KR100318140B1 - Scrap Powder Containing Thermosetting Resin, Compositions Using the Same, and Uses thereof - Google Patents

Abstract

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to the invention of the present invention, which can be used for various applications as additives by recycling laminated scrap, and relates to various compositions produced using the scrap. The present invention is intended to recycle all thermosetting scraps, including laminates prepared by impregnating a thermosetting resin with a reinforcing material such as kraft paper, and do not need to separate the thermosetting synthetic resin component and the reinforcing material component, and reduce these scraps to a predetermined size or less. The pulverized product can be used as a synthetic resin additive that retains the functional characteristics of the thermosetting resin composition, which is the parent of scrap, or can improve specific physical properties such as flame retardancy, insulation resistance, heat resistance, flexural strength, and the like. It is for use as an additive. In addition, the present invention also includes a varnish composition for a laminate, a thermosetting or thermoplastic resin composition, a coating composition, an adhesive composition, a building brick, a cement mortar composition, and a synthetic resin flooring composition including the laminate scrap scrap.

Description

Scrap powder containing thermosetting resin, composition using same, and use thereof {Scrap Powder Containing Thermosetting Resin, Compositions Using the Same, and Uses}

The present invention relates to a laminated plate scrap pulverized product obtained by pulverizing it to a predetermined size or less without discarding a laminated plate scrap prepared by impregnating a reinforcing material such as kraft paper with a thermosetting resin and various compositions using the same as an additive.

Laminates are one of the most commonly encountered materials in everyday life, and in the process of producing, processing, or using the products produced therein, an enormous amount of scrap is generated. Due to various harmful substances, the problem with the treatment of these laminate scraps has attracted attention as social, economic and environmental concerns.

Accordingly, many methods have been proposed for the recycling of scrap containing thermoplastic resins. These methods are inherently due to the properties of thermoplastics that are repeatedly melted by heat, and in reality, there is no big problem in industrially utilizing these methods.

However, as for the recycling of scraps containing thermosetting resins, no special recycling plan has yet been prepared, and most of the thermosetting resin scraps are disposed of almost entirely. Most of the thermosetting resin scraps contain harmful substances such as epichlorohydrin, phenol, formaldehyde, amines, and isocyanates and environmental hormones such as bisphenol A. Or it is classified as general waste and incinerated or landfilled. In addition, since the scrap is not easily decomposed, and there is a high possibility that various harmful substances are eluted, there is a problem in landfilling, and even when incinerated, it releases dioxin, which is known as the strongest carcinogen, and thus, the burden of environmental pollution is very serious. to be.

Therefore, many attempts and efforts have been made to recycle scraps containing thermosetting resins, which are very difficult to dispose of. However, once cured, they have a distinctive recycling method due to the characteristics of thermosetting resins that do not dissolve in ordinary solvents and are not melted again by heat. I can't find it.

In addition, since most thermosetting resins are impregnated with reinforcement materials such as paper or glass fiber and processed into a composite material form, it is difficult to separate the used thermosetting resin and the reinforcing material components, which makes it more difficult to recycle them.

As part of recycling, copper clad laminate scrap is recovered by burning scrap or by chemical treatment such as sulfuric acid or nitric acid to recover copper. However, the method does not provide a way to use the thermosetting resin and the reinforcing material components which occupy more than 90% by weight of the copper clad laminate scrap.

Accordingly, the present inventors use the functional properties of the thermosetting resin, which is the mother of the scrap, to recycle the scrap containing the thermosetting resin without discarding it, and then, regardless of the composition, composition, and form of the scrap, the thermosetting resin scrap is crushed to a predetermined size or less. New uses have been developed for use as additives in other synthetic resins or other compositions.

As the most representative application, the laminate scrap recycling method of the present invention is for recycling all thermosetting laminate scraps, in the form of board-like laminate scraps, as well as prepreg or foam, and sawdust-shaped cutting chips. Laminate scrap is to be recycled.

Looking at the functional properties of thermoset laminate scrap that has been discarded because of no special recycling, to date, most of the printed circuit boards are made by impregnating a reinforcement such as paper or fiberglass with a thermosetting resin such as phenolic resin or epoxy resin. It has excellent characteristics such as UL-94-V-0 flame retardancy, insulation resistance of 10E12Ω or more, dielectric constant of 5.0 or less, flexural strength of 14 kgf / mm2 or more.

As such, the characteristics of the printed circuit board scrap are significantly improved, and the recycling method of the laminated sheet scrap according to the present invention uses the dramatically improved functional properties.

It is an object of the present invention to provide a scrap mill as a new additive retaining the inherent functional properties of the scrap matrix for recycling and use of thermosetting resin-containing scrap having excellent functionality without disposal.

It is still another object of the present invention to provide various compositions that can be used for various applications by using a thermosetting resin-containing scrap pulverized product.

The above and other objects of the present invention can be achieved by the present invention described below. Hereinafter, the content of the present invention will be described in detail.

Hereinafter, the present invention will be described in detail.

The present invention includes a laminate produced by impregnating a reinforcing material such as paper or glass fiber in a thermosetting resin such as a phenol resin or an epoxy resin, and a pulverized product obtained by grinding all types of scrap containing a thermosetting resin to a predetermined size or less. It relates to a method for use as an additive in various compositions and to a composition containing said scrap grinding material.

The thermosetting resin scrap mentioned in the present invention is impregnated with a reinforcing material such as paper or glass fiber in the state of being alone, mixed or copolymerized with a thermosetting resin such as phenol, epoxy, melamine, urea, polyurethane, or unsaturated polyester resin, It refers to all kinds of scraps generated in the process of the process of extrusion, injection and the like and the process of using the workpiece. Therefore, all scraps in which the thermosetting resin is used, including prepreg or board-shaped laminates, foamed foams, and composite materials represented by FRP, are the subject of the present invention. There is no limitation on the shape and size.

For example, in the case of a printed circuit board, 'prepreg scrap' in the process of impregnating a thermosetting resin in the reinforcement material, 'copper laminated plate scrap' in the process of hot press molding the prepreg, and in order to cut the formed disc to a predetermined standard Various processes can be used in each process such as 'cutting scrap' due to routing, sawing, etc., 'punching powder (drilling powder)' generated during processing into printed circuit boards, and 'scrap scrap of printed circuit board' in the form of finished products. Scraps of various shapes and sizes are generated due to the cause, and all of them become recycling objects of the present invention.

The present invention has a number of novel features over conventional partial and limited recycling attempts for such thermoset scraps. As mentioned above, recycling for the purpose of recovering copper is limited to copper clad laminate scrap containing copper, but the present invention includes all thermosetting resin scrap not containing copper for recycling.

In addition, the present invention improves properties such as flame retardancy, electrical insulation, and mechanical strength based on the inherent difference of utilizing the inherent properties of the synthetic resin composition of the scrap's parent, unlike the initial recycling, which is not simply discarded. In addition to the properties of the functional additives that can be made in the case of composite material scraps have a characteristic that the synthetic resin and reinforcement components are not used separately.

In addition, the present invention is limited to the particle size and distribution used as an additive, so that the median diameter of the scrap grinding material is 150 μm or less, the maximum particle size is 400 μm or less, and 90% by weight of the total particles. The basic feature is a fine powder form having a size of 300 μm or less. Such a restriction on particle size and distribution is an important restriction condition related to processability and addition amount, and the smaller the particle size of the fine powder is, the better the processability is, and the amount of addition that can be added. This is because the smaller the particle size, the wider the surface area per unit weight, the slower the sedimentation speed of the particles, the mechanical damage or overload phenomenon in the processing process, and the damage of the reinforcement can be minimized. In addition, the larger the particle size is, the more defects such as pin-holes appear in the appearance of the produced product. In addition, uniform dispersion and distribution of additives are necessary to eliminate the variation of physical properties of each part of the product and to maximize the effect of addition, because the smaller the particle size is advantageous.

However, it is more effective to crush the sand into particles of similar size to replace conventional colored sand for epoxy mortar flooring, or to replace sand used for building bricks. .

Therefore, the optimum particle size of each is different depending on the intended use and the purpose of recycling, and the recycling process. It is evident to those skilled in the art that the determination of the optimum particle size is common sense.

In the present invention, it is possible to use the pulverized product of the scrap as an additive having the same functionality as the mother, and in the case of the reinforcing material, the chemical reaction does not occur and does not decompose, and the cured thermosetting resin is not dissolved by a general solvent, This is because it does not melt, and because it has a property that does not decompose in the crushing process or the synthetic resin processing process of the scrap, because only the size and shape is changed by the crushing. That is, it is different from the case of impregnating by adding a fine powder inorganic material such as Sb ₂ O ₃ , TiO ₂ to the varnish for manufacturing laminates, or by extrusion or injection by physically mixing thermoplastic pellets such as ABS and these inorganic materials. Without, it means that the scrap mill of the present invention can be used as a non-reactive, dispersible additive.

Moreover, the specific gravity of the scrap pulverization is smaller than those of these inorganic materials, and due to the specific gravity characteristics similar to those of general synthetic resins, physical mixing is much easier than those of these inorganic materials. In addition, most processing equipment includes a compulsory mixing device, and since the apparent specific gravity can be adjusted by changing the particle size of the scrap grinding powder, there is no problem in using it as a non-reactive dispersion additive in the resin composition. Regardless of the type of scrap, these can be added to add inherent functionality.

However, in order to facilitate processing and increase the amount of use, there is a restriction on the particle size of the scrap crushed material, which is the same as in the case of Sb ₂ O ₃ or TiO ₂ , which may vary depending on the application, but the particle size may be small. The higher the addition effect and the workability are as described above.

For example, when the scrap of FR-1 copper clad laminated board (specific gravity 1.1-1.2) is grind | pulverized into fine powder, and it is added to the phenol resin varnish (specific gravity 0.9-1.1) used for manufacture of FR-1 copper laminated laminated board, an inorganic substance Compared to the case of using as an additive, the physical mixing is relatively good, there is relatively less problem occurrence such as non-uniform dispersion, as well as the magnetic properties that the same properties as the parent FR-1 copper clad laminate is used By being a replica type recycling, not only can the consumption of phenolic resins, flame retardants, and plasticizers used be reduced, but the mechanical and electrical properties can be improved. In other words, the copper clad laminate scrap component pulverized to a particle size small enough to be added to the varnish so as not to cause processing problems can be an optimum copper clad laminate varnish additive.

This not only eliminates the common common sense of deterioration of physical properties due to the use of additives, but also provides the advantage of reducing the amount of heat required for curing in the press molding process of the laminate by using a cured additive.

Furthermore, when the scrap of the FR-4 laminate, which is a glass fiber reinforced epoxy resin copper clad laminate, is pulverized into fine particles and added to the varnish for producing FR-1 copper clad laminate, it exhibits much superior properties than the effect of the self-replicating type. As in the case of mixing an epoxy resin having better mechanical and electrical properties than phenolic resin under glass fiber reinforcement conditions, it is possible to expect a significant improvement in physical properties.

In addition, in the case where the thermosetting resin composite material scrap pulverized product of the present invention is added as an additive to the extrusion or injection process of the thermoplastic resin, the mechanical properties of the thermoplastic resin composition are imparted by giving the thermoplastic resin excellent mechanical properties, which is the greatest advantage of the composite material. It is possible to improve the strength, impart the chemical resistance, heat resistance, etc., which are the relative advantages of the thermosetting resin to the thermoplastic resin compounding composition, and when the flame retardant component is included, the amount of expensive flame retardant added as mentioned above The effect can be reduced.

In general, synthetic resin compositions often use inorganic materials such as calcium carbonate, aluminum hydroxide, and talc as additives or fillers, which are used for the purpose of reducing costs, controlling fluidity, improving appearance, and improving physical properties. Basically, it has the problem of increasing the specific gravity and especially the deterioration of chemical resistance. On the contrary, when the above-mentioned inorganic material is replaced with the thermosetting resin scrap pulverized product of the present invention, not only does the problem of specific gravity increase, but also shows excellent effects in terms of chemical resistance. In addition, it can be used more effectively to improve the specific physical properties, which effect and properties vary depending on the type and composition of the thermosetting resin composition, which is a scrap matrix, it is also affected by the inclusion and type of reinforcement. Basically, the scrap pulverized powder of the present invention can be used as an organic additive corresponding to the existing conventional inorganic additives, and a synthetic resin composition which reflects the characteristics of the components of the organic substance can be obtained. Accordingly, the synthetic resin composition may be newly made for the purpose of improving and modifying specific physical properties as well as the synthetic resin composition of the above-described self-replicating type.

In the case of the organic additives, as in the case of the inorganic additives, the performance as an additive varies greatly depending on the particle size and distribution of the powder, the particle form, the absorption capacity, the filling efficiency, etc., and therefore, it is natural to select an optimum condition. In addition, the scrap component may require purification other than grinding. For example, copper clad laminate scrap contains less than 10% by weight of copper in addition to the synthetic resin and the base component, unlike other scraps. The purpose determines the need for copper removal. In particular, in view of electrical properties and durability, it is preferable to remove the copper contained in the scrap grinding material. For example, in the case of self-replicating recycling in which copper is added to a varnish for copper clad laminates, copper particles remain, which hinders durability of the printed circuit board due to residual phenomenon after etching or ion migration. In the case of injection molded articles in which scrap powder containing copper is kneaded together with ABS resin and used as a flame retardant additive, discoloration occurs due to ion transfer phenomenon, and thus, removal of the copper component is preferable.

In order to sort and separate the copper contained in the copper clad laminate scrap, both a physical method using a difference in specific gravity and a chemical method using a chemical that dissolves copper may be applied.In any case, the separated copper may be used for electrolytic copper foil production or copper plating. Can be. However, the separation of the copper component by a chemical method is not a preferred method because the risk of corrosion of the synthetic resin component.

The physical method of separating copper is based on the specific gravity difference between composite components (thermosetting resin and substrate) and copper (specific gravity = 8.94), which is separated from the atmosphere like a fluidized bed reactor and has a specific gravity between composite components and copper. Although a method using a liquid is possible, separation in the atmosphere is not only a problem of dust, but inherently, when the pulverized powder has a particle distribution such as a normal distribution, the separation efficiency is greatly reduced. Thus, for FR-1 copper clad laminates (specific gravity = 1.2), chloroform (CHCl ₃ (specific gravity = 1.484)), carbon chlorides (CCl ₄ (specific gravity = 1.589) or C ₂ Cl ₄ (specific gravity = 1.6230)) or iron chloride When using a medium specific gravity liquid such as (FeCl ₂ , specific gravity = 3.16), it is possible to remove copper with high efficiency without generating dust.

In the present invention, an additive obtained by pulverizing to a predetermined size or less and a recycling use for adding the same to a synthetic resin composition without discarding the thermosetting resin scrap as described above are presented, but the following uses are not limited thereto.

Use 1: thermosetting resin composition additive

Use 2: thermoplastic resin composition additive

Use 3: paint and adhesive composition additive

Use 4: building brick and cement mortar composition additive

Use 5: Epoxy, Polyurethane, and PVC Resin Flooring Composition Additives

The thermosetting resin-containing scrap pulverized product according to the present invention comprises a thermosetting resin-containing scrap such as a laminated board, a copper-clad laminate, a prepreg, a foam, a composite material, or sawdust-shaped scraps containing a thermosetting resin. The average particle size is 150 µm or less and the maximum particle size is 400 µm or less, and the particle size of 90% by weight of the total particles is 300 µm or less. The thermosetting resin-containing scrap mill may further comprise a flame retardant or non-combustible component containing nitrogen, phosphorus, bromine, chlorine, and / or antimony. In addition, the thermosetting resin-containing scrap pulverization may further comprise a nitrogen component of melamine or urea.

According to another embodiment of the present invention, a thermosetting resin-containing scrap pulverized material is used to separate a reinforcement component from a thermosetting resin-containing scrap such as a laminate, a copper laminate, a prepreg, a foam, or a composite material containing a thermosetting resin. Particle size is 0.5 mm or more and 3 mm or less without or without separation. The thermosetting resin-containing scrap mill may further comprise a flame retardant or non-combustible component containing nitrogen, phosphorus, bromine, chlorine, and / or antimony. In addition, the thermosetting resin-containing scrap mill may further comprise a nitrogen component of melamine or urea.

The thermosetting resin-containing scrap pulverized product of the fine powder is used as an additive in the varnish for the laminate, in which case it is preferably added in an amount of 0.1 to 30% by weight.

The thermosetting resin-containing scrap grind having a particle size of 0.5 mm or more and 3 mm or less is used as an additive in an epoxy mortar, cement mortar, or building brick composition, in which case it is preferably added in an amount of 0.1 to 50% by weight.

The thermosetting resin-containing scrap pulverized product of the fine powder is used as an additive in the thermoplastic resin composition, in which case it is preferably added in an amount of 0.1 to 40% by weight.

The thermosetting resin-containing scrap pulverized product of the fine powder is used as an additive in the thermoplastic resin composition, in which case it is preferably added in an amount of 0.1 to 60% by weight.

The thermosetting resin-containing scrap pulverized product of the fine powder is used as an additive in the paint, in which case it is preferably added in an amount of 0.1 to 80% by weight.

The thermosetting resin-containing scrap pulverized product of the fine powder is used as an additive in the thermoplastic resin foam composition, in which case it is preferable to add 0.1 to 60% by weight.

The thermosetting resin-containing scrap pulverized product of the fine powder is used as an additive in the adhesive composition, in which case it is preferably added in an amount of 0.1 to 50% by weight.

The present invention by inventing the additives obtained by recycling the thermosetting resin scrap treated as waste, the basic principles and effects thereof can be used, a new recycling method of high-functional materials in line with industrial advancement and new technologies that contribute to environmental protection While presenting the main uses as described above, the use is not limited to the above uses, various substitutions, modifications and changes are possible without departing from the technical spirit of the present invention.

Hereinafter, in the specific examples of the present invention, the characteristics of the additive obtained by pulverizing the thermosetting resin scrap, the recycling use thereof, and the composition including the same are described, but the present invention is not limited thereto.

Effect of Scrap Powder Particle Size :

In the present invention, the copper-clad laminate scraps were cut to a length of 30 cm or less using a sharing machine, and then classified into powders having a constant size and distribution using a conventional grinder and a powder machine. The copper clad laminate scrap is a FR-1 punching powder scrap generated in a printed circuit board processing process, and is composed of 35-65% by weight of the paper substrate part and 35-65% by weight of the thermosetting phenol resin part, and about 2% by weight. It contains negative copper. In addition, since flame retardant components such as cancellation, phosphorus, nitrogen, chlorine, aluminum and antimony are included, there is no limitation on the type and content of these components.

Example 1-4

In Example 1-4 of Table 1 below, different particle sizes and distributions of copper clad laminate scrap powders obtained by varying the number of repetitive additions in a powder mill to determine the effect on particle size are shown, and their characteristics. In addition, the characteristics of the epoxy resin composition and the polypropylene resin composition obtained by mixing 20 parts by weight of these powders were shown.

Item Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Milling Iterations One 2 3 4 - Particle Size and Distribution (μm) Mean 377.2 143.0 48.9 35.2 - Median 304.0 136.5 31.7 27.7 - Mode 859.9 139.2 38.9 33.5 - 90% wt. 831.4 279.7 119.8 79.6 - Max particle 952.1 371.8 292.6 143.4 - Deposition time (sec) 248 772 1054 1123 - Epoxy composition Flexural Strength (Kg / ㎡) 10.4 12.0 12.3 12.5 11.9 Tensile Strength (Kg / ㎡) 7.5 7.7 7.9 7.9 7.7 Flexural modulus (Kg / ㎡) 183 257 274 285 268 Pin Holes 19 8 2 2 2 PP composition E '(MPa) 130.6 134.8 143.1 146.4 132.5 Impact strength (J / ㎡) 0.48 1.02 1.22 1.27 1.32

Comparative Example 1

Comparative Example 1 of Table 1 shows the properties of the epoxy resin composition and the polypropylene (PP) resin composition to which no scrap powder was added.

The particle size and distribution of Table 1 are the results of particle size analyzer analysis by dispersing the powder in methanol: water = 1: 1 mixture, and the deposition time is mixed with methyl alcohol in the ratio of 1: 3 in 100 ml mass cylinder. 100 ml of the obtained dispersion liquid was added and the time required until the boundary line of the sinking particle layer reached 50 ml.

The epoxy composition was prepared by mixing 40 parts by weight of a polyamine curing agent and 28 parts by weight of a scrap pulverized powder to 100 parts by weight of a liquid epoxy having an epoxy equivalent of 187 and curing at 80 ° C. and 150 ° C. for 2 hours, respectively. 20 parts by weight of the scrap pulverized powder was mixed with 100 parts by weight of a general purpose PP resin of 12 g / min, kneaded with a single screw extruder at 210 ° C, and injection molded at a pressure of 1100 bar at 240 ° C to prepare a specimen. At this time, the temperature of the injection molding mold was maintained at 40-50 ℃. The physical properties of the molded specimens were measured by UTM (Universal Test Machine) and DMA (Dynamic Mechanical Analyser).

In Example 1-4 of Table 1, it can be seen that the deposition time gradually increases as the particle size decreases, and a significant difference is revealed based on Example 2. This shows that the smaller the particles, the better the workability based on the excellent dispersibility, and that the particle size used as an additive causes a noticeable difference in the appearance of the workpiece as shown by the number of pin holes found in the epoxy composition. .

Smaller particle sizes in both the epoxy and PP compositions show better mechanical properties, again revealing significant differences based on Example 2. This is a result of the difference in physical properties depending on the size and the degree of dispersion of the dispersed particles in the polymer blend system, or the importance of the particle size as well as the effect of the particle size of the various fillers.

As a result of Example 1-4, it was found that the difference in both processability and physical properties occurred based on the particle size and distribution of Example 2, and thus, in the present invention, the median diameter of the scrap is 150 μm. It was understood that the fine powder state having a maximum particle size of 400 μm or less and a particle size of 300 μm or less of 90% by weight of all the particles is an upper limit point that does not cause a decrease in physical properties using the synthetic resin additive.

Grinding of various scraps and their particle size :

In the present invention, the thermosetting resin scraps having different shapes, sizes, and components were classified and used in a regular size by using a conventional sharing machine, a pulverizer, and a powder machine. In order to manufacture the fine powder, any device such as Zet Mill, Vibrational Mill, Turbo Mill, etc. may be used in addition to the device used in the present invention, but there is a great difference in the productivity of grinding scrap according to the characteristics of the scrap and the characteristics of the device. Therefore, it is necessary to select an appropriate device and optimum grinding conditions, and it is most preferable to use a multi-stage device by connecting several grinding and powder devices in series.

Example 5-9

In the present invention, FR-1 and FR-4 copper clad laminate scrap, polyurethane foam scrap, melamine resin prepreg, unsaturated polyester (hereinafter USPE; unsaturated polyester), FRP scrap was used by grinding and powdering. However, the object is not limited to this kind of scrap, it can be applied to all kinds of thermosetting resin scrap as described above.

The FR-1 copper clad laminate scrap used in the present invention is as described above, and similar scraps of FR-4 copper clad laminate are drilling powders generated during the manufacturing process of printed boards, respectively, 40-60% by weight of glass fiber and epoxy resin parts. It consists of. Polyurethane foam scrap is composed of 10-30% by weight of the glass fiber base portion and 70-90% by weight of the rigid polyurethane resin portion, and the inner foam of the steel panel, which is often used as the exterior wall material of the factory, is its mother. In the case of the matrix, it has excellent thermal conductivity of 0.016 kcal / m 2 h ° C., and has about 20 times higher thermal insulation performance than the red brick for general construction. Melamine resin prepreg is a so-called LPM impregnated paper used as a decorative surface material, each composed of 35-65% by weight of melamine resin and paper reinforcement. Melanin resin is a water-soluble resin polymerized under the condition that the molar ratio of melamine and formaldehyde is 1: 2, and paper having a basis weight of 70 g / m2 is used as a reinforcing material, and is a scrap in a state of drying with a volatile content of 6.0-7.0. . Polyester FRP scrap is also a glass fiber reinforced composite material based on the broken FRP of molded products produced by SMC process. It consists of 20-50% by weight of roving glass fibers and 50-80% by weight of unsaturated polyester resin.

Item Example 5 Example 6 Example 7 Example 8 Example 9 Scrap ingredients FR-1 Copper Clad Laminated Plate FR-4 Copper Clad Laminated Plate Polyurethane foam Melamine prepreg Polyester FRP Particle Size and Distribution (μm) Mean 35.19 42.72 49.62 47.46 40.64 Median 27.72 33.03 38.43 34.07 31.49 Mode 38.91 70.45 80.61 68.99 61.34 90% wt. 79.53 98.45 109.0 97.34 90.16 75% wt. 52.66 66.13 75.79 67.16 60.38 50% wt. 27.72 35.97 38.43 34.07 31.49 25% wt. 11.23 14.29 17.52 16.04 14.07 10% wt. 2.91 4.25 5.55 4.20 3.95

Table 2 shows the main components and various particle size analysis results of the various thermosetting resin scrap powders used in the present invention. Particle size analysis was performed under the same conditions as in Example 1-4.

The particle size distribution in Table 2 is obtained by repeating Hammer Mill four times, and shows the difference in particle size and distribution according to the scrap component, which is dependent on the intrinsic properties of the scrap, and depends on the type of thermosetting resin and the base component included. will be. However, even though the composition, type, and shape of the scrap are different, the average particle size limited by the present invention by a general grinding and powdering device is 150 μm or less, and the maximum particle size is 400 μm or less, and the particle size of 90% by weight of all particles is 300. It was confirmed that the production in a fine powder state of less than or equal to μm, which can be used as a synthetic resin additive is as described above.

On the other hand, the copper foil laminate scraps of Examples 5 and 6 contained about 2% by weight of copper, and in order to remove these copper, 1 to 4 parts by weight of the scrap powder and chloroform were mixed and sufficiently stirred, followed by centrifugation. The components were separated and the synthetic resin and reinforcement components were dried and used. While the copper component was completely removed in this process, the difference in particle size and distribution was within the measurement error of the instrument, and it was confirmed that the removal of copper did not affect the particle size.

FR-1 Copper Clad Laminate Varnish Additive :

The FR-1 copper clad laminate punching powder scrap made by impregnating a phenolic resin on a paper substrate was pulverized through a pulverizer and a powder mill to obtain a powder having a median particle size of 27.72 μm as in Example 5 of Table 2 (hereinafter, 'powder-A' ) To obtain a powder (hereinafter 'powder-B') by removing the copper by the difference in specific gravity using chloroform.

Example 10-13

According to the mixing ratio shown in Table 3, powder-A and B were mixed and uniformly dispersed in FR-1 copper clad laminate using conventional phenol resin, and then it was impregnated in kraft paper having a basis weight of 128 g / m 2 and then 130 ° C. After drying for 5 minutes at 52.5-54.0% of resin and 1.7-2.8% of volatile content, prepreg was prepared, and 8 sheets of prepreg and adhesive-coated copper foil were overlapped with each other at 155 ° C and 100 kgf / ㎠. It pressed for 60 minutes, and obtained the copper clad laminated board of 1.5-1.6 mm in thickness. Table 3 shows the characteristics of the copper-clad laminate obtained in this way.

Comparative Example 2

According to the blending ratio shown in Table 3 to produce a varnish for FR-1 copper-clad laminate using a conventional phenolic resin and copper-clad laminate was molded under the same conditions as in Example 10-13, the characteristics are shown in Table 3.

The compounding ratios specified in Table 3 are described based on the solid component, phenolic resin-1 is a rheologically phenolic resin containing a flame retardant and a releasing agent, and phenolic resin-2 is a low molecular weight melamine-modified phenolic resin for the purpose of improving substrate permeability.

Item Example 10 Example 11 Example 12 Example 13 Comparative Example 2 Compounding cost Phenolic Resin-1 80 75 65 65 65 Phenolic Resin-2 15 15 15 15 15 Powder-A 5 10 20 - - Powder-B - - - 20 - characteristic thickness mm 1.54 1.54 1.57 1.55 1.55 Flame retardant (seconds) Average / Max 3.9 / 9 3.5 / 10 4.1 / 9 3.5 / 7 3.9 / 9 Heat resistance (seconds) 260 ℃ 35 34 34 31 35 Insulation Resistance Ω 1.6E12 8.9E11 4.7E11 7.2E12 7.4E12 CTI Volt 650 600 575 650 650 Punching crack none None none none none Delamination none none none none none Hardness Barcol 53 55 55 56 54 Flexural strength Kgf / mm2 15.3 15.3 15.5 15.6 15.1

The properties of the molded laminates were evaluated according to the general evaluation criteria for copper-clad laminates. Heat resistance means solder blister, and punching crack and interlayer separation were observed with punched specimen at 60 ° C. CTI was measured with a CTI meter.

In the case of Comparative Example 2, the flame retardancy of UL-94-V-0 is satisfied by the conventional general manufacturing method without using the laminated plate scrap powder. In the compositions of Examples 10-13, if Powder-A and B were nonflammable without the flame retardant component, it would not be possible to maintain the flame retardancy of V-0 as it is in the laminate using these powders. In this case, additional flame retardants should be added to maintain flame retardancy. In this case, even if the flame retardancy is improved, heat resistance, flexural strength, insulation resistance, etc. will appear. However, Examples 10-13 use Powder-A, B to maintain the flame retardancy of V-0 without the use of additional flame retardants. Furthermore, as shown in Example 13, Powder-B with copper removed shows a composition that does not inhibit electrical properties such as CTI and insulation resistance. In addition, the pulverized powder showed the same effect as the general inorganic additives, and as the amount of addition increased, the progressive flexural strength and the hardness increased. In addition, the punching crack and the interlayer separation did not appear, it was confirmed that the particle size of the powder-A, B does not inhibit the workability.

This is a typical case of self-recycling scrap powder recycling. The scrap of FR-1 copper clad laminate is pulverized and the average particle size is 150 μm or less and the maximum particle size is 400 μm or less, and the particle size of 90% by weight of all particles is 300. By producing in a fine powder state of less than or equal to μm, it can be used as a flame retardant additive or as an additive for improving mechanical and electrical properties can be used for varnish for copper clad laminate.

Additives for Epoxy Mortar:

The most common form of punching scrap of copper clad laminate is a cylindrical scrap with a diameter of about 1 mm, which is a scrap that is generated during punching for mounting parts on a printed circuit board. Striking. In the present invention, the punching scrap passed through 5 Mesh and filtered through 12 Mesh was separated to obtain a FR-1 copper clad laminate scrap crush having a cylindrical shape of 0.5-1.7 mm in diameter and 1.4-1.7 mm in height.

Example 14

Color mortar for building flooring using epoxy resin by replacing the existing colored silica sand (colored sand) with the punched powder pulverized product (hereinafter 'powder-C') of FR-1 copper clad laminate according to the mixing ratio shown in Table 4. Got. As the epoxy composition used, a liquid epoxy having an equivalent weight of 187 and a polyamine curing agent capable of room temperature curing were used. Nonylphenol was used as a curing accelerator, and benzyl alcohol was used as a diluent.

Comparative Example 3

According to the mixing ratio shown in Table 4, a color mortar for building flooring using an existing color silica sand and an epoxy resin was obtained. The epoxy composition used was the same as in Example 14.

Example 14 Comparative Example 3 Compounding cost Epoxy resin 100 100 Hardener 40 40 Curing accelerator One One diluent 15 15 Powder-C 150 - Cala silica - 150 Hardness (Shore-D) 86 86 Weight (g, 200㎠) 140.5 239.2 color Brown, Green, and Copper Mixes Solid color (green)

In Comparative Example 3 and Example 14, these epoxy compositions were mixed with color silica sand and their replacement copper-clad laminate punching powders, respectively, and applied to a thickness of 6-7 mm using a trowel, followed by curing at room temperature for 3 days. The characteristics were compared.

The flooring of Example 14 included a green portion of the solder resist ink of the punching powder scrap, a brown portion of the laminate, and copper foil, which combined with the metallic texture of copper to give a different appearance characteristic from the conventional color silica sand mortar. It not only gives aesthetic beauty but also shows no lack of surface hardness compared to color silica. This is because the Shore-D hardness of the copper foil laminate itself is about 92-96 and has a higher hardness than the epoxy composition used. This hardness property is one of the most important properties of epoxy mortar, and exhibits the same level of physical properties but weight loss of about 40% per unit area, which reduces the overall load as a building material.

Building Brick Additives :

A cylindrical copper clad laminate punching powder scrap having a diameter of 0.5-1.7 mm and a height of 1.4-1.7 mm was obtained as in Example 14 described above.

Example 15-16

According to the mixing ratio of Example 15-16 shown in Table 5 to replace the existing sand with the powder-C of Example 14 to obtain a cement mortar for building bricks using building cement, 4cm in diameter, 5cm in height Poured into a cylindrical mold of and left for 3 days at room temperature and molded, the molded specimen was measured for compressive strength using UTM.

Comparative Example 4

Cement mortar was obtained according to the blending ratios shown in Table 5, and molded in the same manner as in Example 15-16 to evaluate its properties.

Example 15 Example 16 Comparative Example 4 Compounding cost cement 120 120 120 water 80 80 80 Powder-C 120 60 - sand - 60 120 Weight (g, 60cc) 72.1 96.3 112.8 Compressive strength (Kg / ㎠) 2.61 2.85 2.85

Table 5 shows that the mortar of Example 15-16 had the characteristics of 36% light weight and 15% light weight, respectively, while maintaining the same compressive strength as the conventional mortar using sand. This shows a special advantage of reducing the total load as a building material, and in particular, it shows a significant advantage to reduce the overall load when building a high-rise building.

Additives for FR-4 Copper Clad Laminates:

The scrap of FR-4 copper-clad laminate made by impregnating the glass fiber substrate with epoxy resin was obtained through a pulverizer and a powder mill to obtain scrap powder (hereinafter, 'powder-D') having an average particle size of 33.03 µm as in Example 6. The obtained copper was separated from the glass fiber and the epoxy resin component by the specific gravity difference using chloroform to obtain a scrap powder (hereinafter, 'powder-E') from which copper was removed.

In addition, a sheet of melamine prepreg (aka LPM) scrap for cosmetic plates made by impregnating a water-soluble melamine resin onto a paper substrate was scrap powder having a mean particle size of 34.07 µm as in Example 8 (hereinafter, 'powder F') through a paper shredder and a powder mill. Got.

Example 17-19

Impregnated with glass fiber having a basis weight of 210 g / m 2 in a varnish uniformly dispersed by mixing powder-D, E, and F in a varnish for FR-4 copper clad laminates using conventional epoxy resins according to the mixing ratios shown in Table 6. After drying, a prepreg having a resin content of 41-44% and a volatile content of 0.2% or less was prepared, and eight pieces of these prepregs and an uncoated copper foil were laminated for 40 minutes under conditions of 165 ° C and 40 kgf / cm2 between stainless plates. Hot pressing was carried out to obtain a copper foil laminate having a thickness of 1.5-1.6 mm. Table 6 shows the characteristics of the copper foil laminate thus obtained.

Comparative Example 5

According to the compounding ratios shown in Table 6, using a varnish for FR-4 copper-clad laminate using a conventional epoxy resin, the copper-clad laminate was molded under the same conditions as in Example 17-19. Table 6 shows the characteristics of the copper foil laminate thus obtained. The physical property evaluation of the molded laminated board was performed by the same method and reference | standard as Example 10-13.

Item Example 17 Example 18 Example 19 Comparative Example 5 Compounding cost Epoxy resin 84.2 84.2 84.2 99.2 Hardener 0.7 0.7 0.7 0.7 Curing accelerator 0.1 0.1 0.1 0.1 Powder-D 15 - - - Powder-E - 15 - - Powder-F - - 15 - characteristic thickness mm 1.55 1.56 1.59 1.53 Flame retardant (seconds) Average / Max 3.5 / 9 4.1 / 8 2.7 / 5 3.7 / 8 Heat resistance (seconds) 280 ℃ 59 62 48 61 Insulation Resistance Ω 1.4E14 6.9E14 1.0E15 7.8E14 CTI Volt 300 375 450 375 Drilling crack none none none none Drilling Delamination none none none none Hardness Barcol 64 65 61 63 Flexural strength Kgf / mm2 18.7 18.6 19.1 18.5

The mixing ratios specified in Table 6 are described based on the solid component, and the epoxy resin used is a flame retardant epoxy having a bromine content of 19.5%, and DICY (dicyandiamide) as a curing agent, and 2E4MZ (2-ethyl-4-methyl imidazole). ) Was used as a curing accelerator.

In Comparative Example 5, as a result of a conventional manufacturing method without using a scrap powder, it satisfies the flame retardancy of the UL-94-V-0 grade, but the CTI is 375V to 600V, which is a high-CTI standard. It is under the level.

Also in the case of Example 17-19 of Table 6, if the powder used does not contain a flame retardant component, as in Example 10-13 for FR-1 copper clad laminate, it will not be able to maintain the flame retardancy of 94-V-0. Although additional flame retardant will be required, in Example 17-18 of self-replicating type, FR-4 copper clad laminate scrap powder can be used to secure the flame retardancy of 94-V-0 without the use of a separate flame retardant and not to inhibit other physical properties. In addition, it was possible to secure higher economics and excellent physical property levels.

More specifically, as shown in Example 18, by using the scrap powder in the state of removing copper was confirmed a composition that can also improve the electrical insulation and CTI.

In the case of Example 19, it was confirmed that the addition of melamine resin scrap powder significantly improved the CTI property, which is one of the biggest disadvantages of the bromine-containing epoxy resin, and further showed the same effect as the addition of nitrogen-based flame retardant independent of dioxin emissions. In addition, the flame retardancy was greatly improved, thereby ensuring an environmentally friendly flame retardant composition. In addition, the increase in insulation resistance was also confirmed.

The improvement of the electrical properties and flame retardant properties using the melamine resin scrap powder can obtain the same effect not only in the field of copper foil laminate plate, but also in the field of various molding compounds used as electrical materials.

In addition, although there are some differences depending on the scrap components, the powder can be observed the increase in flexural strength and hardness, like the general inorganic additives, and there is no cracking and delamination due to drilling, so particles of powder-D, E, F It was confirmed that the size did not impair processability.

ABS Resin Compounding Additive :

ABS resin is a representative thermoplastic resin used for housing applications of home appliances because of its excellent toughness and dimensional stability resulting from such an elastic body. In particular, in order to be used in the above-mentioned home appliances, it is necessary to secure the flame retardancy of UL-94-V-0, which is processed into a composition containing a flame retardant epoxy, phosphate ester flame retardant, antimony, etc. Solving the price problem by the ingredients and determining the flame-retardant composition of the environmentally friendly halogen-free state has emerged as a technical task, and various attempts and efforts have been made to solve the problem.

Example 20-22

FR-1 copper-clad laminate powder-B of Example 13 and FR of Example 6 were added to the compounding composition containing the flame-retardant ABS resin and the flame-retardant epoxy, phosphate ester, and antimony in the existing pellets according to the mixing ratios shown in Table 7. -4 copper clad laminate powder-E and the melamine prepreg powder-F of Example 8 were mixed, extruded and injection molded to prepare an injection specimen, and the characteristics thereof were shown in Table 7.

Compounding extrusion for specimen fabrication was carried out at 210 ° C., with a back pressure of 18 MPa. Injection molding was performed at 250 ° C. and 100 Mpa conditions. Thermal properties of the ejected specimens were measured by DSC and mechanical properties were measured using UTM and Impact Tester.

Comparative Example 6

According to the compounding ratio shown in Table 7, an injection specimen using a conventional flame-retardant ABS resin was obtained, and the characteristics of the specimen thus obtained are shown in Table 7. Extrusion and injection conditions and characteristics evaluation conditions were the same as in Example 20-22.

Comparative Example 6 is a case of a conventional manufacturing method, the general physical properties of the specimen is relatively good, but in order to satisfy the higher grade 94-V-0 as the UL-94 94-V-1 grade In the ABS resin composition, an increase in the amount of flame retardant additives is required. In this case, the flame retardant performance is improved, but there is a concern that the thermal and mechanical properties are deteriorated.

Item Example 20 Example 21 Example 22 Comparative Example 6 Compounding cost ABS resin 85 85 85 100 Powder-B 15 - - - Powder-E - 15 - - Powder-F - - 15 - characteristic Flame Retardant (sec, Average / Max) 6.0 / 15 5.9 / 13 4.6 / 8 6.7 / 13 Glass transition temperature (℃) 92.4 112.6 107.6 103.5 Tensile Modulus (Gpa) 2.355 2.630 2.592 2.569 Hardness (Rockwell, R) 88 111 96 92 Flexural Modulus (GPa) 2.59 2.70 2.66 2.55 Izod Impact (J / m) 209 225 215 237

However, Example 20-22 uses the pulverized powder of scrap to ensure the flame retardancy of 94-V-0, or 94-V-1 without using an additional additional flame retardant additive. This is because the mother powder of the added powder is a state of securing flame retardancy of 94-V-0 grade, especially in the case of Example 22 to confirm the possibility of halogen free flame retardant composition.

Example 21 using scrap of the FR-4 laminate is a composition showing that an increase in glass transition temperature is possible. As shown in Examples 20-22, scrap powders of different components are used to show different properties in heat resistance, flame retardancy, hardness and various mechanical properties, which can be improved through the selective application of scrap powder. The result shows that there is.

Polypropylene Resin Compounding Additives :

Polypropylene resin is a typical thermoplastic resin that is used not only for general injection molding but also for film or fiber, etc., and is a general-purpose resin having its general use due to its cost advantages and easy processability.

Example 23-25

According to the blending ratio shown in Table 8, the injection specimen was prepared by mixing and extruding pelletized polypropylene resin and USPE FRP scrap pulverized powder (hereinafter, 'powder-G') specified in Example 9 to produce an injection specimen, and characteristics Was evaluated and shown in Table 8.

Compounding extrusion for the specimen was carried out at 240 ℃, the back pressure was 15 MPa. Injection molding was performed at 275 ° C. and 100 Mpa conditions. In addition, the thermal properties of the injected specimens were measured by DSC, and the mechanical properties were measured using UTM and Impact Tester.

Comparative Example 7

According to the blending ratios shown in Table 8, injection specimens using polypropylene resin alone were obtained, and the properties of the specimens thus obtained are shown in Table 8. Extrusion, injection, and physical property evaluation conditions are the same as in Example 23-25.

Item Example 23 Example 24 Example 25 Comparative Example 7 Compounding cost Polypropylene resin 95 90 80 100 Powder-G 5 10 20 - characteristic Melting temperature (℃) 165.24 167.30 168.51 162.22 Glass transition temperature (℃) 30.64 32.45 39.03 29.15 Melt Calorie (J / g) 69.25 65.11 53.24 78.60 Yield Strength (N) 776.55 762.35 690.21 836.75 Loss Modulus (MPa) 134.8 157.5 178.3 130.6 Impact Strength (J / mm) 0.92 0.72 0.48 1.32

As shown in Example 23-25 of Table 8, the yield strength and impact strength of the polypropylene composition are lowered as the content of the powder-G obtained by pulverizing the polyester FRP scrap decreases, but the heat of fusion decreases more easily. It can be confirmed that the processing is possible, and also shows that the thermal properties such as glass transition temperature can be increased.

For reference, as a result of examining the fracture surface of the specimen subjected to the impact test in Example 23-25 by scanning electron microscopy (SEM), the powder-G is evenly dispersed in the polypropylene resin, Wetting could be confirmed. This can be visually confirmed that the various scrap powder of the present invention can be used in a general thermoplastic resin compounding composition including an olefinic thermoplastic resin, the selectivity for the type of scrap may vary depending on the characteristics to be improved and modified Is as described above.

Unsaturated Polyester SMC Additive :

The most common molding method for unsaturated polyester fiberglass reinforced plastics (FRP), which is treated like a pronoun of thermoset composites, is the sheet molding compound (SMC). This is because the molding cycle is short, which is advantageous for mass production and relatively excellent in physical properties. The broken scrap of the USPE SMC molded product is pulverized to obtain the powder of Example 9 (hereinafter 'powder-G'), which is used for the SMC process of USPE FRP It was added to the molding to evaluate its properties.

Mechanical properties were measured using UTM and Impact Tester, and chemical resistance was evaluated by immersing in prescribed chemicals for 6 hours and observing changes in appearance.

Example 26-28

According to the compounding ratios shown in Table 9, USMC resin using propylene glycol and maleic anhydride was obtained by using t-butyl perbenzoate and t-butyl peroxyoctate as a composite curing agent to obtain an SMC molded product. The glass fiber content was 32-34% by weight of the compound prepared by batch mixing and impregnated with a pressed steel roller. MgO was used as a thickener, and aluminum foil was used as a barrier film to thicken by standing at 40 ° C. for 48 hours. At the time of SMC compression molding, the molding pressure was 55 kg / cm 2 and the mold temperature was 150 ° C. The properties of the specimens thus obtained were evaluated and shown in Table 9.

Comparative Example 8

According to the blending ratio shown in Table 9, without using the powder-G, the test piece was obtained by a general USPE SMC manufacturing method, and its properties are shown in Table 9. Processing conditions are the same as in Examples 26-28.

As shown in Examples 26-28 of Table 9, as the pulverized powder content of the unsaturated polyester FRP scrap is increased, the adhesion, impact strength and tensile strength are improved without deterioration of mechanical properties such as flexural strength. This is because SMC itself is used for chopping glass fibers, and inorganic thickeners such as MgO are used as thickeners for thickening. Therefore, even powder-G does not show any particular difference in composition or structural dimensions. Moreover, there is a problem in that the chemical resistance is particularly weak when the inorganic material is used as a thickener, but since the powder-G used as a self-replicating type is a thermosetting resin composite material, the chemical resistance is rather improved. These results indicate that the higher the glass fiber or inorganic thickener content in the existing general SMC composition, the more effective the replacement of powder-G is.

Item Example 26 Example 27 Example 28 Comparative Example 8 Compounding cost USPE composition 95 90 80 100 Powder G 5 10 20 - characteristic Tensile Strength (Psi) 10300 10800 10800 9700 Flexural Strength (Psi) 25700 26100 25000 25800 Impact Strength (Notched, ft-lb / in) 20 20 18 19 Adhesive force (lbs) 501 472 480 447 10% HCl Resistance X △ O X 5% NaOHResistance △ O O X

Thickener :

Thermoplastic resins generally use plasticizers to improve their processability, and in general, the lower the viscosity of thermosetting resins, the easier it is to process. In some cases, it is necessary to increase the viscosity. As a representative example, in the SMC process as in Examples 26-28 above, in order to impregnate the glass fiber with resin, a low viscosity state is advantageous for preparing a compound, but once impregnated, the glass fiber and the resin component have to be high in viscosity. Since the separation does not occur and shrinkage is reduced, it is common to use a separate thickener. In addition, even after the adhesive is applied to the adhesive surface, it is necessary to use a suitable thickener because a high viscosity can reduce the requirement per unit area and increase the adhesive strength.

Example 29-30

According to the blending ratio shown in Table 10, the room temperature-curable Resorcinol resin composition was mixed with the polyurethane foam scrap pulverized powder (hereinafter referred to as 'powder-H') specified in Example 7 to make an adhesive, which was applied between a copper plate and a copper plate, and 10 It was allowed to stand for 24 hours at a pressure of kgf / cm 2 to achieve adhesion by curing at room temperature. The pot life at this time was 35 minutes, and its characteristics are shown in Table 10 together.

The used Resorcinol resin composition is a composition capable of curing at room temperature by mixing 40 parts by weight of 37% formalin with 100 parts by weight of a 60% solids resin.

Comparative Example 9

According to the blending ratios shown in Table 10, an adhesive using a Resorcinol resin composition alone was obtained, and the properties thereof are shown in Table 10.

Composition and characteristic evaluation conditions of the composition are the same as in Example 29-30.

Example 29 Example 30 Comparative Example 9 Compounding cost Resorcinol Resin 100 100 100 37% formalin 40 40 40 Powder-H 15 30 - Viscosity (cps, 25 ℃) 570 6300 65 Adhesive force (kgf / cm, 180) 7.04 8.42 2.67 Adhesive weight (g / 100㎠) 5.4 6.2 1.8

As shown in Example 29-30 of Table 10, as the content of powder-H increases, a sharp increase in viscosity is observed, and thus, the adhesion strength is improved by sufficiently forming an adhesive layer during curing. This can be checked by comparison with the weight of the cured adhesive of Comparative Example 9.

This thickening phenomenon is shown not only in Examples 29 and 30, but also in other paints, adhesives, composite materials, and the like, and similar thickening occurs when other scrap powder is used in addition to Powder-G. However, the degree of thickening is somewhat different depending on the particle size and particle shape of the pulverized powder.

Water festival :

One of the biggest disadvantages of thermosetting resins is shrinkage due to curing. For example, in the case of an unsaturated polyester resin, the hardening shrinkage is severe, resulting in a volume shrinkage of 7-8%. As a result, the dimensional stability of the molded product is deteriorated, and molding defects such as cracks and sink marks are likely to occur. In order to prevent such shrinkage, the volume change according to temperature uses a thermosetting resin and another thermoplastic resin, which is called a low profile additive (PMMA, PVC, PVA, Polycaprolactam, etc.).

Example 31-32

The broken scrap of the SMC molded article of the USPE resin having a high cure shrinkage was pulverized to obtain Powder-G of Example 9, which was added to the USPE composition to compression molding to evaluate its properties, which are shown in Table 11.

Under the same conditions as in Example 26-28, the USPE resin using propylene glycol and maleic anhydride was compression molded using t-butyl perbenzoate and t-butyl peroxyoctate at a pressure of 55 kg / cm2 and a temperature of 150 ° C. using a composite curing agent. Was produced. In this process, the volumetric shrinkage and the electron microscope were used to evaluate the compatibility, the mechanical properties were evaluated by the UTM, and the paint was sprayed on the surface of the specimen to evaluate the paintability.

Comparative Example 10-11

According to the compounding ratios shown in Table 11, specimens obtained with and without the use of PMMA as a low shrinkage agent were obtained, and their properties are shown in Table 11. Processing and physical property evaluation conditions are the same as in Examples 31-32.

Item Example 31 Example 32 Comparative Example 10 Comparative Example 11 Compounding cost USPE composition 100 100 100 100 PMMA - - 3 - Powder G 15 30 - - Curing shrinkage (%) 5.19 4.58 4.34 7.92 Compatibility O O X O Tensile strength (psi) 10700 11000 8400 9700 Flexural strength (psi) 25800 26000 21700 25800 Paintability (staining) none none Occur none

As shown in Examples 31 and 32 of Table 11, as the content of Powder-G increases, a gradual improvement in cure shrinkage is seen. This is the same principle as in the case of minimizing cure shrinkage by using a reinforcing material such as filler or glass fiber, since Powder-G is a thermosetting resin in the already cured state. The use of the thermosetting resin scrap powder of the present invention as such a low shrinkage agent can expect similar effects based on the same principle for all the thermosetting resin compositions as well as Examples 31 and 32 above.

In Comparative Example 10, the addition of PMMA showed much improvement in terms of dimensional stability, but the SEM showed a decrease in compatibility. This suggests that the mechanical properties of the composition are significantly lowered, which was confirmed by the measurement of tensile strength and flexural strength. In addition, such compatibility problems hinder the coating properties, which is one of the advantages of the USPE, resulting in unevenness of the paint during coating.

blowing agent :

In the case of synthetic foams, which are referred to as styropoll, as blowing agents for forming foams, expensive materials such as sodium bicarbonate and sulfonyl hydrazides, which have a function of generating gas by forming gas during molding, are produced. Blowing agents have been used.

In the case of the scrap pulverized powder, the smaller the particle size, the larger the surface area, and the surface is uneven, so that fine air particles exist, and when these particles are entangled, the amount of air contained is greatly increased. Therefore, these air protrudes due to the heat of curing of the thermosetting resin, and voids are formed in the process to form a foam.

Example 33

The foam was formed by mixing the punching powder powder-A of the FR-1 copper clad laminate of Example 5 with the phenol resin composition in which the acid was cured at room temperature with a curing agent according to the blending ratio shown in Table 12.

Comparative Example 12

The phenol resin composition was cured according to the blending ratios shown in Table 12.

Example 14 Comparative Example 4 Compounding cost Phenolic resin 100 100 Mountain-1 13 13 Mountain-2 7 7 Powder-A 20 - Cell formation (foaming) Occurred none Volume (ml / 10g) 36.7 9.6

As shown in Table 12, the foam was formed only by the addition of Powder-A without a separate blowing agent. The formed foam is a closed cell, the size of the cell is not constant, but due to the particle size distribution of the powder, it is also possible to control the size of the cell by controlling the particle size distribution. The foams also maintain their inherent non-combustibility.

Phenolic Resin Coated Wood Powder Substitute :

In the case of PVC flooring, which is known as a floor covering, new products are added with various additives to meet various tastes and desires of consumers. Representative examples of the recent elvan rock-containing flooring, copper-containing vein blocking flooring, and the like, natural wood-containing flooring to meet the needs of nature. This is produced by calendering method by adding sawdust to PVC compound. In this case, wetting problem between sawdust and PVC occurs, and sawdust acts like crack tip, which causes big problems in durability and mechanical properties of flooring. The sawdust is coated with phenolic resin and then added to the PVC compound to solve this wetting problem.

However, in this case, a problem arises that a compounding process with a phenol resin for the coating of the sawdust occurs, the production process is complicated, and thus the manufacturing cost increases rapidly.

In contrast, the powder-A of Example 5 contains copper having a vein blocking effect, and since the base component is a chip leaf pulp, the phenol resin-coated sawdust may be used in terms of function and composition.

Example 34

The injection molding was performed by mixing the punching powder powder-A of the FR-1 copper clad laminate of Example 5 with the PVC compound composition according to the blending ratio shown in Table 13.

Comparative Example 13

The PVC composition was molded according to the blending ratios shown in Table 13.

Example 34 Comparative Example 12 Compounding cost PVC composition 100 100 sawdust - 12 Phenolic Resin - 8 Powder-A 20 - Sawdust Compounding not needed Required Wetting state Good Good

As shown in Example 34 of Table 13, it was possible to maintain the same level of wetting property by adding powder-A without a separate compounding process, which eliminated unnecessary processes. In addition, Example 34 is expected to use a smaller particle size of Powder-A than the sawdust compounding product of Comparative Example 12, so that the mechanical properties of the PVC compound composition are also much better.

The present invention described above is not limited to the above-described embodiments and the like, and various substitutions, modifications, and changes can be made without departing from the technical idea of the present invention, which is within the technical scope of the present invention.

The present invention is based on the inherent differences in the characteristics of recycling all thermosetting scraps regardless of the type of thermosetting resin and the reinforcing material and whether or not the reinforcing material is included, as well as the recycling method using the unique characteristics of the scrap mother. The thermosetting resin scrap is ground to an average particle size of 150 μm or less and a maximum particle size of 400 μm or less, and ground to 90% by weight of the total particles to 300 μm or less thereof, and then added to the synthetic resin composition. This has a particular feature of its use as a functional additive capable of improving specific physical properties such as flame retardancy, electrical insulation, abrasion resistance and mechanical properties of the composition. In addition, the present invention has the advantage that the synthetic resin and the base component is not used separately. Accordingly, the present invention contributes to the protection of the environment as well as the improvement of specific physical properties by suggesting new methods and technologies that can be recycled without disposing of high-performance thermosetting resin scrap in response to industrial advancement. A new synthetic resin composition is provided.

Claims (25)

Thermosetting resin-containing scraps, such as laminated plates, copper-clad laminates, prepregs, foams, composites, or sawdust-shaped cutting chips containing thermosetting resins, with or without separate reinforcement components, A thermosetting resin-containing scrap pulverized product in the form of a fine powder, characterized in that the median diameter) is 150 μm or less and the maximum particle size is 400 μm or less, and the particle size of 90% by weight of all the particles is 300 μm or less. The thermosetting resin-containing scrap mill of claim 1, further comprising a flame retardant or non-flammable component containing nitrogen, phosphorus, bromine, chlorine, and / or antimony. 2. The thermosetting resin-containing scrap mill of claim 1, further comprising a nitrogen component of melamine or urea. Thermosetting resin-containing scraps, such as laminates, copper-clad laminates, prepregs, foams, or composites containing thermosetting resins, with or without separating stiffener components, have a particle size of 0.5 mm or more and 3 mm or less A thermosetting resin-containing scrap pulverized product, characterized in that. 5. The thermosetting resin-containing scrap mill of claim 4, further comprising a flame retardant or nonflammable component containing nitrogen, phosphorus, bromine, chlorine, and / or antimony. The thermosetting resin-containing scrap crushed product according to claim 4, further comprising a nitrogen component of melamine or urea. Use of the thermosetting resin-containing scrap pulverized product according to any one of claims 1 to 3 as an additive in a varnish for laminates. The varnish composition for laminated sheets comprising 0.1-30% by weight of the thermosetting resin-containing scrap pulverized product according to any one of claims 1 to 3 as an additive. Use of the thermosetting resin-containing scrap mill according to claim 4 as an additive to an epoxy mortar. An epoxy mortar composition comprising 0.1 to 50% by weight of the thermosetting resin-containing scrap crushed product according to any one of claims 4 to 6 as an additive. Use of the thermosetting resin-containing scrap milled product according to any of claims 4 to 6 as an additive to cement mortar. A cement mortar composition comprising 0.1 to 50% by weight of the thermosetting resin-containing scrap pulverized product according to any one of claims 4 to 6 as an additive. Use of the thermosetting resin-containing scrap crushed product according to claim 4 as an additive in a building brick composition. A building brick composition comprising 0.1 to 50% by weight of the thermosetting resin-containing scrap crushed product according to any one of claims 4 to 6 as an additive. Use of the thermosetting resin-containing scrap pulverized product according to any one of claims 1 to 3 as an additive in a thermoplastic resin composition. A thermoplastic resin composition comprising 0.1 to 40% by weight of the thermosetting resin-containing scrap crushed product according to any one of claims 1 to 3 as an additive. Use of the thermosetting resin-containing scrap pulverized product according to any one of claims 1 to 3 as an additive in a thermosetting resin composition. A thermosetting resin composition comprising 0.1 to 60% by weight of the thermosetting resin-containing scrap pulverized product according to any one of claims 1 to 3 as an additive. Use of the thermosetting resin-containing scrap pulverized product according to any one of claims 1 to 3 as an additive in a paint. A coating composition comprising 0.1 to 80% by weight of the thermosetting resin-containing scrap pulverized product according to any one of claims 1 to 3 as an additive. Use of the thermosetting resin-containing scrap milled product according to any one of claims 1 to 3 as an additive in a thermoplastic foam composition. A thermoplastic resin foam composition comprising 0.1 to 60% by weight of the thermosetting resin-containing scrap pulverized product according to any one of claims 1 to 3 as an additive. Use of the thermosetting resin-containing scrap mill according to any one of claims 1 to 3 as an additive in an adhesive composition. An adhesive composition comprising 0.1 to 50% by weight of the thermosetting resin-containing scrap pulverized product according to any one of claims 1 to 3 as an additive. The thermosetting resin-containing scrap pulverized product according to any one of claims 1 to 3, wherein the copper is removed from the thermosetting resin-containing scrap containing copper.