JP2006233141A - Phenolic resin molding material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a phenolic resin molding material reusing a regenerated base material obtained through a decomposing and/or solubilizing treatment of a fibrous glass reinforced plastic containing thermosetting resins which is contained in large quantities in an industrial waste discharged from factories and a domestic waste. <P>SOLUTION: This phenolic resin molding material contains a regenerated base material of a glass fiber compounded with organic components, which is obtained by decomposing and/or solubilizing a fibrous glass reinforced plastic containing thermosetting resins in a solvent containing a phenolic compound as an essential component. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a phenol resin molding material. More specifically, the present invention relates to a phenol resin molding material containing a recycled base material obtained by processing a glass fiber reinforced plastic containing a thermosetting resin.

  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. Once a thermosetting resin is cured, it is not softened or melted by heat and does not dissolve in a solvent. Therefore, it is technically difficult to regenerate a valuable chemical raw material from the cured product. However, in recent years, the necessity of environmental conservation and the construction of a resource recycling society has been studied, and various studies have been conducted on the recycling of thermosetting resins.

  In order to overcome these problems, studies have been made on a method for recovering chemical raw materials by solubilizing a thermosetting resin using a supercritical fluid. For example, a method of solubilizing a thermosetting resin in a solution of a mononuclear phenol compound or water / mononuclear phenol compound in a supercritical or subcritical state and recovering an oligomer of a resin component has been studied ( For example, refer to Patent Document 1 and Non-Patent Document 1.) In this method, the thermosetting resin can be 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 can be recovered. It is said that it can be reused as a raw material.

  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 polymerized carbon compound is generated, a decomposition residue composed of an undecomposed component or a polymerized carbide is generated. However, in the recycling method, when the decomposition residue is reused as it is without being subjected to the step of adjusting the decomposition residue to a specific range, the organic content, particle size, or composition of the recycled substrate Depending on the amount, etc., the mechanical strength of the recycled plastic may decrease.

  On the other hand, in the study aimed at recovering the filler, for example, only a resin component is removed using a supercritical liquid or a subcritical liquid, and a study of recovering recycled carbon fiber is also performed (for example, Patent Documents). However, 2) is not clear regarding the mechanical strength of recycled materials using recovered recycled carbon fibers.

JP 2001-151933 A (page 3-4) JP 2003-190759 A (page 3-4) Proceedings of the 52nd Network Polymer Lecture Conference, 56-59 (2002)

  The present invention relates to a phenolic resin molding material containing a recycled base material obtained by processing a glass fiber reinforced plastic containing a thermosetting resin. Even if the recycled base material is used, the phenolic resin has better mechanical strength than the conventional method. A molding material is provided.

That is, the present invention
(1) It includes a recycled base material having glass fibers obtained by decomposing and / or solubilizing a glass fiber reinforced plastic containing a thermosetting resin in a solvent containing a phenol compound as an essential component. Phenolic resin molding materials,
(2) The phenol resin molding material according to (1), wherein a particle size of the glass fiber reinforced plastic containing the thermosetting resin is 0.1 μm or more and 10,000 μm or less,
(3) Item (1) or Item (2), wherein the recycled base material is a composite of an organic component and / or a phenol compound contained in a solvent and an inorganic component contained in a glass-reinforced fiber plastic. ) Phenol resin molding material according to item
(4) The phenol resin molding material according to any one of (1) to (3), wherein the inorganic component includes glass fibers contained in glass fiber reinforced plastic.
(5) The recycled base material contains 1 to 100 parts by weight of the decomposed resin component of the plastic and / or the undecomposed organic component of the plastic with respect to 100 parts by weight of the inorganic component contained in the glass fiber reinforced plastic. The phenol resin molding material according to any one of (1) to (4), characterized in that
(6) The reclaimed base material according to any one of (1) to (5), wherein the reclaimed base material contains 10 to 99% by weight of glass fiber contained in the glass fiber reinforced plastic with respect to the entire reclaimed base material. The described phenolic resin molding material,
(7) The phenol resin molding material according to any one of (4) to (6), wherein the fiber length of the glass fiber contained in the recycled base material is 0.1 μm or more and 5,000 μm or less.
(8) The phenol resin molding material according to any one of (4) to (7), wherein L / D of the glass fiber contained in the recycled base material is 0.01 to 500.
(9) The reclaimed substrate according to any one of (1) to (8), wherein a size of the regenerated substrate is 0.1 μm or less and / or 5,000 μm or more is removed. Phenolic resin molding material,
(10) The phenol resin molding material according to any one of (1) to (9), including 1 to 300 parts by weight of the recycled base material with respect to 100 parts by weight of phenol resin.
Is to provide.

  According to the present invention, it is obtained by decomposing and / or solubilizing glass fiber reinforced plastic containing a thermosetting resin, which is contained in a large amount in industrial waste and general waste discharged from factories and the like. A phenol resin molding material in which the recycled base material is reused can be provided.

  The present invention includes a phenolic resin molding comprising a recycled base material obtained by decomposing and / or solubilizing a glass fiber reinforced plastic containing a thermosetting resin in a solvent containing a phenol compound as an essential component. Material. In addition, the process of the plastic in this invention includes the process by chemical decomposition and / or the process by physical solubilization.

  The glass fiber reinforced plastic containing the thermosetting resin treated in the present invention includes a cured resin, an uncured or semi-cured resin, a varnish containing these resins, and the like. In addition to a single thermosetting resin, it contains glass fibers. In addition, the other components include inorganic fillers such as metals and metal oxides and hydroxides, and organic fillers such as wood, paper, and cloth as fillers. Examples of the recycled base material in the present invention include organic components and inorganic components contained in the glass fiber reinforced plastic containing the thermosetting resin, and the organic component is contained in the plastic and obtained by decomposition / solubilization treatment. Examples of the inorganic component include glass fibers contained in the plastic and obtained by decomposition / solubilization treatment, and inorganic fillers other than glass fibers.

  Although it does not specifically limit as a thermosetting resin in the glass fiber reinforced plastic applied to this invention, A phenol resin, an epoxy resin, a melamine resin, and a urea resin can be applied especially effectively. Furthermore, what contains a phenol resin is more preferable. Moreover, the particle size of the glass fiber reinforced plastic used for the treatment is preferably in the range of 0.1 μm or more and 10,000 μm or less. When the particle size is smaller than the above range, the effect as a reinforcing material may not be obtained because the particle size of the recycled substrate obtained by the treatment is also small. Moreover, when larger than the said range, since the time which a decomposition | disassembly and / or solubilization process requires increases, and process efficiency falls, it is not practical. Examples of the method for adjusting the particle size of the glass fiber reinforced plastic include a method by pulverization, a method by sieving, a method by a gravitational classifier, a method by mixing the adjusted material by the adjustment method, etc. The method is not limited to these methods as long as the range can be adjusted. Examples of the pulverization method include a method of coarsely pulverizing with a pulverizer such as a hammer mill and a Raymond mill, and a method of finely pulverizing with a pulverizer such as a ball mill. After these pulverizations, the particle size is adjusted by sieving. It is preferable to use the above.

1 Decomposing and solubilizing glass fiber reinforced plastic The glass fiber reinforced plastic containing the thermosetting resin is decomposed and / or solubilized in a solvent containing a phenol compound as an essential component, and a specific recycled base material is formed. By using it, a recycled base material that can be reused as a reinforcing material can be obtained.
(A) Solvent The phenol compound used in the present invention is one in which at least one hydrogen bonded to carbon of the aromatic ring is substituted with a hydroxyl group, and this is used alone or as a solvent in a mixture with water, and glass fiber reinforced plastic. If it is a phenolic compound which can be decomposed | disassembled and / or solubilized on the conditions mentioned later, it will not specifically limit. Usually, mononuclear phenol compounds such as phenol, cresol, xylenol, resorcin, and alkyl-substituted phenol, or phenol compounds such as 1-naphthol and 2-naphthol are preferably used, and one or more of these are used. It is done. Of these, phenol is preferred because of its cost and its effect on decomposition and / or solubilization reactions. Moreover, the said phenol compound can use what contains the phenol compound obtained by isolate | separating and refine | purifying, after decomposing | disassembling and / or solubilizing a plastic with the processing method of the glass fiber reinforced plastics of this invention.

  When a mixture with another solvent other than the phenol compound is used as the solvent, the other solvent includes water, monomer alcohols such as methanol and ethanol, glycols such as ethylene glycol and propylene glycol, and ketones. Any of those used as a solvent in a normal chemical reaction such as ethers, ethers, esters, organic acids, and acid anhydrides may be used, and a plurality of solvents may be used. Further, the mixing ratio of the other solvent to the phenol compound is preferably used by mixing at a ratio of 1 to 500 parts by weight of the other solvent with respect to 100 parts by weight of the phenol compound, more preferably 100 parts by weight of the phenol compound. To 1 to 100 parts by weight of the other solvent.

  In the present invention, the proportion of the solvent containing a phenol compound as an essential component is preferably in the range of 50 to 1000 parts by weight, more preferably in the range of 100 to 400 parts by weight with respect to 100 parts by weight of the glass fiber reinforced plastic. It is. When the reaction solvent is less than the lower limit, it may be difficult to smoothly proceed the decomposition and / or solubilization reaction of the glass fiber reinforced plastic. On the other hand, if the amount exceeds the upper limit, a great amount of heat is required to heat the reaction solvent and the consumption of heat energy increases, but a special effect may not be obtained.

(B) Process conditions As a decomposition | disassembly and / or solubilization process condition in this invention, the solvent which uses the said phenol compound as an essential component can be adjusted with temperature and pressure. As said temperature, the range of 100-500 degreeC is preferable normally, More preferably, it is the range of 200-450 degreeC. When the temperature is lower than the lower limit, the decomposition and / or solubilization rate of the glass fiber reinforced plastic may be reduced, and it may be difficult to process in a short time. 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 composition of the recovered glass fiber reinforced plastic resin component and the recycled base material changes. May be difficult to reuse. Moreover, as said pressure, 1-60 MPa is preferable normally, More preferably, it is the range of 2-40 MPa. If the pressure is lower than the lower limit, the decomposition and / or solubilization rate may be reduced, and the processing of the glass fiber reinforced plastic itself may be difficult. If the pressure is higher than the above upper limit value, equipment that can be operated under severer conditions is required, and energy required to maintain a high pressure is increased, but the decomposition and / or solubilization rate is hardly improved, and it is extremely high. May not be effective. Furthermore, as an atmosphere for the decomposition and / or solubilization treatment, either an air atmosphere or an inert gas atmosphere such as nitrogen may be selected, and the treatment container should be either an open system, a sealed system or a system. Although it is not limited in particular, an example is a heat and pressure treatment container such as an autoclave. The time for the decomposition / solubilization step can be adjusted in the range of 1 to 60 minutes, but the treatment is usually completed in about 3 to 30 minutes.

(C) Catalyst In the decomposition and solubilization of the glass fiber reinforced plastic, it is more effective to use a catalyst that accelerates the processing speed. The catalyst in that case is not particularly limited. For example, a Bronsted acid base / Lewis acid base, or a natural inorganic / organic compound, or a compound that exhibits an equivalent effect by a hydration reaction or the like with a metal oxide, etc. 1 type, or 2 or more types of these can be used.
Moreover, it is preferable that the addition amount of the said catalyst is 0.1-30 weight part with respect to 100 weight part of said thermosetting resins, More preferably, it is 1-10 weight part.

2. Method for adjusting recycled base material The recycled base material is obtained by separating from the contents of the heat and pressure processing container subjected to the above-mentioned treatment from a solvent (phenol compound, water, etc.) and an organic component, and phenol resin molding It can be reused as a material reinforcement.
The separation method is not particularly limited, and examples thereof include a method such as cyclone, filtration, and gravity sedimentation, which are used in ordinary solid-liquid separation. Moreover, after diluting the mixture containing the reproduction | regeneration base material and organic component which were obtained by the process with the organic solvent, you may perform solid-liquid separation operation, such as a cyclone, filtration, and gravity sedimentation.

  It is preferable to use a regenerated substrate whose size is adjusted in the range of 0.1 μm or more and 5,000 μm or less. As a method for adjusting the size of the regenerated substrate, there can be mentioned a method using a material which has not passed through a sieve having an opening diameter of 0.1 μm and passed through a sieve having an opening diameter of 5,000 μm. When a recycled base material having a particle size smaller than the above range is blended, the fiber length of the glass fiber obtained as the recycled base material is unnecessarily shortened and the effect as a reinforcing material is reduced. In some cases, the mechanical strength of the phenol resin molding material is reduced. Moreover, when the reproduction | regeneration base material with a larger particle size than the said range is mix | blended, the reproduction | regeneration base material in a phenol resin molding material may not disperse | distribute uniformly, but a molding defect may arise. The step of sieving the recycled base material can be performed either after the recycled base material is dried or dispersed in a solvent.

The recycled base material is contained in 1 to 100 parts by weight of the glass fiber reinforced plastic and 100% by weight of the inorganic component contained in the glass fiber reinforced plastic. More preferably, the decomposition organic component is combined.
In the present invention, the organic component may physically adsorb the inorganic component, particularly the surface of the glass fiber, while the organic component may be complexed by a chemical reaction on the surface of the glass fiber. .
Further, the surface of the glass fiber in the recycled substrate obtained by the present invention is physically and / or chemically combined with phenol used as a solvent during the decomposition and / or solubilization treatment of the glass fiber reinforced plastic. There may be. As described above, the inorganic component and the organic component in the recycled base material are physically and / or chemically combined to improve the adhesion at the interface between the recycled base material and the newly blended resin component. The mechanical strength of the phenol resin molding material using the material is improved.

  It is preferable that the glass fiber contained in the said reproduction | regeneration base material is a ratio of 10 to 99 weight% with respect to the whole reproduction | regeneration base material. When the proportion is less than the above range, the effect as a reinforcing material of the recycled base material may not be obtained. When the proportion is more than the above range, the organic component is hardly contained. In some cases, a great effect cannot be obtained on the adhesion to the resin component, and in other cases, the effect of the resin component as a binder for focusing the inorganic component in the recycled substrate cannot be obtained. The fiber length of the glass fiber is preferably in the range of 0.1 μm to 5,000 μm, and the L / D of the glass fiber is more preferably in the range of 0.01 to 500. When L / D is smaller than the above range, the effect of glass fiber as a reinforcing material may not be sufficiently obtained. In order to obtain a glass fiber larger than the above range, it is necessary to increase the particle size of the glass fiber reinforced plastic used in the decomposition and / or solubilization process, and the energy required for the treatment is greatly increased. Absent.

  The glass fiber in the recycled substrate is present in a state where the surface is combined physically or chemically, or both by the organic component contained in the glass fiber reinforced plastic and / or the phenol compound used as a solvent. . For example, when the organic component is physically coated on the surface of the glass fiber, the organic component may be chemically bonded to silicon, oxygen of a siloxane bond, or a hydroxyl group.

  The organic component usually contains a compound mainly composed of a resin component having a molecular weight of 200 to 100,000. Here, the molecular weight in the present invention means a weight average molecular weight. Necessary because the molecular weight of 200 to 100,000 is the same as that of a chemical raw material (prepolymer) used when producing a molding material, especially a plastic composed of a thermosetting resin such as a normal phenol resin. By refining accordingly, it can be reused as a prepolymer. As a typical example of the resin component, when the plastic is composed of a phenol resin, a phenol resin or an oligomer in which nuclei of the phenol skeleton are bonded by a methylene bond can be given. Other examples include a melamine resin other than a phenol resin, a phenol resin or oligomer containing a melamine resin structure in which the melamine skeleton nuclei are bonded by a methylene bond, and a urea resin other than a phenol resin. A phenolic resin or oligomer having a urea resin structure in which the nuclei of the urea skeleton are bonded by a methylene bond, or when each of these is included, each of the above resins or oligomers, the phenol skeleton, the melamine skeleton, or the urea skeleton is methylene. Examples thereof include a phenol resin including a structure copolymerized by bonding, but these components are examples, and the resin components are not limited at all. Here, having a resin component having a molecular weight of 200 to 100,000 as a main component means that the resin component having a molecular weight shown here is contained in an amount of 50% or more. More than 000 resin components are also included. Moreover, as a resin component which has a molecular weight of 200-100,000, in the case of a normal phenol resin, it is about 2-1,000 nuclei of a raw material monomer. In addition, the compound mainly composed of a resin component having a molecular weight of 200 to 100,000 is not only a component obtained from a resin component such as a phenol resin in a plastic, but also an organic filler or a substrate contained in the plastic. The resulting component may be included.

3. Phenolic resin molding material containing a recycled base material In the phenolic resin molding material of the present invention, a recycled base material obtained by the method for treating a glass fiber reinforced plastic containing the thermosetting resin and the method for adjusting the recycled base material, It is reused as a raw material for phenolic resin molding materials.

  As a method of reusing a recycled base material obtained from a plastic containing the thermosetting resin as a raw material of the molding material, the recycled base material can be mixed with other raw materials and reused by a known manufacturing method. In this case, only the recycled base material may be used as a raw material without using a new base material, or may be used in combination with other chemical raw materials and / or fillers. As content of the said reproduction | regeneration base material, what is necessary is just the range of 1-300 weight part with respect to 100 weight part of phenol resins, Preferably it is 2-80 weight% with respect to the whole phenol resin molding material. More preferably, it is 5 to 60% by weight.

Examples of the phenol resin used for the phenol resin molding material include novolac type phenol resins and resol type phenol resins.
When a novolac type phenol resin is used in the phenol resin molding material, hexamethylene tetramine is usually used as a curing agent. The content of hexamethylene tetramine is 10 to 25 wt. Part is preferred. The content of the novolak type phenol resin is preferably 20 to 80% by weight, more preferably 30 to 60%, based on the whole phenol resin molding material, including hexamethylenetetramine as a curing agent. % By weight. Moreover, in order to adjust the hardening rate of a phenol resin molding material, magnesium oxide, calcium hydroxide, etc. can be used as a hardening adjuvant as needed.

  In addition, when the recycled base material is used in combination with a normal filler as a raw material of the phenol resin molding material, the filler to be used in combination is not particularly limited, but the inorganic base material used in the normal phenol resin molding material and / or Alternatively, an organic substrate can be used. Examples of the inorganic base material include calcium carbonate, calcined clay, talc, silica, diatomaceous earth, alumina, and magnesium oxide. These inorganic base materials can be selected as necessary depending on the use of the molded product. Examples of the organic substrate include wood powder, pulp, plywood powder, paper pulverized powder, and cloth pulverized powder.

The phenol resin molding material of the present invention can be obtained by mixing and mixing the above components as appropriate, kneading the mixture using a kneader such as a heating roll or a heating kneader, and then forming the powder.
Moreover, the phenol resin molding material obtained in this way is shape | molded by methods, such as a compression molding method, a transfer molding method, and an injection molding method, and can be used for various uses as a molded article.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited at all by this.

[Example 1]
(1) Preparation of cured glass fiber reinforced plastic Novolac type phenolic resin (manufactured by Sumitomo Bakelite, PR-51714): 35 parts by weight, hexamethylenetetramine (manufactured by Wako Pure Chemicals, special grade): 10 parts by weight of cooking mill (Matsushita Electric) Made by a fiber mixer), 55 parts by weight of E glass fiber (manufactured by Nippon Sheet Glass, chopped strand) was added to the mixture, and dry-mixed in a bag to obtain a phenol resin molding material. This was molded by a press molding machine (temperature: 175 ° C., pressure: 10 MPa, molding time: 3 minutes) to obtain a glass fiber reinforced plastic cured product.
(2) Treatment of cured product of glass fiber reinforced phenolic resin molding material After pulverizing the cured product of glass fiber reinforced plastic obtained above, sieving and adjusting the particle diameter to 0.1 μm or more and 1,000 μm or less Using.
When mixing the above phenol resin molding material cured product: 58.3 g and a reaction solvent comprising a mixture of phenol: 85.6 g and water: 21.3 g, as a basic catalyst, powdered calcium hydroxide ( 0.6 g of Kanto Chemical Co.) was added. After charging the above mixture in an autoclave (Nitto High Pressure Co., Ltd., internal volume 200 cm ³ ), stirring the mixture at 300 rpm and setting the internal temperature to 300 ° C., the reactor internal pressure was increased to 5.0 MPa, After maintaining for 20 minutes for decomposition and solubilization treatment, it was cooled to air and returned to room temperature and normal pressure. Methanol was added to the mixture of the product obtained by the treatment and the unreacted solvent to dissolve the resin component, followed by filtration with a filter having a pore size of 1.0 μm, and the residue was collected. Furthermore, an equal amount of methanol is added to the recovered filter residue, washed with stirring at 40 ° C. for 30 minutes, filtered through a 1.0 μm filter again, and dried at 120 ° C. for 2 hours to regenerate the base. 30 g of material was obtained.

  The recycled substrate obtained above was adjusted to a particle size in the range of 0.1 μm to 1,000 μm by sieving. Moreover, the organic component contained in the regenerated substrate was determined by measuring the weight loss after burning at 500 ° C. for 5 hours, and as a result, it was 10 parts by weight with respect to the inorganic substance. In addition, since the calcium hydroxide used for the decomposition / solubilization treatment is contained in the inorganic substance in the recycled base material, the ratio of the glass fiber in the inorganic substance is 98% by weight, and the ratio to the entire recycled base material is 88% by weight. Furthermore, when 99 parts by weight of potassium chloride was blended with 1 part by weight of the recycled base material and analyzed by a Fourier transform infrared spectrophotometer, in addition to the spectrum derived from the glass component, phenol, phenol resin or its It was confirmed that there was a peak derived from the cured product.

(3) Recycling of glass fiber reinforced phenolic resin molding material cured material Using the recycled substrate obtained by the above processing method, a recycled phenolic resin molding material is produced, and the mechanical strength of the molding material is flexural strength and flexural elasticity. The rate was evaluated by measuring.

  Novolak-type phenolic resin (Sumitomo Bakelite, PR-51714): 35 parts by weight, hexamethylenetetramine (Wako Pure Chemicals, special grade): 10 parts by weight are dry-mixed in a cooking mill (Matsushita Electric, fiber mixer), Phenolic resin molding by adding 45 parts by weight of E glass fiber (made by Nippon Sheet Glass, chopped strands) to the mixture and 10 parts by weight of the regenerated substrate obtained by the above processing method, followed by dry mixing in the bag Obtained material. This was molded by a press molding machine (temperature: 175 ° C., pressure: 10 MPa, molding time: 3 minutes) to prepare a test piece of bending strength and bending elastic modulus. The flexural strength and flexural modulus were measured according to JIS-K6911 “General Test Method for Thermosetting Plastics”. As a result, bending strength: 210 MPa and bending elastic modulus: 18,000 MPa were obtained.

[Example 2] Treatment and recycling of cured product of glass fiber reinforced phenolic resin molding material Example 1 except that in Example 1, the recycled substrate was washed with methanol at 40 ° C for 30 minutes. The same operation as in No. 1 was performed to obtain a recycled phenol resin molding material. The results are summarized in Table 1.

[Example 3] Treatment and recycling of cured product of glass fiber reinforced phenolic resin molding material In Example 1, the composition of the recycled phenolic resin molding material was changed from 10 parts by weight to 20 parts by weight of recycled base material, and 45% by weight of E glass fiber. The recycled phenol resin molding material was obtained by performing the same treatment as in Example 1 except that the amount was changed to 35 parts by weight. The results are summarized in Table 1.

[Example 4] Treatment and recycling of cured glass fiber reinforced phenolic resin molding material In Example 1, the treatment was performed in the same manner as in Example 1 except that the decomposition / solubilization treatment time was changed from 20 minutes to 0 minutes. A recycled phenolic resin molding material was obtained. The results are summarized in Table 1.

[Example 5] Treatment and recycling of cured glass fiber reinforced phenolic resin molding material In Example 1, the treatment was performed in the same manner as in Example 1 except that the decomposition / solubilization treatment time was changed from 20 minutes to 120 minutes. A recycled phenolic resin molding material was obtained. The results are summarized in Table 1.

[Example 6] Treatment and recycling of cured product of glass fiber reinforced phenolic resin molding material In Example 1, the composition of the recycled phenolic resin molding material was changed from 10 parts by weight to 40 parts by weight of the recycled base material, and 45 weights of E glass fiber. A recycled phenol resin molding material was obtained in the same manner as in Example 1 except that the part was changed to 15 parts by weight. The results are summarized in Table 1.

[Example 7] Treatment and recycling of cured product of glass fiber reinforced phenolic resin molding material Recycled phenolic resin molding was performed in the same manner as in Example 1 except that the step of sieving the recycled base material was omitted. Obtained material. The results are summarized in Table 1.

[Comparative Example 1] Preparation of phenolic resin molding material using only glass fiber of virgin material and evaluation of mechanical strength In Example 1, blending of recycled phenolic resin molding material was performed using 10 parts by weight of recycled base material and 45 E glass fiber. A phenol resin molding material was obtained in the same manner as in Example 1 except that the E glass fiber was changed to 55 parts by weight from parts by weight. The results are summarized in Table 1.

[Comparative Example 2] Preparation of phenolic resin molding material using recycled substrate treated only with water and evaluation of mechanical strength In Example 1, the composition of the solvent was 85.6 g of phenol, 21.3 g of water to 106.9 g of water. A phenol resin molding material was obtained in the same manner as in Example 1 except that the decomposition / solubilization treatment temperature was changed from 300 ° C. to 380 ° C. and the treatment pressure was changed from 5 MPa to 25 MPa. The results are summarized in Table 1.

表１．ガラス繊維強化フェノール樹脂成形材料硬化物の処理結果及びリサイクル結果

Table 1. Processing results and recycling results of cured glass fiber reinforced phenolic resin molding materials

  As can be seen from the results shown in Table 1, the bending strength of the phenol resin molding material using the recycled base materials of Examples 1 to 3 is the same as the phenol resin molding material using only the glass fiber of the virgin material of Comparative Example 1. It is almost equivalent. Moreover, when there are many organic components in a reproduction | regeneration base material (Example 4), or when an organic component is not included (Example 5), the compounding quantity of a reproduction | regeneration base material is 10 weight with respect to 100 weight part of phenol resins. When a part is added (Example 6) and when the sieving step is not performed (Example 7), a slight decrease in bending strength and elastic modulus is confirmed, but it is within a range that does not cause any practical problems. On the other hand, when only water is used without including phenol, which is an essential component, in the decomposition / solubilization treatment solvent (Comparative Example 2), the effect as a reinforcing material of the recycled base material is small, and bending strength is increased.・ It can be seen that the elastic modulus has decreased.

Claims (10)

  A phenol resin molding comprising a recycled substrate having glass fibers obtained by decomposing and / or solubilizing a glass fiber reinforced plastic containing a thermosetting resin in a solvent containing a phenol compound as an essential component. material.   The phenol resin molding material according to claim 1, wherein the glass fiber reinforced plastic containing the thermosetting resin has a particle size of 0.1 μm or more and 10,000 μm or less.   The phenol resin molding material according to claim 1 or 2, wherein the recycled base material is a composite of an organic component contained in a glass-reinforced fiber plastic and / or a phenol compound contained in a solvent and an inorganic component.   The phenol resin molding material according to any one of claims 1 to 4, wherein the inorganic component includes glass fiber contained in glass fiber reinforced plastic.   2. The recycled base material includes 1 to 100 parts by weight of a plastic decomposition resin component and / or an undecomposed organic component of the plastic with respect to 100 parts by weight of an inorganic component contained in a glass fiber reinforced plastic. The phenol resin molding material in any one of thru | or 4.   The phenolic resin molding material according to any one of claims 1 to 5, wherein the recycled base material contains 10 to 99% by weight of glass fibers contained in the glass fiber reinforced plastic with respect to the entire recycled base material.   The phenol resin molding material according to any one of claims 4 to 6, wherein the fiber length of the glass fiber contained in the recycled base material is 0.1 µm or more and 5,000 µm or less.   L / D of the glass fiber contained in the said reproduction | regeneration base material is 0.01 or more and 500 or less, The phenol resin molding material in any one of Claim 4 thru | or 7   The phenol resin molding material according to any one of claims 1 to 8, wherein the recycled base material has a size of 0.1 µm or less and / or 5,000 µm or more removed.   The phenol resin molding material according to any one of claims 1 to 9, comprising 1 to 300 parts by weight of the recycled base material with respect to 100 parts by weight of the phenol resin.