JP2003306575A - Process for treating additive-containing resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a treatment process for efficiently separating an additive component from a resin component for treating and recycling an additive- containing resin composition. <P>SOLUTION: The additive-containing resin composition is wet ground with water to achieve a particle size of ≤400 μm. The wet-ground resin composition is brought into contact with a solvent which dissolves at least part of the additive to separate and remove at least part of the additive from the resin composition. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a treatment method for separating and removing additive components from a resin composition containing various additives. For example, it is useful for separating and removing additive components from resin casings containing additive components in home appliances collected by the Home Appliance Recycling Law, especially flame retardants used as casings for TVs and PC monitors. It is effective for separating and removing the flame retardant and the like from the resin composition containing.

[0002]

2. Description of the Related Art At present, propylene resin, styrene resin, ABS (acrylonitrile? Butadiene? Styrene) resin, and high-impact polystyrene resin with improved impact resistance are used as housings for televisions and personal computer monitors, and housings for various home appliances. Thermoplastic resins such as polycarbonate and polycarbonate, and thermosetting resins such as phenolic resins and epoxy resins are generally used for electric product parts, and they are additive components for the purpose of imparting various functions to the resin itself. Is mixed and used. An example in which a relatively large amount of additives are mixed in the resin is a flame retardant used for the purpose of flame resistance. Although it varies depending on the combination of the resin and the flame retardant, it is often mixed in a ratio of about 10 to 20 wt%.

[0003]

Among the flame retardants, the brominated flame retardants are inexpensive and have excellent flame retardant effects on thermoplastic resins and thermosetting resins, and have hitherto been used in home appliances and personal computers. It has been used in large quantities in housings and component materials. Therefore, a large amount of the resin composition containing the brominated flame retardant is discarded together with the disposal.

Generally, incineration and landfill are the main methods of treating resin waste, and only a part of them is reused by heating and melting. Considering the tightness of the landfill disposal site, it is desirable to incinerate the waste plastic, but the resin composition containing flame retardant is difficult to incinerate due to its high degree of flame retardancy, and the treatment Is getting difficult.

Further, awareness of environmental problems has increased, and it has been pointed out that the halogenated organic substances are harmful to the environment, and the use of halogenated organic substances is being regulated. Currently, manufacturers are considering switching from halogen-based flame retardants to flame-retardants that do not contain halogenated organic compounds such as phosphorus compounds, but phosphorus compounds are more flame retardant than halogenated organic substances. Is weakly applied, and conversion from halogenated organic matter is
It is in a current situation where it does not progress easily.

Furthermore, in recent years, there has been a strong demand for reusing resources derived from petrochemicals, and treatment of resin waste and establishment of a recycling method have become important issues. In particular, the Home Appliance Recycling Law that came into effect in April 2001 requires appropriate recycling treatment for four products: TV, refrigerator, air conditioner, and washing machine. The recycling rate for the time being is around 50 to 60%, and efforts are being made to clear the current target value by actively promoting the recycling and utilization of glass and metal, which account for a relatively large proportion of each product. However, it is expected that the recycling rate will increase in the future, and it is hoped that a resin recycling method will be established.

Various studies have been conducted as a method for treating a resin composition containing a flame retardant. However, acid treatment (JP-A-6-157812) and high-temperature treatment (JP-A-8-299759, JP-A-9-262565, JP-A-2000-198874) are the main contents, and it is difficult to treat with resin. There were few efforts aimed at material recycling of resins, centering on thermal recycling treatment methods such as complete decomposition of combustion agents. Further, Japanese Patent Application Laid-Open No. 10-195234 proposes a method of modifying and separating a resin among resins containing a flame retardant. Although it is intended to be used for other purposes by functionalizing the resin, we conclude that there is an urgent need to establish a recycling law mainly for recycling for general purposes.

The present invention has been proposed in view of the above circumstances, and a processing method and a processing apparatus capable of easily material recycling in a resin casing containing an additive such as a flame retardant. The purpose is to provide.

[0009]

Means for Solving the Problems As a result of intensive studies on the above problems, the present inventors have found that a resin composition containing an additive such as a flame retardant is pulverized and then treated with a specific solvent. The present invention has been completed by finding a method for efficiently separating and removing the additive component such as the flame retardant from the resin by contacting the resin component.

The first aspect of the present invention (corresponding to claim 1) is that the resin composition containing an additive is wet-ground with water to a particle size of 400 μm or less, and then the wet-ground resin composition and the additive are added. The method for treating a resin composition containing an additive is characterized in that at least a part of the additive is separated and removed from the resin composition by contacting with a solvent that dissolves at least a part of the additive.

A second aspect of the present invention (corresponding to claim 2) is a resin composition containing an additive, wherein the additive contains a flame retardant and is wet pulverized with water to a particle size of 400 μm or less, and then the wet type. Addition of the first invention, characterized in that a pulverized resin composition and a solvent that dissolves at least a part of the flame retardant are brought into contact with each other to separate and remove at least a part of the flame retardant from the resin composition. A method for treating a resin composition containing an agent.

According to a third aspect of the present invention (corresponding to claim 3), in a resin composition containing an additive, a solvent in which at least a part of the additive is dissolved is an alcohol solvent group, a glycol solvent group, or a glycol. A method for treating a resin composition comprising the first or second additive of the present invention, which comprises at least one selected from the group consisting of ether solvents and the group consisting of lactate esters.

A fourth aspect of the present invention (corresponding to claim 4) is a resin composition containing an additive, wherein the resin component is a thermoplastic resin, and at least one of the additives contained in the thermoplastic resin composition. The solvent that dissolves the parts is ethanol, 1
? Propanol, 2? Propanol, 1? Butanol,
2? Butanol, 2? Methyl-2? Propanol, 2?
Methyl-1? A third method for treating a resin composition containing the additive of the present invention is characterized by containing at least one selected from propanol.

A fifth aspect of the present invention (corresponding to claim 5) is a resin composition containing an additive, wherein the resin component is a thermoplastic resin, and the thermoplastic resin composition containing the additive,
Treatment of a resin composition containing a first or second additive of the present invention, characterized in that a solvent that dissolves at least a part of the additive is contacted at a temperature not higher than the glass transition temperature of the thermoplastic resin. Is the way.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention relates to a treatment method for obtaining a resin from which at least a part of an additive has been removed by wet pulverizing a resin composition containing the additive with water and then bringing the resin composition into contact with a specific solvent. It is about.

The resin composition described here refers to a non-conforming material or an end material generated in a molding process at a manufacturing site or the like, or a casing resin recovered as a waste home electric appliance or the like at a recycling base or the like.

The resin component may be a thermoplastic resin or a thermosetting resin. The thermoplastic resin composition can be applied to any general-purpose plastic such as ethylene-based resin, propylene-based resin and styrene-based resin, general-purpose engineering plastic such as carbonate-based resin, amide-based resin and GF reinforced polyethylene terephthalate. is there. For example, styrene resins include polystyrene and poly? α? Methyl styrene, styrene? Butadiene, styrene? Acrylonitrile, styrene? butadiene? Acrylonitrile, styrene? Examples of the resin include maleic anhydride and high-impact high-impact polystyrene. As the thermosetting resin, a phenolic resin,
Examples thereof include epoxy resins, unsaturated polyester resins, and resins obtained by crosslinking them.

The above resin composition may be used alone,
You may mix and use two or more. Further, it may be a mixture with another resin. The molecular weight of the resin component is also arbitrary, but the weight average molecular weight is 3,000 to 3,000.
About 10,000 is preferable.

The types of additives include antioxidants, ultraviolet absorbers, stabilizers, plasticizers, foaming agents, crystal nucleating agents, lubricants,
Coloring agents, compatibilizers, cross-linking agents, flame retardants, flame retardant aids, fillers, antistatic agents, antifungal agents, mold release agents, etc. are materials that are preferably reused or removed at the time of reuse. . Further, the surface may be coated with acrylic or the like. The additive contained in the resin composition may be a single kind or a mixture of plural kinds.

Examples of the flame retardant include phenyl ether type flame retardants such as decabromodiphenyl ether, octabromodiphenyl ether and tetrabromodiphenyl ether, and bisphenol A type flame retardants such as tetrabromobisphenol A (TBA) and hexabromocyclo. Dodecane, bistribromophenoxyethane,
Brominated flame retardants such as tribromophenol, ethylenebistetrabromophthalimide, TBA polycarbonate oligomers, brominated polystyrene, TBA epoxy oligomers, chlorinated paraffins, perchlorocyclopentadecane, chlorendic acid, and other phosphorus flame retardants. Known are flame retardants, flame retardants containing nitrogen compounds, and inorganic flame retardants. The content of the flame retardant may be any, but generally 10 to 20w relative to the weight of the resin composition.
It is often mixed with t%.

The processing method of the present invention will be described in detail below.

In the method for treating a resin composition containing an additive in the present invention, at least a part of the additive is dissolved after wet pulverizing the resin composition containing the additive into a particle size of water which is not more than a certain value. At least a part of the additive is separated and removed from the resin composition by bringing it into contact with a solvent.

The average particle size is 400 μ, for example.
It was found that the removal efficiency of the additive was not sufficient when it was larger than m. As a result of various studies, it was found that if the thickness is about 400 μm or less, the solvent penetrates into the resin and the additive components diffuse into the solvent relatively easily, and the removal can be performed with high efficiency. More preferably, it is 100 μm or less.
If the particle size is 400 μm or less, the removal efficiency of the additive becomes higher as the particle size becomes smaller, which is desirable. However, since the burden on the device and energy consumption increase, the removal rate should be the maximum particle size above a certain level. It is judged that it is preferable to carry out, and the maximum value is a particle size of 400 μm.

Further, in the resin composition containing the additive of the present invention, when the additive component contains a flame retardant, the above treatment makes it possible to separate and remove the flame retardant from the resin composition. Become. At this time, the resin may be thermoplastic or thermosetting.

The solvent used at this time is preferably one containing at least one selected from the group consisting of alcohol solvents, glycol solvents, glycol ether solvents, and lactate ester solvents.

As a more specific solvent, ethanol, 1
? Propanol, 2? Propanol, 1? Butanol,
2? Butanol, 2? Methyl-2? Propanol, 2?
Methyl-1? Propanol and the like can be mentioned, and it is preferable to contain at least one of these solvents. The higher the concentration of these compounds in the solvent used in the present invention, the higher the solubility of the compound in the additive. Therefore, it is desirable to increase the concentration of the compound as much as possible. The concentration is preferably contained as a main component, and is preferably at least 50% by weight or more of the weight of all solvents.

Any method may be used as the method of contacting with a solvent for dissolving at least a part of the additive after wet-milling with water. For example, after separating water and resin, drying is performed, and then stirring treatment is performed in a container containing a solvent. Also, without directly applying to the solvent,
By contacting with steam, the separation process from the liquid can be simplified. At this time, in order to increase the separation efficiency of the additive, it is also possible to heat the solvent, but since the crushed resins soften above the deformation temperature of the thermoplastic resin, the surface area per unit weight is reduced. There is a possibility that Therefore, the point of utilizing the method of the present invention is to bring them into contact with each other under favorable crushing conditions before softening.

Further, the solvent used for dissolving the additive of the present invention can be repeatedly used by carrying out a distillation operation or an filtering operation of the additive utilizing the temperature dependence of the solubility of the additive, The amount used can be reduced. Moreover, the additive recovered as a residue after removing the solvent can be recovered without being diffused into the atmosphere. Further, their bulk is very small compared to the initial weight of the entire resin composition, and they can be handled under special control.

As described above, according to the present invention, it is possible to carry out the treatment in consideration of the environment, such as proper treatment, recovery, recycling treatment of the environmental pollutant and reduction of the amount of solvent used.

[0030]

The present invention will be described in detail with reference to the following examples.

Example 1 In this example, a resin composition (weight average molecular weight of resin 900,000) comprising a flame retardant component: tetrabromobisphenol A and a resin component: polystyrene was prepared as a waste plastic to be treated. The flame retardant component and the resin component contained in this resin composition were separated. At this time, the flame retardant was adjusted to be contained in 10 parts by weight with respect to the resin composition.

First, the resin composition to be treated is roughly crushed into blocks of about 5 mm square, and 1 kg of this is squeezed with water using a supermass colloider (manufactured by Masuyuki Sangyo Co., Ltd.) in an amount 5 times the amount of the resin charged. While wet pulverizing, average particle size 4
950 g of 00 μm pulverized product was recovered. After drying
Stirring was carried out for 10 minutes in a 10 times amount of ethanol solution, after which the resin was taken out and dried again.

When the weight of the flame retardant remaining in the recovered resin component was measured by GPC, the initial flame retardant weight was 10% based on the total weight of the resin composition.
It was found to have decreased to 7% and it was found that the flame retardant in the composition could be removed.

(Example 2) In this example, the same resin composition as in Example 1 was used, and after wet pulverization treatment with water, stirring was performed in a heated solvent. The temperature was 60 ° C. The size of the crush is 100 μm. The results are shown in the table below. The solvent used is ethanol, 1? Propanol, 2? Propanol, 2? It is butanol.

[0035]

[Table 1]

It became clear that the removal rate in ethanol was increased by heating.

Example 3 In this example, as a waste plastic to be treated, a polycarbonate resin composition containing 10 parts by weight of a flame retardant containing tetrabromobisphenol A as a main component (weight average molecular weight of resin: 330,000). Was used to separate the flame retardant component and the resin component contained in this resin.

First, 100 g of the resin composition to be treated, which was roughly crushed into blocks of 10 mm square or less, was wet pulverized while flowing water to obtain a pulverized product of 100 μm. These two
? After stirring in a solvent of propanol, the mixture was put into a centrifugal separator, separated into a resin and a solvent, and collected.

It was confirmed by IR that tetrabromobisphenol A was contained in the recovered solution and that the precipitate was a polycarbonate resin component. When the weight of the flame retardant remaining in this resin was measured, the initial flame retardant weight was 10% based on the total weight of the resin composition.
It was found to have decreased to 1.7%. When the weight average molecular weight before and after the treatment was examined, no significant difference was observed in the change in molecular weight, and it was found that the recovered polycarbonate can be reused as a raw material. Used again 2? Propanol could be recovered in high yield (94.0%).

Example 4 In this example, as a waste plastic to be treated, a polypropylene resin composition containing 0.5 parts by weight of a phenolic antioxidant (polystyrene-equivalent weight average molecular weight of 100,000) was used. Was used to separate the additive component and the resin component contained in this resin.

First, 100 g of a resin composition to be treated, which was roughly crushed into blocks having a size of 10 mm square or less, was flowed with 1 while flowing water.
After wet pulverizing to 00 μm, the mixture was stirred in a propylene glycol solution, put into a centrifugal separator, separated into a resin and a solvent, and collected.

It was confirmed by IR that the recovered solution was a phenolic antioxidant and the precipitate was a polypropylene resin component. Further, the weight of the antioxidant remaining in the resin was measured, and it was found that the initial weight was 0.5% with respect to the total weight of the resin composition.
It was found to have decreased to%. Further, when the weight average molecular weight before and after the treatment was examined, no significant difference was observed in the change in molecular weight, and it was found that the recovered polypropylene resin can be reused as a raw material. The propylene glycol used could be recovered in high yield (94.0%).

Example 5 In this example, the same resin composition as that used in Example 4 was used for the examination.

First, 100 g of a resin composition to be treated, which was roughly crushed into blocks having a size of 10 mm square or less, was flowed with 1 while flowing water.
Wet pulverized to 00 μm and then heated to 70 ° C. After stirring in propanol, add it to the centrifuge,
The resin and solvent were separated and collected.

It was confirmed by IR that the recovered solution was a phenolic antioxidant and the precipitate was a polypropylene resin component. Further, the weight of the antioxidant remaining in this resin was measured, and the initial weight was 0.5% with respect to the total weight of the resin composition.
It was found to have decreased to%. Further, when the weight average molecular weight before and after the treatment was examined, no significant difference was observed in the change in molecular weight, and it was found that the recovered polypropylene resin can be reused as a raw material. Used again 2? Propanol could be recovered in high yield (95.0%).

[0046]

Industrial Applicability As described above, by using the treatment method of the present invention, only additives which are unnecessary from the resin composition used for waste home electric appliances and the like, which are expected to be discarded in a large amount in the future and become a problem. Can be separated and removed.
Furthermore, in the case of thermoplastic resins, by reusing the resin components from which those additives have been removed, the amount of waste can be reduced, and the solvent used for recycling can be reused. It helps to solve problems.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Takahiko Terada             1006 Kadoma, Kadoma-shi, Osaka Matsushita Electric             Sangyo Co., Ltd. (72) Inventor Hiroshi Onishi             1006 Kadoma, Kadoma-shi, Osaka Matsushita Electric             Sangyo Co., Ltd. F term (reference) 4F301 AA14 AA15 AA22 AA24 AA25                       AB01 AB03 CA04 CA09 CA12                       CA34 CA53 CA71 CA72

Claims (5)

[Claims] 1. A resin composition containing an additive is wet pulverized with water to a particle size of 400 μm or less, and then the wet pulverized resin composition is contacted with a solvent in which at least a part of the additive is dissolved. A method for treating a resin composition containing an additive, characterized in that at least a part of the additive is separated and removed from the resin composition. 2. A resin composition containing an additive, wherein the additive contains a flame retardant, and after wet grinding with water to a particle size of 400 μm or less, at least one of the wet ground resin composition and the flame retardant. The method for treating a resin composition containing an additive according to claim 1, wherein at least a part of the flame retardant is separated and removed from the resin composition by contacting with a solvent that dissolves a part of the resin composition. 3. A resin composition containing an additive, wherein the solvent in which at least a part of the additive is dissolved is selected from alcohol solvent group, glycol solvent group, glycol ether solvent group, or lactate ester solvent group. A method for treating a resin composition containing an additive according to claim 1 or 2, comprising at least one selected from the above. 4. A resin composition containing an additive, wherein the resin component is a thermoplastic resin, and a solvent for dissolving at least a part of the additive contained in the thermoplastic resin composition is ethanol, 1? Propanol, 2? Propanol, 1? Butanol, 2? Butanol, 2? Methyl-2
? Propanol, 2? Methyl-1? 4. At least one selected from propanol is included.
A method for treating a resin composition containing the additive as described. 5. A resin composition containing an additive, wherein the resin component is a thermoplastic resin, the thermoplastic resin composition containing the additive, and a solvent for dissolving at least a part of the additive, The method for treating a resin composition containing an additive according to claim 1 or 2, wherein the resin composition is contacted at a temperature not higher than the glass transition temperature of the thermoplastic resin.