JP5066790B2 - Resin composition - Google Patents

Description

  The present invention relates to a polycarbonate-containing resin composition having good fluid moldability and excellent mechanical properties.

Polycarbonate (PC) resins are excellent in transparency, heat resistance, hardness, moldability, and mechanical properties, and are widely used as electrical and optical applications, various cases, and window materials.
For example, it is used as a substrate material for optical discs represented by digital video discs (DVD), compact discs (CD), magnetic discs (MD), optical / magnetic discs (MO), etc. Used as panels, lighting window materials, and various packaging materials.

When the optical disk as described above is discarded after use or when reusing defective products and molding waste generated in a large amount in the manufacturing process, attention must be paid to the environmental aspect and cost.
Conventionally, it has been mainly incinerated and discarded. However, considering the recent resource situation and energy situation, there has been an increasing demand for a technology for recycling and recycling without incineration disposal.

  However, the optical disc has deposits such as a metal reflective layer, a recording material layer, an adhesive layer, a protective layer, a printing ink layer, a label, and various additives depending on the function and application. Therefore, if the material is recycled as it is, the quality, moldability, mechanical properties and the like are lowered, and it is difficult to recycle the material.

In contrast to the fact that such material recycling is practically difficult, in the past, a technique for using a new high molecular weight polycarbonate material and a technique for adding an inorganic filler material to this have been proposed (for example, (See Patent Documents 1 and 2.)
In these, new polycarbonate materials with a certain molecular weight or more are used, the content rate of the recovered optical disk is low, it cannot be said that it is a complete recycling technology, and there is room for improvement in terms of cost. is there.

JP-A-8-311326 JP-A-8-142054

As described above, all of the conventionally proposed recycling technologies have problems in terms of quality, physical properties, and cost, and are not necessarily practical methods from the concept of recycling waste. .
Therefore, in the present invention, in view of such a conventional problem, using a low molecular weight PC resin for an optical disk, it has excellent mechanical properties, good fluidity, and excellent moldability. It was decided to provide a polycarbonate-containing resin composition.

  In the present invention, at least a resin composition composed of a mixed resin composed of a polycarbonate resin (PC resin) and a modifier, and the mixed resin and the PC resin are 220 ° C. and 10 kgf. The melt flow ratio (MFR ratio: according to JISK7210) under the conditions is mixed resin / PC resin = 0.1 to 1.5, and the Izod impact strength ratio (according to JISK7110) is mixed resin / PC resin = 2. A resin composition that is zero or more is provided.

According to the present invention, a resin composition that can contribute to the recycling of PC resin, has excellent mechanical properties, and has good moldability and processability is obtained.
In addition, even if there is a recording material layer, protective layer, label, surface hardened layer, various coatings, plating, etc. on the optical disk used as the PC resin of the material, practically sufficient moldability and physical properties are secured. This makes it possible to recycle excellent materials at an extremely low cost.

  Hereinafter, although the resin composition of this invention is demonstrated concretely, this invention is not limited to this.

  In the present invention, it is a resin composition composed of a mixed resin comprising at least a polycarbonate resin (PC resin) and a modifier, and the conditions of the mixed resin and the PC resin are 220 ° C. and 10 kgf. The lower melt flow ratio (MFR ratio: according to JISK7210) is mixed resin / PC resin = 0.1 to 1.5, and the Izod impact strength ratio (according to JISK7110) is mixed resin / PC resin = 2.0 or more. A resin composition is provided.

The polycarbonate resin (PC resin) is not particularly limited as long as it is generally used.
PC resin is not only new PC resin, but also waste materials, scraps, etc. generated in the manufacturing process, or recovered products and waste materials of products (for example, DVD, compact disc, MO, various housings, window materials, sheets, etc.) There may be.
The PC resin can be synthesized by the reaction of bisphenol A and phosgene and has a structure represented by the following formula (1) or formula (2). However, a part of the chemical formula may be substituted or may have a copolymer component.

However, Ar in the said Formula (1) shows a bivalent C5-200 aromatic residue.
For example, a phenylene group, a naphthylene group, and the like, and the H group may be substituted with another element.

In the above formula (2), Ar ₁ and Ar ₂ are allylene groups similar to the phenylene group and naphthylene group in the above formula (1), and R represents a lower alkyl group, an aryl group, or an aralkyl group. , Some or all of the H groups may be substituted with halogen atoms.

The moldability and mechanical properties of the PC resin are greatly influenced by the molecular weight of the polymer. In view of this point, the weight average molecular weight of the PC resin used in the present invention (polystyrene equivalent molecular weight by GPC using the tetrahydrofuran solvent method). ) Is preferably about 40,000, more preferably 10,000 to 37,000.
If the weight average molecular weight of the PC resin exceeds 40,000, the mechanical properties of the molded product of the final resin composition will be good, but the fluidity will decrease, making it difficult to mold precision parts. Or the molding efficiency decreases.
On the other hand, if the weight average molecular weight is less than 10,000, the fluidity is very good, but the occurrence of burrs in the minute portions and the physical properties of the molded body, such as impact strength, tensile physical properties, bending physical properties, etc., are reduced, and practical aspects are reduced. A problem arises.

Further, when the recovered optical disk is used as the PC resin, there are various deposits such as a metal reflection layer, a plating layer, a recording material layer, an adhesive layer, and a label. You may use it, and you may use the thing after isolate | separating and removing such an impurity and submaterial by a conventionally well-known method.
Specifically, metal reflective layer such as Al, Au, Si, etc., organic dye containing cyanine dye, Te, Se, S, Ge, In, Sb, Fe, Tb, Co, Ag, Ce, Bi, etc. Material layer, acrylic acrylate, ether acrylate, vinyl monomer or oligomer, adhesive layer composed of at least one of polymers, UV curable monomer, oligomer, at least one polymer, polymerization initiator, pigment, auxiliary agent Is not limited to these, but may include a film forming material or a coating material usually used in an optical disk.
From the viewpoint of recycling, since it is desirable that the raw material is low-cost, it is preferable to reuse the resin while impurities from various materials are included.

For example, an optical disk can be finely crushed and used as a PC resin raw material as it is, or kneaded and melted with a predetermined additive and pelletized.
Alternatively, depending on the structure of the injection molding machine, the recovery disk may be directly put into a hopper or the like of the injection molding machine together with a modifying material described later to obtain a molded body made of the resin composition.

When using a PC resin that does not contain the above-mentioned various impurities, deposits such as a metal reflection layer, a recording material layer, an adhesive layer, a surface hardened layer, and a label are disclosed in, for example, It can be removed by a mechanical or chemical method proposed in JP-A No. 223416, JP-A-10-269634, JP-A-10-249315, or the like.
However, in order to remove the deposits and impurities, a large amount of energy is usually required, resulting in high costs. It is preferable to select a PC resin as a raw material in consideration of the performance in

Next, the modifying material will be described.
As a modifier, the melt flow ratio (MFR ratio: according to JISK7210) of the resin composition mixed with the PC resin and the PC resin before mixing under the condition of 220 ° C. and 10 kgf is mixed resin / PC resin = 0. 0.1 to 1.5, and an Izod impact strength ratio (according to JISK 7110. Sample with back notch) is at least 2.0.

The MFR value represents the ease of flow of the polymer at the time of heating and melting, and the larger the value, the easier the resin flows.
When the MFR ratio is large, the resin can be sufficiently supplied even in small and narrow portions when performing melt molding, and a uniform molded body can be obtained. On the other hand, the large MFR ratio means that the molecular weight of the resin composition is small. In general, the physical properties of the molded article, for example, impact strength, tend to be greatly reduced.
In view of this, the MFR ratio of the resin composition of the present invention was set to 0.1 to 1.5.
When the MFR ratio is greater than 1.5, the fluidity is large and precise and high-speed molding is possible, but the impact strength is reduced.
On the other hand, if the MFR ratio is less than 0.1, the melt fluidity becomes poor and precise molding becomes impossible.
The properties of the resin composition, which is a mixed resin of PC resin and modifier, can be basically defined by the MFR ratio and the Izod impact strength ratio, but only the PC component from the resin composition, for example, tetrahydrofuran For example, the molecular weight of the PC component may be evaluated by GPC (gel permeation chromatography).
When the resin composition of the present invention is evaluated by the above method, the weight average molecular weight (Mw: polystyrene equivalent molecular weight) of the PC component is preferably about 40,000, and more preferably 10,000 to 37,000.
When the molecular weight of the PC resin component exceeds 40 million, the MFR ratio of the finally obtained resin composition becomes small and the moldability deteriorates. When the molecular weight is less than 10,000, excellent moldability can be obtained, but mechanical properties such as impact strength deteriorate.

The ratio of the Izod impact strength of the resin composition of the present invention to the raw material PC resin (according to JIS K7110 method, with post-notch) is 2.0 or more, more preferably 2.5 to 50.
If the Izod impact strength ratio is less than 2.0, the molded article properties are insufficient.
On the other hand, in order to produce a resin composition having an impact strength ratio exceeding 50, it is necessary to increase the purity of the raw material PC resin or to increase the usage ratio of the modifier, resulting in high costs. Or a decrease in flexural modulus or tensile modulus.

In order to increase the Izod impact strength ratio of the material, it is effective to select a PC resin having a large molecular weight in advance or to blend a resin having a high viscosity with side chains and branches.
When a high molecular weight PC resin is blended, the melt viscosity of the resin composition in which the PC resin and the modifying material are mixed is increased, the moldability is lowered, and the blend ratio of the recycled material (recovered optical disk) is increased. It becomes difficult to raise.
In the present invention, the above numerical value range is specified in order to achieve both a practically sufficient impact strength ratio and maintaining excellent formability.

Next, the modifying material will be specifically described.
As the modifying material, materials conventionally used for modifying polymers can be applied.
For example, ABS (acrylonitrile-butadiene-styrene), AS (acrylonitrile-styrene resin), HIPS (high impact polystyrene), SBR (styrene-butadiene rubber), SBS (styrene-butadiene-styrene rubber), methyl methacrylate-styrene resin MBS (methyl methacrylate-butadiene-styrene) resin, isoprene-styrene rubber, isoprene rubber, PB (polybutadiene), butadiene-acrylic rubber, isoprene-acrylic rubber, ethylene-propylene rubber, PC / ABS, PC / HIPS, etc. Can be mentioned.

Among the above materials, ABS, HIPS, SBR, SBS, MBS, isoprene-styrene rubber, isoprene rubber, PB (polybutadiene), butadiene-acrylic rubber, isoprene- can be obtained even if the addition amount is small. Examples thereof include resins having rubber components such as acrylic rubber and PC / ABS.
In particular, ABS is a suitable material because the copolymer composition can be changed relatively easily.
The ratio of the rubber component in the ABS resin greatly affects toughness and the like, but is preferably 9% by weight or more, and more preferably 11 to 70% by weight.
When the content of the rubber component is less than 9%, it is difficult to obtain a modification effect. On the other hand, when the content of the rubber component exceeds 70% by weight, the hardness of the mixed resin composition itself may be lowered, or the heat resistance may be lowered.

When the ABS resin is used alone as the modifier, the amount of the rubber component in the ABS resin is preferably 9% by weight or more, and more preferably 11% by weight or more.
The morphology of the ABS resin also affects the reinforcing effect of the PC resin.
That is, AS (acrylonitrile-styrene polymer), which is a plastic component of the ABS resin, and butadiene are separated from the rubber component in a state where the rubber component is present alone as rubber component particles. It was confirmed that a high effect of improving physical properties was obtained when a composite structure in which existing domains were formed, that is, a so-called salami-like structure was formed.
This is because when the amount of rubber in the ABS resin is the same, the structure in which the rubber component particles are separated and scattered, rather than being a dispersion system of the rubber component particles alone, This is because the area of the rubber component particles in the ABS resin is increased, and the substantial reinforcing effect is also increased.

A suitable example of such a so-called salami-like structure is shown in FIG.
In FIG. 1, in the ABS resin, rubber components (butadiene) are interspersed as island-like components 2, and acrylonitrile-styrene copolymer components become sea-like components 1 and are separated from each other. Further, in the island-shaped component 2, the interspersed component 3 in which the acrylonitrile-styrene copolymer is dispersed in the form of particles.
The rubber component in the ABS resin preferably has a relatively large diameter.
That is, the number of rubber component particles having a major axis of 250 μm or more is usually 30% or more, more preferably 35% or more of the total number of rubber component particles, and the number of rubber component particles having a major axis of less than 100 μm is the same standard. It is desirable that the number of rubber component particles having a major axis of 250 μm or more is 40% or more.

Specifically, when a recovered optical disk and an ABS resin are blended to prepare a resin composition, the ratio of the number of rubber component particles having a major axis of 250 μm or more in the total number of rubber component particles as ABS resin is 41%. When TECHNO ABS170 manufactured by Polymer Co., Ltd. was used, the impact strength of the resin composition obtained according to the mixing ratio was a sufficiently good value for practical use.
However, when the ABS resin is UBMABS Psycolac EX10U containing only 10 to 20% of rubber component particles having a long diameter of 250 μm or more, or Toyorac manufactured by Toray Industries, Inc., the amount of ABS resin added is increased. However, the impact strength of the resin composition finally obtained was not as high as in the above examples, and when added in a large amount, the impact strength was improved, but other physical properties were lowered.

Accordingly, it has been found that the size of the rubber component particles and the ratio of those having a major axis of 250 μm or more are important factors in the morphology of the ABS resin.
For example, if the ratio of the rubber component particles having a major axis of 250 μm or more is less than 30%, a sufficient reinforcing effect may not be obtained. In such a case, the amount added must be increased. This is because the cross-sectional area that absorbs external impact is large, and the affinity of the AS (acrylonitrile-styrene) copolymer scattered in the rubber component particles with the PC resin is improved.
Further, since the rubber component particles having a major axis of less than 100 μm are not easily deformed by external stress and the reinforcing effect may not be sufficiently exhibited, the content is preferably 25% or less. It has been confirmed that when such a small particle rubber component exceeds 25%, sufficient impact strength cannot be obtained in the finally obtained resin composition.

A compatibilizer may be applied as the modifier.
The compatibilizer may be used in combination with the ABS resin or may be used alone.
Examples of the compatibilizer include styrene-ethylene-butadiene-styrene copolymer (SEBS), styrene-butadiene-styrene copolymer (SBS), styrene-hydrogenated butadiene-styrene copolymer, and acrylonitrile-butadiene polymer. Grafted polycarbonate, styrene-vinyloxazoline copolymer, petroleum-based resin, surface modification product by polymer of rubber fine particles, ethylene-glycidyl group (meth) acrylate copolymer, various silane coupling agents, various titanium coupling agents, etc. Coupling agent, polyurethane resin, epoxy resin, epoxy-modified block copolymer, various maleic anhydride-modified polymers (for example, MAH-g-PS, MAH-g-PMMA, MAH-g-AS (MAH is maleic anhydride Or d) Carboxy-modified polymers (e.g., EGMA-g-PS, EGMA-g-PMMA, EGMA-g-AS, (although, EGMA ethylene -. Glycidyl methacrylate copolymer) and the like.

The above-mentioned compatibilizer alone is effective in improving the toughness and elongation of PC resin, and in the mixed system of PC resin and ABS resin, it is compatible with or partially reacts with both. To improve the mechanical properties and moldability of the mixed resin.
The structure and function of the compatibilizing agent are the above-mentioned SEBS, SBS, styrene-hydrogenated butadiene-styrene copolymer, polycarbonate grafted with acrylonitrile-butadiene polymer when ABS resin is used as a modifier for PC resin, Coupling agents such as styrene-vinyloxazoline copolymer, petroleum resin obtained by polymerization of C5-C9 fraction, ethylene-glycidyl group (meth) acrylate copolymer, various silane coupling agents, various titanium coupling agents , Polyurethane resin, epoxy resin, epoxy-modified block copolymer, various maleic anhydride-modified polymers (for example, MAH-g-PS, MAH-g-PMMA, MAH-g-AS) or epoxy-modified polymers (for example, EGMA) -G-PS, EGMA-g-PMMA, EGM -G-AS or the like is preferable, and when added directly to the PC resin, styrene-hydrogenated butadiene-styrene copolymer, polycarbonate grafted with acrylonitrile-butadiene polymer, styrene-vinyloxazoline copolymer, ethylene plant Various petroleum resins produced by polymerizing C5 fraction and C9 fraction produced as by-products, surface modification products by polymer of rubber fine particles, ethylene-glycidyl group (meth) acrylate copolymer, various silane coupling agents, various Coupling agents such as titanium coupling agents, polyurethane resins, epoxy resins, epoxy-modified block copolymers, various maleic anhydride-modified polymers (for example, MAH-g-PS, MAH-g-PMMA, MAH-g-AS) ) Or epoxy-modified polymers (eg EGMA) g-PS, EGMA-g-PMMA, may be mentioned as preferred combination of EGMA-g-AS, and the like.
Note that the various modifiers described above may be used alone or in combination.

  As described above, in the resin composition of the present invention, PC resin and ABS resin, PC resin and ABS resin and compatibilizing agent, PC resin and compatibilizing agent can be mentioned as the optimum combination. Thus, a resin composition which is advantageous in terms of cost and has both mechanical properties and moldability was obtained.

Since the modifier is generally inferior in heat resistance as compared with the PC resin, if the content is increased, the mechanical properties and thermal / optical properties of the finally obtained resin composition will be reduced. % Or less, and more preferably 3 to 40% by weight.
When the content exceeds 50% by weight, the effect of the modifier reaches saturation, and further, the cost increases, and the thermal physical properties and mechanical physical properties may be greatly reduced.
In view of this point, the content of the modifier is appropriately determined depending on the properties of the PC resin, the required performance of the final resin composition, the molding method, the shape of the molded body, and the like.
Specifically, when the molded body is a low-load casing or container, the amount of the modifying material may be relatively small, but in the case of a thin container with relatively high impact strength. A relatively large amount of modifying material is required.

Next, the manufacturing method of the resin composition of this invention is demonstrated.
The resin composition of the present invention comprises the above-mentioned PC resin and modifier, and a conventionally known polymer mixing device such as a Banbury mixer, a single screw extruder, a twin screw extruder, a multi screw extruder, It can be produced using a lab plast mill, a conida or the like.
In the mixing step, the material resin may be dry blended and supplied to a predetermined mixing device, or the modifier may be supplied while melting and kneading the PC resin. The modifier may be added in one step, or may be added in several steps. In these methods, an optimum method is selected according to the properties, intended use, required performance, etc. of the final resin composition.

  When the collected used optical disc is used as a PC resin, the metal reflective layer, adhesive layer, label ink, surface hardened layer, etc. adhering to it are broken or crushed into an organic solvent or inorganic acid. PC resin is obtained by removing the solution obtained by using an inorganic alkali solution or by removing the deposits by a physical / mechanical method. It was confirmed that an excellent resin composition was obtained.

In the step of melting and kneading the raw materials, a higher melting temperature can achieve a compatibility promoting effect. However, in order to prevent deterioration, decomposition, coloring, etc. of the modifier, it is 200 to 330 ° C., more preferably 230 to A range of 300 ° C. is preferable.
Furthermore, it is preferable to apply a biaxial kneader with a vacuum vent in the kneading step in order to remove various contaminants and air between the disks. By drawing from the vacuum vent with vacuum, impurities such as low-boiling substances, air and the like can be removed, and the density of the finally obtained mixed resin composition is improved and the quality is improved.

The obtained resin composition is pelletized and formed into a desired shape by a predetermined method such as an injection molding method, an injection compression molding method, an extrusion molding method, a blow molding method, a press molding method, a vacuum molding method, or a foam molding method. Can be molded.
In addition, although methods using a normal thermoplastic resin, such as injection molding and extrusion molding, can be applied, the injection molding method and extrusion molding method are particularly suitable. The resin composition is applied to general household goods, electrical products, automobile parts, machine parts, and the like.

  Since the resin composition of the present invention contains PC resin as a main component, the flame retardancy is relatively good, but a conventionally known flame retardant may be added to further improve the flame retardancy. For example, halogen flame retardant, phosphorus flame retardant, nitrogen flame retardant, inorganic flame retardant (metal hydroxide, etc.), boron flame retardant, silicon flame retardant, metal salt flame retardant, fluorine flame retardant, etc. Is mentioned.

  The resin composition of the present invention and the molded product produced thereby include, as necessary, pigments, dyes, lubricants, ultraviolet absorbers, hindered amine light stabilizers, antioxidants, halogen supplements, light shielding agents, You may mix | blend various additives, such as a metal deactivator, a quencher, an antistatic agent, an electroconductive filler, a reinforcing agent, and a filler.

Next, the resin composition of the present invention will be described with specific examples, but the present invention is not limited to the following examples.
As shown below, samples of various resin compositions were prepared using predetermined materials, and the impact strength and moldability were evaluated.
In addition, the unit of content shall be a weight part.

[Materials used]
(PC resin)
Recovery disc A: Coating film (recording material layer, label, adhesive layer, hardened layer, metal reflective layer, etc.) is removed by treating the used DVD after grinding (2 to 20 mm) with an alkaline hot water solution. What you did.
Recovery disc B: A used DVD that has been crushed (2 to 20 mm) as it is.
Commercially available PC resin: high molecular weight PC (Teijin Chemicals Panlite L-1225L).
(Compatibilizer)
Tuftec M1943 (trade name, manufactured by Asahi Kasei): Hydrogenated styrene / (butadiene / ethylene) copolymer Neopolymer DP90 (manufactured by Shin Nippon Petrochemical): Petroleum resin (polymer of C5 fraction)
Oxazoline compounds: Nippon Shokubai Co., Ltd. Epocross RPS1005

[Preparation of resin mixture]
PC resin and modifier were dry blended in a predetermined amount, using a biaxial kneader (Technobel Co., Ltd., cylinder diameter: 15 mm L / D = 45) while applying a reduced pressure at the first vent to 230 ° C. The mixture was melt-kneaded and extruded from a die having a diameter of 3 mm, cooled, and then cut to a length of about 3 to 5 mm to obtain a resin composition pellet.

[Injection molding]
The resin composition pellets prepared above were dried at 100 ° C. for 17 hours in a ventilating dryer, and then molded using a small injection molding machine (manufactured by Nissei Plastic Industry Co., Ltd., HM7-DENKEY). A sample was made.
The shape of the sample was molded into a shape according to the test method described later.
Molding conditions were resin temperature: 220 to 260 ° C. (depending on the resin composition) and mold temperature: 50 ° C.

The following evaluation was performed on the prepared evaluation sample.
〔Evaluation methods〕
(MFR ratio evaluation)
According to JIS K-7210, it performed on 220 degreeC and the conditions of 10 kgf.
Evaluation was performed using a Takara Kogyo melt indexer MX-101-B.
(Impact strength ratio test)
This was performed according to JIS K-7110.
Testing machine: Impact testing machine (Izod No-555, manufactured by Toyo Seiki Seisakusho)
Test method (with V-shaped notch): Weighing: 2.75 J Lifting angle: 150 ° C
Impact speed: 3.5m / sec
Test atmosphere: Temperature: 23 ° C., Humidity: 50% RH

[Experiment 1]
In this experiment, a recovery film A (PC material component obtained by crushing a used DVD (2 to 20 mm)) was treated with an alkaline hot water solution to produce a coating film (recording material layer, label, adhesive layer, curing) Layer, metal reflective layer, etc.) was used.
ABS resin (UMGABS Co., Ltd. Psycolac EX10U) and compatibilizer hydrogenated styrene / (butadiene / ethylene) copolymer (Asahi Kasei Tuftec M1943) were used as modifiers.
This ABS resin is assumed to contain 10% of a rubber component, and an enlarged schematic view is shown in FIG. This is because the ratio of rubber component particles having a major axis of 250 μm or more is relatively small, and is about 11% of the total number of particles.
Each of the above raw materials was dried and blended at the ratio shown in Table 1 below, melt blended in a twin-screw kneader set at a kneading zone temperature of 230 ° C., extruded into a strand having a diameter of about 3 mm, and air-cooled. The resin composition pellets were prepared by cutting to a length of 3 to 4 mm.
In Table 1, Samples 8 to 11 are examples in which a new material of commercially available injection-molded grade Panlite L-1225L (manufactured by Teijin Chemicals Ltd.) is used as the PC resin.
About evaluation of MFR ratio, the pellet of the resin composition was performed after 100-degree C. conditions were dried for 5 hours.
For the above impact test, the dried pellets were tested using an injection molding machine (HM7-DENKEY, manufactured by Nissei Plastic Industry Co., Ltd.) under the conditions of a resin temperature of 260 ° C. and a mold temperature of 50 ° C. Was measured using this, and the ratio with the measured value of the raw material PC resin was calculated.
The measurement results are shown in Table 1. The resin composition is shown in parts by weight. The impact strength and MFR ratio are the numbers obtained by the above method.

As shown in Table 1, in samples 5 to 7 in which ABS resin and a compatibilizing agent were added as modifiers, rather than sample 1 which was the recovered optical disk (PC resin component) itself, the Izod impact strength ratio (according to JISK7110) )) Could be secured at 2.0 or more. Further, in these, the melt flow ratio (MFR ratio: according to JISK7210) is also in the range of 0.1 to 1.5, and a resin composition having practically good workability while having sufficient mechanical strength. Obtained.
In Samples 8 to 11 using a conventionally known new material as the PC resin, the impact strength ratio was less than 2, and sufficient values were not obtained. This is because the PC resin has a large molecular weight, and even if an ABS resin or a compatibilizing agent is added, the improvement effect cannot be expected so much.

[Experiment 2]
Techno ABS170 (manufactured by Technopolymer Co., Ltd.) was used as the ABS resin.
Other conditions were the same as in [Experiment 1], and a sample of the mixed resin composition was prepared and evaluated.
The resin composition and evaluation results are shown in Table 2 below.

In this experiment in which techno ABS was applied as a modifier, the impact strength ratio of the mixed resin was greatly improved even when the ABS resin content was 10 parts by weight. This is apparent when the sample 3 of [Experiment 1] is compared with the sample 11 of [Experiment 2].
As shown in the enlarged view of ABS shown in FIG. 1, techno ABS has a salami structure in which a fine acrylonitrile-styrene copolymer is present as an interspersed component in the island component 2 which is a rubber component. In addition, since it contains many rubber component particles whose major axis is larger than that of the ABS resin of [Experiment 1] (the ratio is about 41% of the total number of rubber particles of 250 μm or more), This is because the impact resistance of the resin has been dramatically improved.

[Experiment 3]
As a compatibilizing agent, a petroleum resin (New Japan Petrochemical Neopolymer DP90) was used. Other conditions were the same as in [Experiment 2], and a resin composition sample was prepared and evaluated.
The evaluation results are shown in Table 3 below.

  As shown in Table 3, the impact strength ratio of the mixed resin is greatly improved even when the compatibilizer petroleum-based resin is applied as the modifier, even if the ABS resin content is 10 parts by weight. ing.

[Experiment 4]
As the PC resin, a recovery disk B (used DVD was directly pulverized (2 to 20 mm)) was used.
A sample of the resin composition was prepared and evaluated using Techno ABS170 used in [Experiment 2] as the ABS resin and Tuftec M1943 as the compatibilizer. The evaluation results are shown in Table 4 below.
Sample 32 in Table 4 is prepared by melt-kneading PC resin and 7 parts by weight of compatibilizer Tuftec M1943, and then adding 3 parts by weight of ABS resin and Tuftech M1943 to melt-knead. Thus, a resin composition is obtained.

As shown in Table 4 above, when an ABS resin was used alone as a modifier, it was necessary to add 50% in order to achieve an impact strength of 10 or more. If a certain Tuftec M1943 is used in combination, the physical strength characteristics can be obtained and the good workability can be ensured as compared with [Experiment 1] using the optical disk A with a content of ABS resin of about 10 to 30%. It was.
That is, it was found that it is effective to use techno ABS, which is an ABS resin, and Tuftec M1943, which is a compatibilizing agent, from the viewpoint of recycling the recovered disc B.

[Experiment 5]
The recovery disk B was used as the PC resin.
As an ABS resin, Psylacac EX10U used in [Experiment 1] was applied.
Epocros RPS1005 having an oxazoline group was used as a compatibilizing agent.
Other conditions were the same as in [Experiment 1], and a sample of the resin composition was prepared and evaluated. The evaluation results are shown in Table 5 below.

  As shown in Table 5 above, when Epocros RPS1005 having an oxazoline group was used as a compatibilizing agent, a practically sufficient impact strength improvement effect could not be obtained.

[Experiment 6]
The recovery disk B was used as the PC resin.
The ABS resin was compared by changing the amount of the rubber component in the resin for each sample.
Tuftec M1943 was used as a compatibilizing agent.
A predetermined amount of these were dry blended, and a resin composition sample was prepared and evaluated in the same manner as in [Experiment 1].
The evaluation results are shown in Table 6 below.

  In Table 6, regarding ABS resin, B2 indicates B200N, the amount of rubber component is approximately 20%, B3 indicates B300N, the amount of rubber component is approximately 30%, and B5 indicates B500N. The amount is approximately 50%. Both are products of UMGABS.

When the amount of the rubber component of the ABS resin is about 20%, practically sufficient impact strength cannot be obtained unless a compatibilizer is added.
Usually, in the case of an alloy of ABS resin / PC resin, it is general that the MFR ratio is improved by adding ABS resin.
However, when an ABS resin containing relatively large rubber component particles having a long diameter is contained, the MFR ratio of the resulting mixed resin composition decreases and the impact strength ratio increases.
In addition, it was confirmed that the effect of improving the impact strength ratio was obtained even with a compatibilizer alone without adding the ABS resin, and the fluidity was sufficiently ensured.

According to the resin composition of the present invention, it was possible to achieve excellent impact strength while ensuring good moldability, not only contributing to recycling of waste materials, but also providing a molded body applicable to new applications. .
In addition to new materials, optical discs, compact discs, and other products and parts, etc., still have disc recording material layers, metal reflective layers, protective layers, labels, hardened surfaces, and various paints and platings. Even in this state, by recycling, practically sufficient moldability and physical properties were obtained, and a resin composition advantageous in terms of cost was obtained.

The schematic which represented the TEM photograph of techno ABS170 typically is shown. The schematic which represented the TEM photograph of psycholac EX10U typically is shown.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Sea component (acrylonitrile-styrene copolymer), 2 ... Island component (butadiene), 3 ... Interspersed component (acrylonitrile-styrene copolymer), 10 ... Acrylonitrile-styrene copolymer, 11 ... ... Rubber component particles

Claims (4)

It is composed of a mixed resin composed of at least a polycarbonate resin (PC resin) for an optical disk and an ABS resin as a modifier,
The content of the ABS resin in the mixed resin is 3% by weight or more and 50% by weight or less,
The ABS resin contains 9% by weight or more of a rubber component;
In the ABS resin, butadiene as a rubber component is separated as an island-like component, and an acrylonitrile-styrene copolymer component is separated as a sea-like component, and in the island-like component, acrylonitrile-styrene copolymer is particulate. And the number of the rubber component particles having a major axis of 250 nm or more is 30% or more of the whole,
MFR (according to JISK7210) of the mixed resin under the conditions of 220 ° C. and 10 kgf is 12.7 to 25.1 g / 10 minutes,
The resin composition whose Izod impact strength (according to JISK7110) of the mixed resin is 5.1 to 38.3 kJ / m ² .   The resin composition according to claim 1, wherein the mixed resin contains a compatibilizer as a modifier. 3. The resin according to claim 1, wherein the PC resin is a used optical disc to which at least one of a metal layer, a recording material layer, an adhesive layer, a label, and a surface hardened layer is attached, or a waste optical disc. Composition. The PC resin separated and removed the deposit from a used optical disc or a waste optical disc to which a deposit consisting of at least one of a metal layer, a recording material layer, an adhesive layer, a label, and a surface hardened layer was adhered. The resin composition according to claim 1, which is a product.

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