi-cured resin, an uncured resin, and the like, and may be a varnish containing a solvent. In addition to fillers and additives in addition to thermosetting resins, molding materials or molded articles containing inorganic fillers such as silica fine particles and glass fibers, and organic fillers such as wood flour, glass cloth, etc. Processing laminates made by impregnating thermosetting resin to organic base materials such as inorganic and paper and cloth, metal-clad laminates laminated with metal foil such as copper foil, and copper-clad laminates And a thermosetting resin product such as a printed circuit board obtained in this manner.

In the present invention, the size of the plastic containing the thermosetting resin used for the decomposition and / or solubilization treatment is not particularly limited, but is preferably 1000 μm or less, more preferably 500 μm or less.
In the decomposition and / or solubilization treatment step, it is preferable to use the material by pulverizing it to a smaller size because the treatment time can be shortened. On the other hand, in the pulverization step before being subjected to the treatment step, pulverization small may lead to an increase in the pulverization cost. Therefore, in the above particle size range, the particle size can balance both the treatment step and the pulverization step. Should be selected.

  The type of thermosetting resin applied to the present invention is not particularly limited, but is suitable for phenol resins, epoxy resins, melamine resins, urea resins, etc. Among these, phenol resins are particularly effective. Is. Moreover, these may contain individually or 2 types or more.

  The phenol compound used as a solvent in the present invention has at least one hydrogen bonded to carbon of the aromatic ring substituted with a hydroxyl group, and functions as a solvent in a supercritical or subcritical state alone or as a mixture with other solvents. Any phenolic compound that can decompose and / or solubilize plastics is not particularly limited. Usually, monocyclic phenol compounds such as phenol, cresol, xylenol, resorcin, and alkyl-substituted phenol, and polycyclic phenol compounds such as 1-naphthol and 2-naphthol are preferably exemplified, and one of these Or 2 or more types are used. Of these, phenol is preferred from the viewpoint of cost and effects on decomposition and / or solubilization.

As the solvent in the present invention, a phenol compound alone or a mixture of a phenol compound and another solvent can be used.
When using a mixture of a phenol compound and another solvent, other solvents include water, monoalcohols such as methanol and ethanol, glycols such as ethylene glycol and propylene glycol, ketones, ethers and esters. Any of organic compounds, organic acids, acid anhydrides and the like used as a solvent in a normal chemical reaction may be used, and a plurality of solvents may be used in combination. Of these solvents, water is preferable because of its effect on decomposition and / or solubilization and availability. Further, the mixing ratio of the other solvent to the phenol compound is preferably a ratio of 1 to 500 parts by weight of the other solvent with respect to 100 parts by weight of the phenol compound, and more preferably the other solvent to 100 parts by weight of the phenol compound. The ratio is 5 to 50 parts by weight. If the amount of other solvent added is more than 500 parts by weight, the decomposition rate may decrease. If the amount of other solvent added is less than 1 part by weight, the decomposition rate may also decrease.

In the decomposition and / or solubilization treatment of the present invention, the ratio of the plastic containing the thermosetting resin and the solvent is preferably in the range of 50 to 1,000 parts by weight of the solvent with respect to 100 parts by weight of the plastic. The range of 100 to 400 parts by weight is more preferable.
If the proportion of the solvent is less than the above range, it may be difficult to smoothly proceed with the plastic decomposition and / or solubilization treatment. On the other hand, if the amount is larger than the above range, a special effect cannot be obtained, and the energy required for heating increases, so that the processing cost may increase.

  In the step (a) of the present invention, the solvent containing the phenol compound as an essential component can be treated by bringing it into a supercritical or subcritical state. It can be set by adjusting the pressure. As said temperature, the range of 200-500 degreeC is preferable normally, More preferably, it is the range of 250-400 degreeC. When the temperature is lower than the lower limit, the plastic decomposition and / or solubilization rate may be reduced, and processing in a short time may be difficult. On the other hand, when the temperature is higher than the upper limit, side reactions such as thermal decomposition and dehydration reaction occur simultaneously, and the chemical structure of the organic component constituting the recovered thermosetting resin changes, so that it can be reused as a chemical raw material. Use may be difficult. Moreover, as said pressure, the range of 1-60 MPa is preferable normally, More preferably, it is the range of 2-25 MPa. When the pressure is lower than the lower limit, the solvent is not in a supercritical or subcritical state, but in a vapor or gas state, so that the decomposition and / or solubilization rate is significantly reduced, and the plastic itself is difficult to process. It may become. When the pressure is higher than the upper limit, facilities that can be operated under severer conditions are required, and energy required to maintain high pressure is increased, but decomposition and / or solubilization rate is hardly improved, There may be cases where a significant effect cannot be obtained. The treatment time can be adjusted in the range of 1 to 60 minutes, but the treatment is usually completed in about 3 to 30 minutes.

  In the step (a) of the present invention, the decomposition and / or solubilization treatment proceeds effectively without adding a catalyst such as an acid and a base catalyst to the solvent containing the phenol compound as an essential component. In this case, it is an advantage that the catalyst separation operation after the treatment becomes unnecessary. On the other hand, when a catalyst such as an acid or base catalyst is added, the reaction temperature can be reduced and the reaction time can be shortened.

  In the step (b) of the present invention, as a method for separating the resin component and the residue, separation operation and separation conditions are not particularly limited, and a normal separation method by solid-liquid separation or gas-solid separation may be used. For example, a solid-liquid separation method such as a cyclone separation method, a filtration method, and a gravity sedimentation method can be used.

  In the present invention, when the resin component and the residue are used as a mixture and reused as a raw material for plastic, it is not necessary to use a solid separation operation such as solid-liquid separation or gas-solid separation. Efficiency can be realized. This is effective when both the resin component and the residue are reused as plastic raw materials.

  The resin component obtained by the above method is usually composed of a compound mainly composed of a resin component having a molecular weight of 200 to 10,000. Here, the molecular weight in the present invention means a weight average molecular weight. Since the molecular weight of 200 to 10,000 is similar to the molecular weight of the prepolymer used when producing a plastic containing a thermosetting resin, the thermosetting resin is included by performing purification as necessary. It can be reused as a chemical raw material (prepolymer) for plastics. Here, having a resin component having a molecular weight of 200 to 10,000 as a main component means that 50% or more of the resin component having the molecular weight shown here is contained, but in addition to the main molecular weight, a molecular weight of 10, More than 000 resin components are also included. Moreover, as a resin component which has the molecular weight of 200-10,000, in the case of a normal thermosetting resin, it is about 2-100 nucleus of a raw material monomer. Further, the compound mainly composed of a resin component having a molecular weight of 200 to 10,000 is obtained not only from components obtained from thermosetting resins in plastics but also from organic fillers and substrates contained in plastics. In some cases.

  Moreover, in this invention, an unreacted solvent is isolate | separated and it can reuse for the isolation | separation and solubilization process of the plastic containing a thermosetting resin by using this as a solvent. Furthermore, the compound mainly composed of the resin component having a molecular weight of 200 to 10,000 can be subjected to a method such as distillation or extraction to separate and recover the phenol compound, which can be reused as a solvent. In the reuse, a phenol compound or water may be newly added as necessary. Here, the method for separating the unreacted solvent is not particularly limited, and any method such as flash distillation, vacuum distillation, solvent extraction and the like may be used. In addition to the above-mentioned compound mainly composed of the resin component having a molecular weight of 200 to 10,000, the obtained treated recovered product may contain a small amount of unreacted solvent such as a phenol compound or water. good.

Examples of the residue generated in the step (a) of the present invention include undecomposed components of plastics including the thermosetting resin, polymerized carbonized products of the plastics, and fillers contained in the plastics.
Examples of the filler include calcium hydroxide, calcium carbonate, magnesium oxide, magnesium hydroxide, talc, silica, and alumina.

  The plastic processing / recovery material consisting of resin components and / or residues obtained by the above plastic recycling method can be reused as plastic raw material to be recycled plastic. In that case, only the processing recovery material is used as the raw material. They may be used, or may be used in combination with other chemical raw materials and / or fillers. The blending amount of the treated recovered product in the recycled plastic raw material is not particularly limited, but is preferably 2 to 80% by weight, and more preferably 5 to 60% by weight with respect to the entire recycled plastic raw material. As the raw material of the recycled plastic, a resin component and a filler can be used in addition to the processed and recovered material, but the resin component is not particularly limited, but for example, thermoplastics such as polyethylene, polypropylene and polystyrene. Thermosetting resins such as resins, phenol resins, epoxy resins, urea resins and melamine resins can be mentioned, and these can be used alone or in combination. Examples of the filler include inorganic base materials such as calcium hydroxide, calcium carbonate, magnesium oxide, magnesium hydroxide, talc, silica and alumina, or organic base materials such as wood powder and plywood powder. It is done.

  Further, in the case of reusing a processing recovery product composed of a resin component and / or residue as a raw material for a thermosetting resin molding material, only the processing recovery product may be used as a raw material in the same manner as described above. You may use together with a resin component and / or a filler. Although the compounding quantity of the said processing collection material is not specifically limited, Preferably it is 2 to 80 weight% with respect to the whole thermosetting resin molding material, More preferably, it is 5 to 60 weight%.

As the resin component of the thermosetting resin molding material, when the resin component of the treated recovered product is used in combination with another resin component, the resin component to be used in combination is not particularly limited. For example, novolac type phenol resin, resol type phenol Examples thereof include resins and epoxy resins.
When the resin component of the treated product and the novolak type phenol resin are used in combination, hexamethylenetetramine is usually used as a curing agent. The blending amount of hexamethylenetetramine is 10 to 25 parts by weight with respect to a total of 100 parts by weight of the resin component of the treated product and the novolak type phenolic resin, as in the case of ordinary phenol resin moldings. The total amount of the resin component of the treated product and the novolak type phenol resin is 20 to 80% by weight based on the whole thermosetting resin molding material, including hexamethylenetetramine as a curing agent. Preferably, it is 30 to 60% by weight. Thereby, while providing sufficient moldability to a molding material, the texture of a molded product can be improved. If the total blending amount of the resin component of the treated product and the novolac type phenol resin is less than the lower limit, the fluidity at the time of molding may be reduced and the moldability may be lowered. On the other hand, when the upper limit is exceeded, there is no problem in forming a molding material or molding, but the blending amount of the filler is reduced, and the texture of the molded product may be insufficient. Further, in order to adjust the curing rate of the thermosetting resin molding material, magnesium oxide, calcium hydroxide, or the like can be used as a curing aid as necessary. Although the compounding quantity of a hardening adjuvant is not specifically limited, It is preferable to set it as 15 weight part or less with respect to a total of 100 weight part of the resin component of the said process collection thing, and a novolak-type phenol resin.

In addition, when the residue is used in combination with a normal filler as a raw material of a thermosetting resin molding material, the filler used in combination is not particularly limited, but is an inorganic base material used in a normal thermosetting resin molding material And / or organic substrates can be used. Examples of the inorganic base material include glass fiber, calcium carbonate, calcined clay, talc, silica, diatomaceous earth, alumina, and magnesium oxide. These inorganic base materials can be selected and used as necessary depending on the use of the molded product. Examples of the organic base material include wood powder, pulp, plywood powder, paper pulverized powder, cloth pulverized powder, and shell pulverized powder represented by coconut shell.
The total amount of the residue and the filler used in combination is preferably 2 to 80% by weight, more preferably 3 to 60% by weight, based on the entire thermosetting resin molding material.
As a method for producing a thermosetting resin molding material as recycled plastic, it can be obtained by a conventionally known method using the above components.

  Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited thereto.

[Example 1] Treatment of phenol resin molding material As a plastic containing a thermosetting resin, a general-purpose phenol resin molding material (PM-8 manufactured by Sumitomo Bakelite Co., Ltd.)
200) was used after pulverizing and adjusting the particle diameter to 250 μm or less.
The above-mentioned phenol resin molding material: 58.3 g, a solvent consisting of a mixture of phenol: 85.6 g and water: 21.3 g were mixed, charged into an autoclave (internal volume 200 cm ³ ), and then heated. By setting the temperature to 400 ° C., the internal pressure of the reactor was increased to 15 MPa to obtain a high temperature and high pressure state. The reaction system was stirred at 300 rpm and maintained at 400 ° C. and 15 MPa for 5 minutes, and then cooled to normal temperature and pressure.
Next, acetone was added to and mixed with the obtained decomposition product, followed by vacuum filtration to separate the filtrate and the residue. Subsequently, the filtrate was heated under normal pressure and reduced pressure to remove acetone, water, and phenol, thereby obtaining 65.3 g of a resin component. When this resin component was analyzed by gel permeation chromatography (hereinafter abbreviated as GPC), it was confirmed that the resin components had molecular weights of Mn: 608 and Mw: 2905. Moreover, 11.7 g of solid residue was obtained by performing the drying process of the filter residue with a dryer at 120 ° C. for 6 hours.

[Example 2] Treatment of phenol resin molding material In Example 1, a glass fiber reinforced phenol resin molding material (PM-9640 manufactured by Sumitomo Bakelite Co., Ltd.) was used as a plastic containing a thermosetting resin. The same operation as in Example 1 was carried out, and the resin component: 40.8
g and a solid residue: 29.2 g. The recovered amounts and molecular weights of the resin components and the recovered amounts of the solid residue are summarized in Table 1.

[Example 3] Treatment of epoxy resin molding material In Example 1, as the plastic containing the thermosetting resin, an epoxy resin molding material for semiconductor encapsulation (EME-6300H manufactured by Sumitomo Bakelite Co., Ltd.) was used. The same operation as in Example 1 was performed, and the resin component: 17.
5 g and a solid residue: 40.8 g were obtained. The recovered amounts and molecular weights of the resin components and the recovered amounts of the solid residue are summarized in Table 1.

[Example 4] Treatment of Melamine Resin Molding Material In Example 1, the same operation as in Example 1 was performed except that a melamine resin molding material (ME-J manufactured by Matsushita Electric Works) was used as the thermosetting resin. 66.1 g of resin component and 11.7 g of solid residue were obtained. The recovered amounts and molecular weights of the resin components and the recovered amounts of the solid residue are summarized in Table 1.

[Example 5] Treatment of urea resin molding material In Example 1, the same operation as in Example 1 was performed except that the urea resin molding material (CU-A manufactured by Matsushita Electric Works) was used as the thermosetting resin. Resin component: 66.9 g and solid residue: 10.5 g. The recovered amounts and molecular weights of the resin components and the recovered amounts of the solid residue are summarized in Table 1.

[Example 6] Treatment of phenol resin molding material Resin component in Example 1 except that ortho-cresol (manufactured by Wako Pure Chemical Industries) was used instead of phenol as a solvent. : 61.2 g and a solid residue: 14.5 g. The recovered amounts and molecular weights of the resin components and the recovered amounts of the solid residue are summarized in Table 1.

[Example 7] Treatment of phenol resin molding material Resin component in Example 1 except that paracresol (manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of phenol as a solvent. : 62.0 g and solid residue: 14.0 g. The recovered amounts and molecular weights of the resin components and the recovered amounts of the solid residue are summarized in Table 1.

[Example 8] Treatment of phenol resin molding material In Example 1, except that 1-naphthol was used instead of phenol as a solvent, the same operation as in Example 1 was carried out, and the resin component: 66.5 g Solid residue: 16.1 g was obtained. The recovered amounts and molecular weights of the resin components and the recovered amounts of the solid residue are summarized in Table 1.

[Example 9] Treatment of phenol resin molding material Resin component in Example 1 except that a mixture of phenol: 53.5 g and water: 53.5 g was used as a solvent. : A mixture of 32.7 g and a solid residue: 34.9 g. The recovered amounts and molecular weights of the resin components and the recovered amounts of the solid residue are summarized in Table 1.

[Example 10] Treatment of phenol resin molding material In Example 1, except that the amount of charge of general-purpose phenol resin molding material (PM-8200 manufactured by Sumitomo Bakelite Co., Ltd.) was changed to 100.0 g, it was the same as Example 1. Operation was performed to obtain 77.70 g of a resin component and 46.0 g of a solid residue. The recovered amounts and molecular weights of the resin components and the recovered amounts of the solid residue are summarized in Table 1.

[Example 11] Treatment of phenol resin molding material In Example 1, except that the reaction temperature was set to 350 ° C, the same operation as in Example 1 was carried out to obtain 57.1 g of a resin component and a solid residue: 17. 5 g was obtained. The recovered amounts and molecular weights of the resin components and the recovered amounts of the solid residue are summarized in Table 1.

[Example 12] Treatment of phenol resin molding material In Example 1, except that 2.9 g of calcium hydroxide (manufactured by Wako Pure Chemical Industries) as a catalyst for promoting the reaction was added and the reaction temperature was set to 300 ° C. The same operation as in Example 1 was performed to obtain 60.1 g of a resin component and 12.0 g of a solid residue. The recovered amounts and molecular weights of the resin components and the recovered amounts of the solid residue are summarized in Table 1.

[Example 13] Treatment of phenol resin molding material A general-purpose phenol resin molding material (PM-8200 manufactured by Sumitomo Bakelite Co., Ltd.) was pulverized and screened as a plastic containing a thermosetting resin, and the particle diameter was adjusted to 250 µm or less. What was done was used.
The above-mentioned phenol resin molding material: 58.3 g, a solvent consisting of a mixture of phenol: 85.6 g and water: 21.3 g were mixed, charged into an autoclave (internal volume 200 cm ³ ), and then heated. By setting the temperature to 400 ° C., the internal pressure of the reactor was increased to 15 MPa to obtain a high temperature and high pressure state. The reaction system was stirred at 300 rpm and maintained at 400 ° C. and 15 MPa for 5 minutes, and then cooled to normal temperature and pressure.
After completion of the reaction, the solvent (phenol, water) is removed by heating under normal pressure and reduced pressure conditions from a mixture of the resin component, solid residue and solvent, and a mixture of the resin component and solid residue: 77 0.0 g was obtained. A portion of this mixture was sampled and dissolved in tetrahydrofuran (hereinafter referred to as THF) to evaluate the ratio between the THF-soluble resin component and the THF-insoluble solid residue. As a result, it was confirmed that the resin component was contained in 84.8% and the solid residue was contained in 15.2%. Moreover, when this resin component was analyzed by gel permeation chromatography (hereinafter abbreviated as GPC), it was confirmed that the resin components had molecular weights of Mn: 608 and Mw: 2905.

[Example 14] Treatment of phenol resin molding material In Example 13, a glass fiber reinforced phenol resin molding material (PM-9640 manufactured by Sumitomo Bakelite Co., Ltd.) was used as the plastic containing the thermosetting resin. The same operation as in Example 13 was performed to obtain 70.0 g of a mixture of a resin component (decomposition product) and a solid residue. The ratio of the resin component to the solid residue in the mixture and the molecular weight of the resin component are summarized in Table 2.

[Example 15] Treatment of epoxy resin molding material In Example 13, as a plastic containing a thermosetting resin, an epoxy resin molding material for semiconductor encapsulation (EME-6300H manufactured by Sumitomo Bakelite Co., Ltd.) was used. The same operation as in Example 13 was performed to obtain a mixture of a resin component (decomposition product) and a solid residue: 58.3 g. The ratio of the resin component to the solid residue in the mixture and the molecular weight of the resin component are summarized in Table 2.

[Example 16] Treatment of melamine resin molding material In Example 13, the same operation as in Example 13 was performed, except that a melamine resin molding material (ME-J manufactured by Matsushita Electric Works) was used as the thermosetting resin. Mixture of resin component (decomposition product) and solid residue: 77.2 g was obtained. The ratio of the resin component to the solid residue in the mixture and the molecular weight of the resin component are summarized in Table 2.

[Example 17] Treatment of urea resin molding material In Example 13, the same operation as in Example 13 was performed, except that a urea resin molding material (CU-A made by Matsushita Electric Works) was used as the thermosetting resin. Mixture of resin component (decomposition product) and solid residue: 77.4 g was obtained. The ratio of the resin component to the solid residue in the mixture and the molecular weight of the resin component are summarized in Table 2.

[Example 18] Treatment of phenol resin molding material In Example 13, the same operation as in Example 13 was carried out except that orthocresol (manufactured by Wako Pure Chemical Industries, Ltd.) was used as the solvent instead of phenol. Mixture of (decomposition product) and solid residue: 75.8 g was obtained. The ratio of the resin component to the solid residue in the mixture and the molecular weight of the resin component are summarized in Table 2.

[Example 19] Treatment of phenol resin molding material In Example 13, the same operation as in Example 13 was performed except that paracresol (manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of phenol as a solvent. Mixture of (decomposition product) and solid residue: 76.0 g was obtained. The ratio of the resin component to the solid residue in the mixture and the molecular weight of the resin component are summarized in Table 2.

[Example 20] Treatment of phenol resin molding material Resin component in Example 13 except that a mixture of phenol: 53.5 g and water: 53.5 g was used as a solvent. Mixture of (decomposition product) and solid residue: 67.6 g was obtained. The ratio of the resin component to the solid residue in the mixture and the molecular weight of the resin component are summarized in Table 2.

[Example 21] Treatment of phenolic resin molding material In Example 13, except that the charge amount of a general-purpose phenolic resin molding material (PM-8200 manufactured by Sumitomo Bakelite Co., Ltd.) was 100.0 g, the same as in Example 13 Operation was performed to obtain 123.0 g of a mixture of a resin component (decomposition product) and a solid residue. The ratio of the resin component to the solid residue in the mixture and the molecular weight of the resin component are summarized in Table 2.

[Example 22] Treatment of phenol resin molding material In Example 13, except that the reaction temperature was set to 350 ° C, the same operation as in Example 13 was performed, and the resin component (decomposition product), the solid residue, Of 74.6 g. The ratio of the resin component to the solid residue in the mixture and the molecular weight of the resin component are summarized in Table 2.

[Example 23] Treatment of phenol resin molding material In Example 13, except that 2.9 g of calcium hydroxide (manufactured by Wako Pure Chemical Industries): 2.9 g was added as a catalyst for promoting the reaction, and the reaction temperature was set to 300 ° C. The same operation as in Example 13 was performed to obtain 77.0 g of a mixture of a resin component (decomposition product) and a solid residue. The ratio of the resin component to the solid residue in the mixture and the molecular weight of the resin component are summarized in Table 2.

[Example 24] Reuse as a phenolic resin molding material As a raw material of a thermosetting resin molding material, the resin component recovered in Example 11: 43 parts by weight of hexamethylenetetramine (manufactured by Wako Pure Chemicals, special grade) : 7 parts by weight, wood powder: 40 parts by weight, calcium carbonate (manufactured by Wako Pure Chemical Industries): 10 parts by weight were mixed and reused as a phenol resin molding material. After the raw materials are dry-mixed with a cooking mill (manufactured by Matsushita Electric, fiber mixer), test pieces of bending strength and heat distortion temperature are prepared under conditions of a mold temperature of 175 ° C., a molding pressure of 10 MPa, and a molding time of 3 minutes. Produced. The bending strength / flexural modulus and thermal deformation temperature were measured according to JIS-K6911 “General Test Method for Thermosetting Plastics”. In addition, the flowability of the molding material was determined by measuring the spiral flow of the molding material and determining that the longer the spiral flow, the better the fluidity. Spiral flow is performed using a spiral grooved mold having a cross-sectional shape of upper base: 5 mm, lower base: 4 mm, height: 4 mm, mold temperature: 150 ° C., injection pressure: 15 MPa, curing time : Evaluated under measurement conditions of 60 seconds. Table 3 shows the measurement results.

[Examples 25 to 35] Reuse as a phenolic resin molding material As a raw material of a thermosetting resin molding material, the resin component recovered in Example 11 or Example 12, and / or in Example 11 or Example 12. Using the collected residue, it was reused as a phenol resin molding material with the formulation shown in Table 3. When a normal phenol resin was used in combination as a chemical raw material, the following three types of novolak type phenol resins having different molecular weights were used in the formulations shown in Table 3.
Novolac type phenolic resin A (Mw: 4100)
Novolac type phenolic resin B (Mw: 8000)
Novolac type phenolic resin C (Mw: 2200)
The bending strength / flexural modulus, thermal deformation temperature, and spiral flow were measured in the same manner as in Example 24 except that the blending of raw materials was changed. The composition of the raw materials and the material properties (bending strength / flexural modulus, thermal deformation temperature, spiral flow) are summarized in Table 3.

[Example 36] Reuse as phenolic resin molding material As a raw material of molding material, a mixture of resin component and residue recovered in Example 22: 51 parts by weight of hexamethylenetetramine (manufactured by Wako Pure Chemical, Special grade): 7 parts by weight, wood powder: 40 parts by weight, calcium carbonate (manufactured by Wako Pure Chemical Industries): 10 parts by weight, except for blending, bending strength, flexural modulus, thermal deformation Temperature and spiral flow were measured. Table 4 shows the measurement results.

[Examples 37 to 44] Reuse as a phenolic resin molding material As a raw material of a molding material, a mixture of a resin component and a residue recovered in Example 22 or Example 23 was used, and phenols having the formulations shown in Table 3 were used. Reused as resin molding material. When a normal phenol resin was used in combination as a chemical raw material, the following three types of novolak type phenol resins having different molecular weights were used in the formulations shown in Table 3.
Novolac type phenolic resin A (Mw: 4100)
Novolac type phenolic resin B (Mw: 8000)
Novolac type phenolic resin C (Mw: 2200)
The bending strength / flexural modulus, thermal deformation temperature, and spiral flow were measured in the same manner as in Example 24 except that the blending of raw materials was changed. Table 4 summarizes the raw material composition and material properties (bending strength / flexural modulus, thermal deformation temperature, spiral flow).

[Comparative Example 1] Characteristic evaluation of ordinary phenol resin molding material As a raw material of the molding material, hexamethylenetetramine (manufactured by Wako Pure Chemicals, special grade) with respect to 43 parts by weight of the novolak type phenol resin A (Mw: 4100): 7 parts by weight, wood powder: 40 parts by weight, calcium carbonate (manufactured by Wako Pure Chemical Industries): 10 parts by weight, except that the ingredients were changed and bending strength and bending elasticity were the same as in Example 24. The rate, heat distortion temperature, and spiral flow were measured. The composition of the raw materials and the material properties (bending strength / flexural modulus, thermal deformation temperature, spiral flow) are summarized in Table 3.

As can be seen from the results shown in Table 3, when the resin component and / or solid residue produced by the method of the present invention is used as a raw material of a phenol resin molding material, it is almost equivalent to a normal phenol resin molding material. A molding material having high mechanical strength, high heat change temperature, and high fluidity can be produced. In addition, by adjusting the conditions of solubilization treatment, the type and blending amount of chemical raw materials to be used together, the blending of raw materials, etc., higher mechanical strength, higher heat change temperature, and higher fluidity than ordinary phenol resin molding materials are achieved. The molding material which has can be produced.
Further, as can be seen from the results shown in Table 4, even if the mixture of the resin component produced by the method of the present invention and the solid residue is used as a raw material for the phenol resin molding material without being separated as it is, A molding material having a high mechanical strength, a high thermal change temperature, and a high fluidity equivalent to the case where it is separated and used as a raw material can be produced.

[Example 45] Reuse as an epoxy resin molding material As a raw material of an epoxy resin molding material, bisphenol A type epoxy resin (manufactured by Japan Epoxy Resin, Epicoat 828): 100 parts by weight of the resin recovered in Example 1 Ingredients: 56 parts by weight, 2-ethyl-4-methylimidazole (manufactured by Shikoku Chemicals, Curazole 2E4MZ): 0.5 parts by weight, spherical fused silica (average particle size 20 μm, maximum particle size 100 μm): 300 parts by weight Then, after dry-mixing with a cooking mill (manufactured by Matsushita Electric Industrial Co., Ltd., fiber mixer), a test piece of bending strength and heat distortion temperature is prepared under conditions of a mold temperature of 175 ° C., a molding pressure of 10 MPa, and a molding time of 3 minutes. did. The bending strength / flexural modulus and thermal deformation temperature were measured according to JIS-K6911 “General Test Method for Thermosetting Plastics”. Table 5 shows the measurement results.

[Examples 46 to 50] Reuse as epoxy resin molding material Table 5 shows the resin components recovered in any of Example 2, Example 3, and Example 11 as raw materials for epoxy molding material. Recycled as an epoxy resin molding material. When a normal phenol resin was used in combination as a chemical raw material, a novolac type phenol resin D (manufactured by Sumitomo Bakelite, PR-51470) was used in the formulation shown in Table 5. The bending strength / flexural modulus and thermal deformation temperature were measured in the same manner as in Example 45 except that the blending of raw materials was changed. Table 5 summarizes the raw material composition and material properties (bending strength, flexural modulus, thermal deformation temperature).

[Comparative Example 2] Characteristic evaluation of ordinary epoxy resin molding material As a raw material of the epoxy resin molding material, bisphenol A type epoxy resin (manufactured by Japan Epoxy Resin, Epicoat 828): 100 parts by weight of novolac type phenolic resin D ( Sumitomo Bakelite, PR-51470): 56 parts by weight, 2-ethyl-4-methylimidazole (manufactured by Shikoku Chemicals, Curazole 2E4MZ): 0.5 part by weight, fused spherical silica (manufactured by Micron, HALIICS-COL): 300 parts by weight The bending strength / bending elastic modulus and heat distortion temperature were measured in the same manner as in Example 45 except that the part was replaced with the part. Table 5 summarizes the raw material composition and material properties (bending strength, flexural modulus, thermal deformation temperature).

  As can be seen from the results shown in Table 5, even when the resin component produced by the method of the present invention is used as a raw material for an epoxy resin molding material, it has a high mechanical strength almost equal to that of a normal epoxy resin molding material and a high heat. A molding material having a variable temperature can be produced.

  High-speed decomposition and / or solubilization of plastics containing thermosetting resins that have been included in industrial waste discharged from factories and general waste and that have not been recyclable until now. Can be processed and reused as a raw material for plastics.

Claims (14)

  (A) a step of decomposing and / or solubilizing the plastic into a resin component by treating the plastic containing the thermosetting resin in a supercritical or subcritical solvent containing a phenol compound as an essential component; and (B) A plastic recycling method comprising a step of separating the resin component and the residue generated by the treatment.   (C) The plastic recycling method according to claim 1, further comprising a step of reusing the resin component and / or the residue as a raw material for the plastic.   The plastic recycling method according to claim 2, wherein the resin component and the residue are reused as a raw material of the plastic as a mixture.   The said thermosetting resin is the recycling method of the plastics in any one of Claims 1-3 which is 1 type, or 2 or more types chosen from a phenol resin, an epoxy resin, a melamine resin, and a urea resin.   The plastic recycling method according to any one of claims 1 to 4, wherein the phenol compound is one or more selected from phenol, cresol, xylenol, resorcin, alkyl-substituted phenol, and naphthol.   The method for recycling plastic according to claim 1, wherein the phenol compound is separated and recovered from a resin component obtained from the plastic.   The said process (a) is a plastic recycling method in any one of Claims 1-6 performed by the temperature of the range of 200-500 degreeC.   The said process (a) is a recycling method of the plastics in any one of Claims 1-7 performed by the range of pressures 1-60 Mpa.   A plastic recovered product comprising a resin component and / or a residue, obtained by the plastic recycling method according to claim 1.   The plastic processing recovery product according to claim 9, wherein the resin component is a compound mainly composed of a resin component having a molecular weight of 200 to 10,000.   10. The plastic processing and recovery according to claim 9, wherein the residue is selected from an undecomposed resin component of a plastic containing the thermosetting resin, a polymerized carbonized product of the plastic, and a filler contained in the plastic. Stuff.   A recycled plastic obtained by reusing the plastic processing recovery product according to any one of claims 9 to 11 as a raw material.   A recycled plastic comprising 2 to 80% by weight of the plastic recovered product according to any one of claims 9 to 11 and recycled as a raw material.   The thermosetting resin molding material formed by reusing the plastic processing collection material in any one of Claims 9-11 as a raw material.