JP3140715B2 - Foam composite molding - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a process for mixing and recycling chip-like, flake-like or fibrous fillers, in particular, cut or crushed card pieces of used cards into a foamable resin. The present invention relates to a technique for forming a composite molded article having excellent strength.

[0002]

2. Description of the Related Art Conventionally, thermoplastic resin composite molded articles obtained by adding a filler such as mica, clay, potassium titanate whisker, potassium carbonate whisker to a polyolefin resin such as a polyethylene resin or a polypropylene resin, or a vinyl chloride resin are known. Are known.

On the other hand, in recent years, the amount of magnetic cards used as prepaid cards has increased dramatically. For example, prepaid cards for telephone calls, which are known by the name of telephone cards, as well as games such as boarding fees, pachinko machines, etc. Rates,
Prepaid cards such as ski lift fees and parking fees have been put into practical use.

[0004] Many of these magnetic cards are used up in one day or several months, but if they are discarded and scattered after use, they damage the environment. Therefore, processing and reuse of used cards is also an important problem.

[0005] Recycling of a plastic molded product is generally performed by separating and pulverizing a different material from the plastic molded product, or by separating the different material after the pulverization and granulating the remaining plastic material, for example, by melt extrusion. It is performed by re-molding and reusing other molded products by melt molding.

[0006]

However, these conventionally known composite molded articles have low mechanical strength such as impact strength, so that they are used in some applications such as indoor building materials and furniture furniture. It is provided for.

A magnetic card is generally made of a biaxially stretched sheet of polyethylene terephthalate (hereinafter sometimes abbreviated as PET) as a base material and a magnetic layer coated thereon. In order to recycle a magnetic card, it is necessary to separate the PET sheet by removing the magnetic layer by grinding or the like, and to re-mold the PET sheet through processes such as pulverization, drying, foreign matter removal, and granulation. Cost. Further, it is difficult to avoid deterioration of characteristics of the obtained reshaped product due to heat history, and it has been difficult to produce a reshaped product having high characteristics. Further, in such a method, the high mechanical strength of the base material of the magnetic card is not utilized at all for the reshaped product.

[0008]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and the gist of the present invention is to cut or crush a used card made of a plastic oriented sheet as a base material by using a foamed card. A foamed composite molded article formed by filling a conductive resin, wherein the card strip has a size of 5 mm
It is a composite molded article characterized by being at least a corner and maintaining the orientation structure of the card strip.

[0009]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.

[0010] The filler of the present invention is a filler in the form of chips, flakes and fibers, and more specifically, card strips obtained by cutting or crushing used cards based on a plastic oriented sheet. Wood strip, biaxially stretched PET
Examples include sheet flakes, PET bottle flakes, and coconut fibers.

In particular, used cards are magnetic cards, and in many cases, PET sheets which are biaxially stretched and heat-set are used as a base material, and are highly molecularly oriented.
As the PET sheet, a sheet having a thickness of 188 μm is often used. A magnetic layer is formed on one surface (back surface), a protective layer is formed thereon, and a printed layer and a protective layer are formed on the other surface (front surface).

The used cards can be used to separate the magnetic material if desired, but can be used simply by performing a simple cleaning / drying process as needed without separating. The card is cut or crushed into small pieces and then reused. This is mainly due to the fact that the strips are more likely to be uniformly distributed in the foamable resin serving as the binder, and that the molding process is easier.

If the size of the material to be cut or crushed is too small, the strength of the substrate itself is not utilized and the reinforcing effect is reduced, and if the size is too large, the arrangement in the plane direction as described later can be easily achieved, but the molding process becomes difficult. It may be set in consideration of both.

That is, in a plate-like (chip-like) form in which the molecular orientation can be substantially maintained while avoiding pulverization, melting, dissolution or the like having a diameter of 100 μm or less, and which can be preferably arranged in layers along the plane. The object is achieved if it is reused.

For example, the strip can be used in the form of a plate (chip) having a length (width) / thickness ratio (aspect ratio) of 5 or more.

Wood, biaxially stretched PET sheet, P
The size of the ET bottle, coconut or the like is preferably 4 mm or less, and more preferably 4 mm to 0.5 mm, because the smoothness of the surface of the composite molded body can be realized.

In order to form chips, flakes and fibers, the blades may be cut into a predetermined shape with a blade or may be crushed into an irregular shape with a crusher.

Then, the foamable resin is filled with a chip-like, flake-like or fibrous filler.

The foamable resin is not particularly limited, and various resins such as polyvinyl chloride, polyethylene, polypropylene, acrylonitrile-butadiene-styrene resin (ABS), acrylic resin and polyurethane can be used.

Among the foamable resins, polyurethane has a polyurethane prepolymer in terms of adhesiveness with a filler.
Since it is liquid at room temperature, it can be mixed with the filler without melting, which is preferable. In particular, a room temperature foamed hard polyurethane resin using water as a foaming agent is suitable from the viewpoint of producing a molded article because it can be foamed at room temperature.

As the polyurethane resin, a diisocyanate component such as toluene diisocyanate or diphenylmethane diisocyanate and a polyol component such as polyester polyol or polyether polyol chain-extended with propylene oxide or ethylene oxide are mixed at about 1: 1. Are preferably used. On the polyol side, a catalyst such as a tertiary amine such as triethylamine or tetramethylhexadiamine or an organic tin compound, or a foam stabilizer and a foaming agent such as polyether siloxane are added.

The foaming agent is not particularly limited as long as it does not deteriorate the foamable resin. For example, a chemical generating gas by chemical decomposition such as azodicarbonamide or azobisisobutyronitrile is used. A blowing agent or an organic gas or a volatile liquid having a boiling point lower than the melting point of the resin, such as butane, pentane, dichlorodifuronmethane, monochlorodifluoroethane, or carbon dioxide, nitrogen, air, argon, or neon Inorganic gas, such as
Alternatively, use water or the like.

These may be used alone or in combination of two or more.

From the viewpoints of safety and environmental protection, inorganic gas and water are preferred. Among them, when a high expansion ratio is desired, a gas having high solubility in the expandable resin such as carbon dioxide is used. In the case of a polyurethane resin, water is preferred. By using a foamable resin, a molded body can be obtained with a small amount of resin,
There is an advantage that a molded article having a desired shape can be easily obtained by expansion at the time of molding the foamable resin.

This filler has a weight ratio of filler / foamable resin in the range of 10/1 to 2/1, in other words, 2 to 10 parts by weight based on the total weight of the polyol component and the isocyanate component or the polyol component 1. Weight.

If the amount of the filler is more than 10% by weight, the expandable resin is insufficient for the filler, the uniformity of the molded article is lost, and the mechanical strength such as impact strength tends to vary. On the other hand, when the content is less than 2% by weight, the effect of improving the mechanical strength such as impact strength due to the addition of the filler is unlikely to occur.

In the case of using strips obtained by cutting or pulverizing used cards, the filling amount is preferably in the range of 10/1 to 3/1 by weight ratio of strips / resin binder. 1
If the number of the strips is larger than 0/1, the integration of the strips is insufficient, and the strips are easily peeled or cracked. When the number of the strips is smaller than 3/1, the effect of improving the mechanical strength of the obtained molded article is small, and the filling amount of the strips is preferably large from the viewpoint of reusing the used card.

Further, when using small pieces of cards,
A molded product having high strength can be obtained by taking advantage of the high strength of the plastic oriented sheet substrate. Further, it is not always necessary to separate the magnetic material from the magnetic card or the like, and the magnetic material can be reused as it is. By using a foamable resin as the binder, the weight used of the binder can be reduced.

The method of mixing the filler and the foamable resin is not particularly limited.

In the case of polyurethane, for example, a polyol and an isocyanate may be uniformly mixed in advance and wetted in a liquid state uniformly on the surface of a filler such as card chips, or the polyol and the isocyanate may be separately separated by a spray gun at a high speed. , And the mixture at the outlet may be atomized and applied to the surface of a filler such as a card strip. In the case of a foamed rigid polyurethane resin at room temperature, a filler such as a card strip is added to a hopper of a fully meshing co-rotating twin-screw extruder, and the mixed polyol, isocyanate and water as a foaming agent are extruded. It may be added and mixed from a central portion of the machine or a vent portion on the discharge port side, for example.

Generally, when a chemical foaming agent is used as a foaming agent, a single-screw or multi-screw extruder used for extrusion molding is used. In addition, when using a physical foaming agent such as an organic gas, a volatile liquid, an inorganic gas, and water, an extruder equipped with a vent-type screw and provided with an inlet through which the foaming agent can be pressed into the vent portion from the middle of the cylinder is used. used.

In particular, a completely meshing co-rotating twin screw extruder is preferable because it has a self-cleaning function in which the grooves of the screws rub against each other so that the mixture of the polyurethane resin and the filler can be prevented from hardening in the staying portion.

The fully meshing co-rotating twin screw extruder is used in combination with a double conveyor type take-off machine as shown in FIGS.

In order to form the foamed composite molded article B, a filler a such as a card or the like is charged from a feeder into a hopper 13 of the extruder 1 and advanced by a screw 11 while the barrel 12 of the extruder 1 is advanced. The mixture is mixed with the room-temperature foamed hard urethane resin b supplied into the extruder 1 from the vent and extruded as a mixed composition A of the urethane resin b and the filler a from the opening at the tip of the barrel 12.

The room-temperature foamed hard urethane resin b is prepared by mixing a predetermined amount of water (foaming agent) and polyol and isocyanate separately stored and stored in containers 151 and 152 with a gear pump (not shown) using a static mixer. After being fed into the extruder 1 and mixed with the filler a, the mixture is mixed with the filler a.
The extruded mixture composition A of the urethane resin b and the filler a contains a screw 11 projecting from the tip of the barrel 12.
Through the opening 121 of the barrel 12 to the outside of the extruder 1.

The discharged mixed composition A falls onto the lower conveyor 21 of the double conveyor type take-up machine 2 installed in advance, moves further on the lower conveyor 21 and is further moved while being sandwiched between the upper conveyor 22. While it is foamed and hardened at room temperature, it is molded into a foam composite molded body B when it exits the take-up machine 2.

The double conveyor type take-up machine 2 comprises a lower conveyor 21 and an upper conveyor 22.
1 is provided with a projection 211 for regulating the mixed composition A that has fallen at the end thereof, and its entire length is longer than that of the upper conveyor 22, and one end is formed by the opening 121 of the extruder 1. It can be located on the extruder side.

The upper conveyor 22 rotates and can move up and down so that the thickness of the foam composite molded body B can be adjusted.

In the figure, a surface material c such as a synthetic resin or a metal is foamed and cured from the mixed composition A to form a foamed composite molded body B, and is bonded to the surface of the molded body B. However, the surface material c such as synthetic resin or metal may not be used.

The foamed composite molded article is obtained by molding a mixture of a filler such as card pieces and a foamable resin, except for molding with an apparatus using a combination of an extruder and a double conveyor type take-up machine.
It is also possible to fill a molding die for regulating the shape, perform foaming by heating or the like, cure and foam, and then remove and mold.

The molding temperature when heating or mixing of the foaming resin with the filler such as a card strip depends on the properties of the foaming resin, the foaming agent and the filler used. The temperature is preferably about 30 ° C. higher than the temperature and slightly lower than the melting temperature of the filler so as not to impair the molecular orientation and directionality of the filler to be added.

In the case of molding with an extruder, the extruder is usually extruded at atmospheric pressure. However, if the extruded atmosphere is kept at a pressure lower than the atmospheric pressure, foaming is completed quickly and bubbles become finer. .

In order to obtain a highly rigid foamed composite molded article according to the present invention, most of the fillers such as card pieces are arranged substantially along the surface direction of the molded article (the filler surface is aligned with the molded article surface). It is preferable that the foamable resin regulates the final shape by adopting the molding method described above and using a filler such as a card-like small piece of an appropriate size. When the resin expands to fill the space between the belts, the flow of the resin allows most of the fillers such as card pieces to be arranged substantially along the surface direction of the molded body.

The foamed composite molded article of the present invention has great utility mainly as a plate-like body. The thickness of the plate is not particularly limited and can be set arbitrarily.
It can be a plate-like body up to the order. In particular, conventionally, it was difficult to stretch-orient a thick plate having a thickness of 5 mm or more. However, the present invention has made it possible to obtain a plate-like body having a stretch-oriented structure without limitation to the thickness. It is a big feature. In this case, it is advantageous to use a filler such as a card strip having a relatively large area such as 5 mm square or more in terms of square shape.

On one or both surfaces of the foamed composite molded article of the present invention, depending on the application, a synthetic resin sheet material such as polyvinyl chloride or PET or a sheet material, a metal sheet material such as steel or aluminum, or a surface material such as a sheet material is used. It is possible to improve the mechanical strength such as rigidity by the composite effect by bonding, and to improve the appearance.

The surface material such as a synthetic resin or metal can be subjected to, for example, wood grain printing or painting to further change the appearance.

Alternatively, the foaming resin may contain reinforcing and filling components such as glass fibers and particulate fillers to further improve the overall mechanical strength such as rigidity.

[0048] The foamed composite molded article thus obtained has high strength and the heat insulating property of the foamed article.
It also has some features such as light weight and cushioning properties, and can be used for various purposes such as civil engineering construction materials, horticultural materials, and furniture top plates.

[0049]

【Example】

"Example 1" Pachinko card (about 50 mm x 80 mm) based on a biaxially stretched PET sheet having a thickness of 188 µm
Was cut to a width of 5 mm × 25 mm by a shredder and mixed with a foamed hard polyurethane to which azocarboxylic acid amide was added as a foaming agent at a mixing ratio (weight ratio) of 3: 1.
The mixture composition is filled in a molding die, heated at 160 ° C., pressurized at 0.5 atm and foamed, and formed into a 200 mm square foam plate having a thickness of 10 mm. A molded article was obtained. The expansion ratio of the polyurethane was about 3 times.

The rigidity (flexural modulus; ASTM D790) of the obtained foamed plate-like molded product was 122 kg / mm ² .

Example 2 Example 1 was repeated except that the mixture ratio (weight ratio) of the crushed product obtained by crushing the pachinko card of Example 1 with a 6 mm through mesh and heated foamed hard polyurethane was 5: 1. The same mixed composition as in Example 1 was molded using the same molding die as in Example 1 under the same molding conditions as in Example 1, and the same 200 mm square as in Example 1 with a thickness of 1
A 0 mm foam plate-shaped molded product was obtained. The expansion ratio of the polyurethane was about 4 times.

The rigidity (flexural modulus; ASTM D790) of the obtained foamed plate-like molded product was 130 kg / mm ² .

Example 3 Biaxial stretching P having a thickness of 200 μm
Pachinko card (about 50mm ×
80 mm) is crushed by a crusher having a mesh of 4 mmφ through, and is supplied to a raw material charging hopper of a fully meshing co-rotating twin screw extruder at a supply amount of 15 kg / Hr.

The fully meshing co-rotating twin screw extruder is a vent type, cylinder temperature: 23 ° C., screw outer diameter: 25.
mm, L / D = 25, and the clearance between the cylinder and the screw is 2-5 mm.

On the other hand, water and polyol as a foaming agent and isocyanate are separately sent to a static mixer by a gear pump, and a room-temperature foamed hard polyurethane stirred by the static mixer is supplied to a vent section provided substantially near the center of the extruder. Was supplied at a rate of 5 kg / Hr, and the ground product and polyurethane were mixed. The mixing ratio (weight ratio) of the pulverized product and the polyurethane was 3: 1.

This mixed composition was discharged from a discharge port of the extruder between the belts of a double-conveyor type take-up machine in which a belt rotating vertically was taken up, foamed and hardened while being taken at room temperature, and was formed into a 300 mm square and 10 mm thick. A foam plate-like molded product was obtained. The expansion ratio of the polyurethane was 10 times.

The rigidity (flexural modulus; ASTM D790) of the obtained foamed plate-like molded product was 300 kg / mm ² .

Further, a surface material was fed from between the discharge port of the extruder and the entrance of the rotating belt, and was laminated on both sides of the foamed plate-like molded product which was foamed. As the surface material, 0.1.
Two types of aluminum plate having a thickness of 3 mm and a vinyl chloride plate having a thickness of 0.3 mm were used.

The characteristic values of the foamed plate-like molded product laminated with the surface material were as follows.

Surface material: aluminum plate Surface material: vinyl chloride plate Flexural modulus (kg / mm ² ) 1600 320 Linear expansion coefficient (L / ° C.) 2 × 10 ⁻⁵ 4 × 10 ⁻⁵ “Example 4” Crushed product Except for using a crushed product obtained by crushing a wood chip mainly composed of Yonetsuga with a 4 mmφ through mesh, a mixed composition made in the same manner as in Example 3,
Molding was performed under the same molding conditions as in Example 3 to obtain a foamed plate-like molded body similar to that of Example 3 having a size of 200 mm square, a thickness of 10 mm, and an expansion ratio of about 10 times.

The rigidity (flexural modulus; ASTM D790) of the obtained foamed plate-like molded product was 320 kg / mm ² .

Further, a surface material was fed in the same manner as in Example 3, and this was laminated on both sides of a foamed foam plate-like molded product.
As the surface material, two types of a 0.3 mm thick aluminum plate and a 0.3 mm thick vinyl chloride plate were used as in Example 3.

The characteristic values of the foamed plate-like molded product obtained by laminating the surface materials were as follows.

Surface material: Aluminum plate Surface material: Vinyl chloride plate Flexural modulus (Kg / mm ² ) 1700 350 Linear expansion coefficient (L / ° C.) 2 × 10 ⁻⁵ 3 × 10 ⁻⁵ “Example 5” crushed product Example 3 except that the mixing ratio (weight ratio) of the polyurethane and the heat-foamable rigid polyurethane was 1: 1.
The same mixed composition as in Example 3 was molded under the same molding conditions as in Example 3, and the same 200 mm square as in Example 3 and a thickness of 10 m
m, a foamed plate-like molded product having an expansion ratio of about 10 times was obtained.

The rigidity (flexural modulus; ASTM D790) of the obtained foamed plate-like molded product was 40 kg / mm ² .

Further, a surface material was fed in the same manner as in Example 3, and this was laminated on both sides of a foamed foam plate-like molded product.
As the surface material, two types of a 0.3 mm thick aluminum plate and a 0.3 mm thick vinyl chloride plate were used as in Example 3.

The characteristic values of the foamed plate-like molded product laminated with the surface material were as follows.

Surface material: aluminum plate Surface material: vinyl chloride plate Flexural modulus (Kg / mm ² ) 1000 50 Linear expansion coefficient (L / ° C.) 2 × 10 ⁻⁵ 6 × 10 ⁻⁵ “Example 6” crushed product The same composition as in Example 3 was molded under the same molding conditions as in Example 3 except that the mixing ratio (weight ratio) between the mixture and the heat-expandable rigid polyurethane was 10: 1. 200mm square and 10 thickness
mm and an expansion ratio of about 10 times were obtained.

The rigidity (flexural modulus; ASTM D790) of the obtained foamed plate-like molded product was 30 kg / mm ² .

Further, a surface material was fed in the same manner as in Example 3, and this was laminated on both sides of a foamed foam plate-like molded product.
As the surface material, two types of a 0.3 mm thick aluminum plate and a 0.3 mm thick vinyl chloride plate were used as in Example 3.

The characteristic values of the foamed plate-like molded product obtained by laminating the surface materials were as follows.

Surface material: aluminum plate Surface material: vinyl chloride plate Flexural modulus (Kg / mm ² ) 1000 50 Linear expansion coefficient (L / ° C.) 2 × 10 ⁻⁵ 6 × 10 ⁻⁵ Comparative Example As foaming agent Filling a molding die with heat-foamable hard polyurethane to which azocarboxylic acid amide is added
Heat at 60 ° C, pressurize at 0.5 atm to foam, 20
A 0 mm square, 10 mm thick foam plate-like molded product was obtained. The expansion ratio of the polyurethane was about 10 times.

The rigidity (flexural modulus; ASTM D790) of the obtained foamed plate-like molded product was 10 kg / mm ² .

[0074]

According to the present invention, there is provided a foamed composite molded article formed by filling a foamable resin with a card strip obtained by cutting or crushing a used card having a plastic oriented sheet as a base material, Since the size of the card strip is 5 mm square or more and the orientation structure of the card strip is maintained, the composite molded article has excellent mechanical strength. Moreover, the present invention does not melt and reshape the crushed product upon reusing the used magnetic card after use. The orientation structure of the plastic orientation sheet base material is utilized as it is, resulting in high strength. By using a foamable resin as a binder, a molded article can be obtained with a relatively small amount of binder.

Further, in the reproduction, the separation of the magnetic material is not necessarily required, so that the reproduction process itself can be greatly simplified.

Further, depending on the application, polyvinyl chloride, PE
Attaching a surface material such as a synthetic resin sheet such as T or a plate or a metal sheet such as steel or aluminum or a plate to improve mechanical strength such as rigidity due to a combined effect,
The appearance can be improved.

These foam composite molded articles have high strength and also have some of the features of the foams such as heat insulating property, light weight and cushioning property, and are used for civil engineering construction materials, indoor / outdoor building materials, horticultural materials. It can be widely used for various applications such as top plates for furniture.

[Brief description of the drawings]

FIG. 1 is a partial cross-sectional side view schematically showing an example of an extruded foam production apparatus of the present invention.

FIG. 2 shows the opening of the extruder according to the invention in a front view.

FIG. 3 is an enlarged cross-sectional view of the double conveyor of the take-up machine of the present invention taken along line XX of FIG.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Fully meshing co-rotating twin screw extruder 11 Screw 12 Barrel 121 Opening 14 Static mixer 151 Container 152 Container 2 Double conveyor type take-up machine 21 Lower conveyor 211 Projection 22 Upper conveyor A Mixed composition B Foam composite molding a Filler b Room temperature foamed hard urethane resin c Surface material

Continuation of the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C08J 9/00-9/42 C08L 75/04-75/10 C08L 101/00-101/16 C08G 18/00-18 / 87

Claims (1)

(57) [Claims] 1. A foam composite molded article formed by filling a foamable resin with a card strip obtained by cutting or crushing a used card having a plastic oriented sheet as a base material, wherein said card strip is Wherein the size of the card is 5 mm or more and the orientation structure of the card strip is maintained.