JP2010241440A - Glass-containing blow-molded container - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a glass-containing blow-molded container capable of molding the glass-containing blow-molded container which can be molded by a conventional blow-molding method using pellets containing a glass powder of ≥40 wt.% in a versatile resin, and having excellent physical properties. <P>SOLUTION: The glass-containing blow-molded container is formed by a blow-molding method while using glass-containing molding pellets containing glass powder in a thermoplastic resin. The glass-containing blow-molding pellets contains solid spherical glass powder in a range of a glass blending ratio of 40-70 wt.% in a resin of one kind to be selected from among a group composed of a polyethylene resin, a polypropylene resin and a polyethylene terephthalate resin as the thermoplastic resin. As the glass blending ratio is increased, the total beam transmittance improving index of the glass-containing blow-molded container is gradually decreased for improvement following a specified formula. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a glass-containing blow container having excellent physical properties, which is molded by a conventional blow molding method using a glass-containing molding pellet in which a glass powder of 40% by weight or more is blended in a thermoplastic resin. About. Specifically, a glass containing a solid spherical glass powder as the glass powder in a range of 40 to 70% by weight in a kind of resin selected from the group consisting of polyethylene resin, polypropylene resin and polyethylene terephthalate resin. The present invention relates to a glass-containing blow container having an excellent appearance, which is obtained by blow-molding a containing molding pellet.

  About 70% of the production volume of plastic containers is blow containers, and the thermoplastic resin that is the material of the blow containers tends to continue to increase, as seen in PET bottles (polyethylene terephthalate resin), for example. As other thermoplastic resins, polyethylene resins and polypropylene resins are used in large quantities. These resins are used in large quantities as materials for blow containers, and are known as versatile resins. Other resins include polyolefin resins containing polystyrene, polyethylene naphthalate, and polyester resins containing polybutylene terephthalate. And polycarbonate resins.

By the way, it is well known that today's global problems, such as global warming problems such as carbon dioxide, and finite oil resource depletion are closely related to the above-mentioned plastic production. However, the relationship between the problem of global warming and the depletion of petroleum resources and the production volume of plastic is described below.
Plastic is a polymer compound synthesized from petroleum, and since it is easy to mold with a mold or the like, it is used as a raw material for various daily necessities, products in the medical field and industrial field that are mass-produced. Since it is possible to synthesize resins with performance that matches the purpose and application of use, plastic production in Japan has been around 14 million tons in recent years.

  In 2004, plastic production in Japan reached about 1.48 million tons, and the plastic production by plastic is the largest (hereinafter referred to as “PE”), followed by polypropylene resin (hereinafter referred to as “PE”). "PP"), polyvinyl chloride resin, polystyrene resin, polyethylene terephthalate resin (hereinafter referred to as "PET"), followed by ABS resin, followed by production of thermoplastic resin among plastics. About 90% of plastic production is thermoplastic resin.

The present inventor is thinking that every day the world must solve the global warming problem such as carbon dioxide and the finite oil resource depletion problem that are urgently solved as a common problem. As a result of careful consideration, I came up with a solution.
One solution is that a large amount of glass powder is blended with a thermoplastic resin synthesized from petroleum, for example, 70% glass powder is blended and kneaded with an extruder and extruded to produce pellets for molding. If so, the amount of thermoplastic resin, that is, petroleum can be reduced by 70%, the amount of carbon dioxide emitted by incineration of the molded body can be reduced by 70%, and the incineration energy can be reduced and the molded body can be reduced. The glass powder that has become a residue after incineration is contained in the resin and can be recycled.

  Therefore, the present inventor blended 40% by weight or more of glass powder into a thermoplastic resin before filing the present application, for example, blended 70% by weight of glass powder, kneaded with an extruder, extruded, and pellets (glass-containing) As a result of diligent research to form a molding pellet), a glass-containing molding pellet containing 40 to 70% by weight of a solid spherical glass powder in a thermoplastic resin was completed. PCT / JP2008 / 68093 (Application No. 2009-504515) (the title of the invention “Pellet for glass-containing molding and its production method”, priority claim date: H19.10.4 (hereinafter referred to as “prior application invention”)).

  In a production method for obtaining a molding composition by mixing glass powder with pellets conventionally used, the pellet and glass powder are first weighed and mixed uniformly with a mixer and then put into a hopper. As the glass powder, a glass fiber that has been coated with a silane compound, that is, silanized, is used by pulverizing glass fibers before being charged and immersing them in a liquid containing a silane compound. There are many cases. The silane compound is a compound composed of an organic substance and silicon, and normally serves as an intermediary between an organic material and an inorganic material that are very difficult to be combined. Is used.

  This silanized glass powder is put into a hopper. Since the frictional resistance of the glass powder is large near the entrance of the hopper, both materials are die-cast in a state where the glass powder bites sand by the shearing force of the screw. When it enters the heater / blower area, the glass powder is mixed in the pellets melted in the vicinity of the inner cylinder of the cylinder by the heating of the heater provided in the outer cylinder of the cylinder. In the phase state and in the vicinity of the outer cylinder of the screw, unmelted pellets exist in the solid state. However, the solid-phase pellets of the screw outer cylinder and the liquid-phase pellets of the cylinder inner cylinder are kneaded and stirred by a high-speed rotating screw to mix the solid-phase pellets and the liquid-phase pellets. It becomes a molten state. As described above, in the vicinity of the inlet of the heater / blower region, the pellet is in a semi-molten state, so that the fluidity is lowered, and the frictional resistance force opposed to the shearing force of the screw is rapidly increased.

Then, if a large amount of glass powder is added to the pellet and kneaded, the above pellets are in a semi-molten state and a large amount of glass powder is present, so the fluidity is drastically reduced, and the frictional resistance against the screw is increased. It is well known to those skilled in the art that the shearing force of the screw becomes larger than that, causing screw thread damage or the like, and stopping the control of the kneading and compressing screw. And since the extruder is an expensive machine with 2 to 30 million units per unit, it is afraid of expensive loss of parts replacement cost, repair cost and inspection cost due to damage or stoppage of the extruder. The actual situation is that the traders only mix up to 35% by weight of the glass powder.
Thus, in the field of plastic molding technology, for the purpose of improving the physical properties of a thermoplastic resin, when a large amount of glass powder is blended and kneaded with a thermoplastic resin with an extruder, the fluidity rapidly decreases. It has been recognized that it is impossible to produce a thermoplastic resin composition that contains more than wt% glass powder.

Therefore, the present inventor has studied carefully in order to elucidate the cause of a sharp drop in fluidity when a large amount of glass powder is blended and kneaded in a thermoplastic resin with an extruder. It has been speculated that there is a sudden drop in fluidity due to the two factors interrelated.
The rapid decrease in fluidity is caused by the fact that a semi-molten state in which a solid phase and a liquid phase are mixed is generated. In general, a dipping method in which glass powder is stirred for 30 minutes, dipped, filtered, and dried at 100 ° C. is performed, and the silane compound is coated in a state where a plurality of glass powders are in contact with each other by the treatment. Therefore, since the glass powder is filtered and dried in the agglomerated state, the agglomerated glass powder (hereinafter referred to as “aggregated glass powder”) exists in the silanized glass powder. In addition, since the glass powder to be blended in the conventionally used thermoplastic resin is obtained by finely pulverizing glass fibers, the shape thereof is polygonal, rectangular, etc. It is composed of various shapes, and the average particle diameter is in a wide distribution range of 10 to 100 μm, the various shapes and the distribution width are wide, and the difference in specific heat between glass and thermoplastic resin is For example, the specific heat of glass is 0.670 J / (kg · K), whereas that of PET is 1.5 J / (kg · K), which is higher than that of glass to raise to a certain temperature. This requires 2.2 times the amount of heat, the large difference in specific heat, and the four causes acting in a complex manner, so that 40% by weight or more of glass powder is added to the thermoplastic resin. When blended and kneaded, the fluidity is drastically reduced, which is considered to be the cause of the inability to produce a molding composition containing glass powder, and the present inventor completed the invention of the prior application by removing these causes. It came to do.

  Since the cause of the rapid decrease in fluidity described above has not been elucidated, a resin composition in which about 35% by weight of glass powder is blended with resin pellets can be produced conventionally. It is impossible to produce a glass-containing resin pellet by mixing a large amount of glass powder, kneading with an extruder and extruding to produce a glass-containing resin pellet. There has been no report that a resin pellet containing a large amount of glass powder of more than 10% has been successfully commercialized.

For example, “In the present invention, the content of the glass filler in the polycarbonate resin composition is 10% by mass or more and less than 40% by mass, and preferably 15 to 35% by mass. Less than 10% by mass. Then, the mechanical properties of the molded product are insufficient, and if it exceeds 40% by mass, the contact area between the resin and the glass filler increases, the transparency of the molded product decreases, and the moldability decreases. (Refer to paragraph [0056] of Patent Document 1), “The thermoplastic resin composition of the present invention contains 0.1 to 50 phosphate glass based on 100 parts by mass of the thermoplastic resin. When the amount is less than 0.1 part by mass, the effect of imparting flame retardancy cannot be obtained, and when it exceeds 50 parts by mass, the molding fluidity of the resin composition may be inferior. The amount of acid salt glass is 0 From 5 to 30 parts by weight. "(Phosphate type glass 50 parts by weight in equivalent 33.3% by weight) it (see paragraph [0026] of Patent Document 2), and the Ag ₂ O in the" present invention The blending amount of the soluble phosphate glass powder to be contained is 0.1 to 40% by weight.If the blending amount is less than 0.1% by weight, the antibacterial performance is not exhibited, and if it exceeds 40% by weight. The viscosity of the resin itself becomes high and it becomes difficult to obtain a uniform dispersion in the compounded resin.The compounding amount of the soluble phosphate glass powder containing Ag ₂ O is preferably 0.3 to 35% by weight. , More preferably 0.5 to 30% by weight ”(see paragraph [0016] of Patent Document 3).

By the way, blow containers made of polyethylene resin, polypropylene resin, etc. are used for containers for storing daily necessities such as cosmetic containers, detergents, shampoos, foods, pharmaceuticals, etc. A container having a polished glass-like appearance (frost feeling) having a low gloss and a translucent feeling is highly demanded by consumers because it can feel a sense of weight and luxury.
The following techniques are known as techniques for imparting a frost feeling to the blow container.

In order to give a feeling of frost like a glass cosmetic bottle, the surface layer has a melt flow rate (HLMFR) of 3.0 to 15 g / 10 min at a temperature of 190 ° C. and a load of 21.6 kg, a temperature of 190 ° C. and a load of 2 Polyethylene having a melt flow rate (MFR) of 0.02 to 0.1 g / 10 min and a density of 0.935 to 0.964 g / cm ³ at .16 kg, and the inner layer has a melt flow rate (HLMFR) Multilayer blow consisting of polyethylene having a melt flow rate (MFR) of 0.1 to 7.0 g / 10 min and a density of 0.935 to 0.964 g / cm ³ over 15 to 680 g / 10 min. Molded products are known. In this multilayer blow molded product, the haze of the molded product body is preferably 70% or more and the total light transmittance is preferably 90% or less, more preferably, the haze is 80 to 95% and the total light transmittance is 60 to 60%. It is 90% and has a frost feeling similar to that of glass products. In particular, it is known that the surface of the container is matte, and the contents and the internal solution can be seen with an opaque feeling like a frosted glass container. (See Patent Document 4).

In order to impart a feeling of frost to a blow container, a multilayer blow container having a structure in which a composition obtained by mixing a specific polypropylene resin and a polyethylene resin is used as a skin layer and a specific polypropylene resin is used as an inner layer (see Patent Document 5) And the multilayer blow container which a surface layer consists of a specific ethylene-propylene block copolymer and a main layer consists of a specific polyethylene resin is known (refer patent document 6).
In addition, a bottle of polyester or polycarbonate resin such as polyethylene terephthalate and polyethylene naphthalate is known as a sand blasting method in which sand is blown together with compressed air as a method for opacifying a transparent body and matting finish of a glossy surface. It is difficult to uniformly treat the outer surface of stretch blown containers that are transparent and have improved rigidity due to orientation, and are difficult to adopt for making PET bottles and wide-mouthed bottles opaque or translucent. A stretch blow container is known in which the surface is formed to be opaque or translucent by peening caused by spraying fine particles having a size of 20 to 40 μm (see Patent Document 7).

JP 2006-022236 A JP 2004-256787 A JP 2001-139932 A JP 2009-012399 A Japanese Patent Laid-Open No. 10-278917 JP-A-10-315359 JP 2000-043888 A

  As described above, since it is impossible to manufacture resin pellets containing 40% by weight or more of glass powder in resin pellets due to a decrease in fluidity of a blend of resin and glass powder, naturally, No case has been reported that a blow container containing 40% by weight or more of glass powder can be made into a product without any trouble at the time of molding by this blow molding method. Therefore, whether or not the product can be produced without causing trouble during molding by the conventional blow molding method using the pellet containing 40% by weight or more of the invention of the prior application, and the above glass powder was contained. It is unclear whether the blow container has excellent physical properties and characteristics.

On the other hand, the multilayer blow molded article of Patent Document 4 has a haze of 80 to 95% and a total light transmittance of 60 to 90%, both of which have large optical properties. In order to require a specific polyethylene having a specific polyethylene melt flow rate (HLMFR), melt flow rate (MFR) and density, the cost of producing the specific polyethylene is increased, and the melt flow rate is increased. In the process of molding the blow molded body to maintain it, strict temperature control or the like is required, which increases the product cost.
The multilayer blow container of Patent Document 5 is obtained by laminating a skin layer of a composition in which a specific polypropylene and polyethylene are mixed and an inner layer of a specific polypropylene. The multilayer blow container of Patent Document 6 is an ethylene-propylene block copolymer. The outer layer of a mixture of polymer and high-density polyethylene and the inner layer of an ethylene-propylene random copolymer are laminated, but these multilayer blow containers have a low gloss appearance, but are characterized by polished glass. It is difficult to obtain a certain translucent appearance, and unlike the frost feeling of a glass container, it is poor in luxury and profound feeling.

Further, as described in Patent Document 7, blow containers using polyethylene terephthalate are known to form the outer surface of the container to be opaque or translucent by sandblasting or peening. If the outer surface of the container is uniformly treated by sand blasting or peening after that, it is difficult to uniformly treat the outer surface of the blow container, and the number of surface processing steps increases, resulting in an increase in product cost.
As described above, the multi-layer blow container has a problem that the product cost is high, and unlike the frost feeling of the glass container, it has poor luxury and heavy feeling. A blow container using polyethylene terephthalate has a problem that it is difficult to uniformly treat the outer surface of the blow container, and the product cost is high.

  Therefore, the present invention uses a glass-containing molding pellet containing 40% by weight or more of glass powder in a general-purpose resin, and is a product of a blow container without trouble when molding by a conventional blow molding method. The appearance of the blow container can be improved, and by the relational expression showing the relationship between the visible light transmitted light of the blow container and the glass blending ratio, the ratio of improvement of the appearance of the blow container can be predicted, An object of the present invention is to provide a glass-containing blow container that can be produced at low cost.

Therefore, the present inventor has commercialized a glass-containing blow container containing a large amount of glass powder by earnestly researching the glass-containing blow container produced using the glass-containing molding pellets of the invention of the prior application, The glass-containing blow container of the present invention has been completed by finding out that the appearance of the blow container can be improved and that the blow container can be manufactured at a low cost.
That is, in order to solve the above-mentioned problem, the glass-containing blow container according to claim 1 of the present application is a glass-containing product formed by a blow molding method using a glass-containing molding pellet containing glass powder in a thermoplastic resin. A solid spherical glass that is a glass powder in a kind of resin selected from the group consisting of polyethylene resin, polypropylene resin, and polyethylene terephthalate resin, wherein the glass-containing molding pellets are the thermoplastic resin. The powder is contained in the range of 40 to 70% by weight of the glass, and as the glass content increases, the total light transmittance improvement index of the glass-containing blow container gradually decreases along the following formula: It is improved.
y = −0.009x + 0.998 (x: glass blending ratio, y: total light transmittance improvement index)
Similarly, the glass-containing blow container according to claim 2 of the present application is characterized in that the total light transmittance improvement index is gradually reduced from 0.64 to 0.37 as the glass blending ratio increases. And
The glass-containing blow container according to claim 3 of the present application is characterized in that the glass-containing blow container of the polyethylene resin or polypropylene resin has a haze value of 90% or more.
The glass-containing blow container according to claim 4 of the present application is characterized in that the appearance of the glass-containing blow container has a polished glass-like texture.
In the glass-containing blow container according to claim 5 of the present application, the glass-containing blow container of the polyethylene terephthalate resin contains in the range of 40 to 70% by weight of the glass blending ratio, and the glass blending ratio increases. The total light transmittance improvement index is gradually reduced from 0.55 to 0.37, and the haze exhibits a value of 90% or more.
The glass-containing blow container according to claim 6 of the present application is characterized in that the appearance of the glass-containing blow container has a ceramic-like texture.
The glass-containing blow container according to claim 7 of the present application is characterized in that the liquid level of the glass-containing blow container can be identified.
The glass-containing blow container according to claim 8 of the present application is characterized in that the glass-containing blow container has a shape of a bottle, a tube, a cup and / or a tray.
In the glass-containing blow container according to claim 9 of the present application, the glass-containing blow container is a beverage container, a cosmetic container, a shampoo container, a rinse container, a body soap container, the tube is a cosmetic container, a pharmaceutical container, and the cup Is a food container, and the tray is a lunch box or a fresh food container.

The glass-containing blow container of the present invention can be commercialized without causing any trouble when molding a blow container in which the glass-containing molding pellets are in the range of 40 to 70% by weight of the glass blending ratio. Since it can be molded by the molding method, it is easy to commercialize with conventional facilities and products can be manufactured at low cost, and the raw material of spherical glass powder is an abundant resource in Japan, and its material cost is low, It is promising as an alternative material for today's soaring oil.
In addition, the glass-containing blow container of the present invention has an amount of carbon dioxide discharged when incinerating a blow container molded using the glass-containing molding composition, compared to a 100% resin blow container. It can be reduced by up to 70% and contributes greatly as a technology to solve the global warming problem, which is a global issue. In addition, the glass-containing blow container of the present invention can reduce the amount of use of thermoplastic resin, that is, petroleum, by up to 70%, and is a technology for solving the finite oil resource depletion problem, which is a global issue. Great contribution.

And the glass containing blow container of the present invention,
Since the index for improving the total light transmittance is 0.37 or more, the liquid level in the bottle can be identified, the PE or PP bottle has a polished glass-like texture, and the PET bottle has a ceramic-like texture. As the glass blending ratio increases, the texture of the appearance increases and a sense of weight and luxury is felt. Therefore, it is a product that meets the demands of consumers because of its excellent ornamentality.
Furthermore, food containers and cosmetic containers having these characteristics are excellent in convenience because the position of the liquid surface storing the liquid is known.
The relational expression showing the relationship between the visible light transmitted light of the blow container and the glass blending ratio makes it possible to predict the rate at which the appearance of the blow container is improved.

It is a longitudinal cross-sectional view of an example extruder used for the manufacturing method which shape | molds the pellet for glass containing shaping | molding of this invention, and manufactures the composition. It is a distribution map which shows distribution of the average particle diameter of spherical E glass powder. It is an electron micrograph of 1000 times of spherical E glass powder. It is the electron micrograph which expanded the cutting | disconnection part which cut | disconnected the pellet perpendicularly | vertically from the side surface obtained by mix | blending 50 weight% of spherical E glass powders with PP 50 times. It is the electron micrograph which expanded and image | photographed the said cutting part by 100 time. It is the electron micrograph which expanded and image | photographed the side surface of the said pellet 100 times. It is the graph which showed the glass compounding rate of PE, and the relationship of MFR. It is the graph which showed the glass blending rate of PP, and the relationship of MFR. It is the graph which showed the glass compounding rate of PET, and the relationship of MFR. It is the graph which showed the relationship of the glass compounding rate and MFR in the glass containing molding pellet of Examples 11-13. It is the graph which showed the relationship between the glass compounding rate and the MFR fall rate in the glass containing molding pellet of Examples 11-13. It is the graph which showed the relationship between the maximum value and minimum value of the glass compounding rate and the MFR fall rate in the glass containing molding pellets of Examples 11-31. It is the graph which showed the relationship between the glass compounding rate of the glass containing blow container of Examples 11-31, and a total light transmittance. It is the graph which showed the relationship between the glass compounding rate of the glass containing blow container of Examples 11-31, and a total light transmittance improvement parameter | index. It is the graph which showed the relationship between the glass compounding rate of the glass containing blow container of Examples 11-31, and the total light transmittance improvement parameter | index of an average value. It is the graph which showed the glass compounding rate of the glass containing blow container of Examples 11-31, and the relationship of haze. It is a graph which shows the relationship of the glass compounding rate of PE, a total light transmittance, and a diffuse transmittance. It is a graph which shows the relationship between the glass compounding rate of PP, total light transmittance, and diffuse transmittance. It is a graph which shows the relationship between the glass compounding rate of PET, total light transmittance, and diffuse transmittance.

First, the glass-containing molding pellets having a glass blending ratio of 40 to 70% by weight and the manufacturing method thereof will be described, and then the glass-containing blow container of the present invention and the physical properties and characteristics thereof will be described.
According to the explanation, as a physical property of the glass-containing molding pellets containing glass powder at a glass blending ratio of 40 to 70% by weight, a melt flow rate (hereinafter referred to as a measure of fluidity of a polymer in a molten state) , "MFR") can be understood, and when using the glass-containing molding pellets, it is possible to understand the MFR value of the glass-containing blow container that can be molded without any trouble when molding by the conventional blow molding method. And the physical property which the blow container has can be understood.

(Molding process of glass-containing molding pellets)
FIG. 1 is a longitudinal sectional view of one extruder used for producing the glass-containing molding pellets of the present invention. The spherical spherical glass powder and thermoplastic resin in the range of 40 to 70% by weight are kneaded and extruded by the extruder to form glass-containing molding pellets.
Based on the extruder of FIG. 1, the process of knead | mixing and extruding the solid spherical glass powder and thermoplastic resin of the range of 40 to 70 weight%, and forming the pellet containing glass containing is demonstrated.
The extruder used in the embodiment of the present invention is provided with two hoppers for charging pellets and spherical glass powder as feed materials. The hoppers of the extruder shown in FIG. 1 are referred to as first and second hoppers in order from the left side. The first hopper is filled with thermoplastic resin pellets, and the second hopper provided near the middle part of the extruder Is charged with spherical glass powder. The arrangement position of the second hopper is provided at a position where the pellets supplied from the first hopper into the screw barrel are in a molten state as they are kneaded and conveyed by the screw.
The extruder shown in FIG. 1 is the same as the conventional extruder except for the structure of the hopper as compared with the conventional extruder, so that the description of the structure of the extruder shown in FIG. 1 is omitted. To do.

  The extruder provided with the first and second hoppers has been conventionally known as a resin material and a plurality of kinds of fillers, pigments and the like that are extruded and molded. The difference between the two hoppers and the conventional one is that the conventional second hopper uses a small hopper because the blending ratio of filler and the like is extremely small relative to the blended amount of the pellets. Since the hopper is charged with a large amount of spherical glass powder, the size of the second hopper should be equal to or larger than that of the first hopper of the pellet, and heating to preheat the spherical glass powder above the hopper The difference is that an apparatus (not shown) is provided. If the said heating apparatus can be heated in the range of 150 to 350 degreeC and can be controlled to a fixed temperature, the heating apparatus normally used can be used.

  The temperature of the filler, pigment, etc. to be charged into the conventional second hopper is used at room temperature, but the spherical glass powder of the present invention is the same as the melting temperature of the thermoplastic resin before being charged into the second hopper, Preheat to a temperature close to that and then charge. The preheating temperature is most preferably the same as the melting temperature, and (the melting temperature ± 10% temperature) is preferable. When the preheating temperature is lower than (the melting temperature−10% temperature), a large amount of glass powder takes heat from the molten thermoplastic resin, so that the fluidity may decrease, and the preheating temperature ( If the temperature is higher than the melting temperature + 10%, the viscosity resistance of the thermoplastic resin is too low and it may be in a liquid state and cannot be pelletized. Therefore, the preheating temperature of the glass powder is (melting temperature ± 10%). (Temperature) range is appropriate.

  First, according to the determined thermoplastic resin and glass blending ratio, the weight of the supplied pellets is weighed and put into the first hopper, and the pellets sent by kneading and conveying by the screw are in a molten state by the heater, That is, at the position where the second hopper is disposed, the spherical glass powder weighed to be supplied is preheated to a temperature equal to or close to the melting temperature of the thermoplastic resin and is put into the second hopper. The solid spherical glass powder charged into the molten thermoplastic resin is extruded while being kneaded to form glass-containing molding pellets, which are then cut to obtain pellets.

  The temperature of the heater is determined according to the melting point of the thermoplastic resin to be used. For example, HDPE is 230 ° C., PP is 220 ° C., and PET is 250 ° C. Then, the number of rotations of the screw of the extruder was 200 times / minute while the compound was kneaded and extruded from a nozzle die having a diameter of 3 mm to form a rod, cooled with water and cut into a length of 4 mm to obtain a pellet. It was.

(Solid spherical glass powder)
The glass material of the solid spherical glass powder of the present invention (hereinafter referred to as “spherical glass powder”) has one or more of SiO ₂ , B ₂ O ₃ , and P ₂ O ₃ as a skeleton component. Examples include alkali glass, soluble glass, alkali-free glass, and silica glass. And in order to make the shape spherical, the distribution of the average particle diameter can be sharpened by using a method of pulverizing glass fibers. When the spherical glass powder has a high alkali content, the thermoplastic resin is likely to be embrittled. Therefore, a soluble glass having a low alkali content is preferable, and an E glass that is an alkali-free glass having no alkali content is more preferable. However, which glassy material is used is determined according to the application, and the solid spherical glass powder of the present invention is not limited to the examples.

  As the spherical glass powder, glass fiber having a diameter of 20 μm is used as a material. Since the diameter of the glass fiber is constant, a pulverized product having a diameter of 20 μm and a length of 10 to 30 μm is obtained by pulverizing the glass fiber so that the length of the glass fiber does not vary from the diameter of 20 μm. This pulverized product is sprayed into a 2500 to 3000 ° C. flame by an oxygen burner provided inside the furnace to be spheroidized, and the sprayed sphere is sprayed with γ-glycidyloxypropylmethyldibenzene from a water injection device provided at the bottom of the furnace. Water containing 0.1% by weight of ethoxysilane was sprayed, silanized in a sprayed state, and collected with a bag filter. The collected glass powder is a spherical glass powder having a spherical average particle diameter of 10 to 40 μm. Thus, the spherical glass powder with an average particle diameter of 10-40 micrometers was obtained by using the said glass fiber whose diameter is 20 micrometers as a material. The obtained spherical glass powder was solid. Hereinafter, the method of performing the silanization treatment performed in the spray state is referred to as “spray method”.

The spherical glass powder is obtained by silanizing the spherical glass powder by the spraying method. In other words, the spherical glass powder is characterized in that its surface is entirely covered with a silane compound.
Examples of the silane compound include those represented by the following formula.
R _4-n -Si- (OR ') _n
(Wherein R represents an organic group, R ′ represents a methyl group, an ethyl group or a propyl group, and n represents an integer selected from 1 to 3)

  Such silane compounds include vinyltriethoxysilane, vinyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidyloxypropyltrimethoxysilane, γ Silane coupling agents having an epoxy group such as glycidyloxypropylmethyldiethoxysilane, silane coupling agents having a mercapto group such as γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β (amino Examples include silane coupling agents having an amino group such as ethyl) γ-aminopropyltrimethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane.

  Conventionally used glass powder is composed of various shapes such as polygons and rectangles, and the average particle size is in a wide distribution range of 10 to 100 μm. The glass powder of the invention is spherical in shape, and its width is very small when the average particle size is in the range of 10 to 40 μm.

FIG. 2 is a graph showing the frequency of distribution of the average particle diameter of the spherical glass powder obtained by the above-described method for producing the spherical glass powder. The horizontal axis of this graph represents the particle size (μm) of the spherical glass powder, and the vertical axis represents the distribution frequency (%). The spherical E glass powder shows the highest distribution frequency when the particle size is 25 μm, and is distributed in a range of 10 to 40 μm on the normal distribution curve centering on the particle size of 25 μm. Is high.
FIG. 3 is a 1000 × electron micrograph of the spherical glass powder. From this photograph, it can be observed that the spherical glass powder has a spherical shape and a solid shape, and has various particle sizes.
From the graph showing the frequency of the distribution of the average particle size of the spherical E glass powder in FIG. 2 and the photograph in FIG. 3, the spherical glass powder in the thermoplastic resin has a perfect circular spherical shape, and has various sizes. Although the thing of a diameter exists, it is shown that the average particle diameter is 10-40 micrometers.

  By the way, when the glass powder is put into the molten thermoplastic resin and kneaded, if the particle size is less than 10 μm, the proportion of fine particles increases, and the glass powder increases the amount of heat from the resin as the specific surface area increases. Because of this, the melt viscosity rises due to a sudden drop in the resin temperature, and the resin temperature during kneading rises extremely due to shearing heat generation, making it difficult to adjust the determined blending ratio of both materials. Become. In addition, by adding glass powder to the thermoplastic resin, in general, improvement of the dimensional stability, mechanical strength (impact strength, bending strength, etc.), warpage, permeation barrier properties, etc. of the molded body can be achieved. When the particle size is less than 10 μm, the bending strength is particularly lowered, which is not preferable.

  When the particle size is larger than 40 μm, the proportion of large particles increases, and the increase in melt viscosity during kneading is small, but when cutting the glass-containing composition into pellets of a certain size, the wear of the cutting blade becomes severe. Therefore, it becomes difficult to continuously produce a large amount of the glass-containing composition, resulting in production problems. On the other hand, when the particle size is larger than 40 μm, the impact strength is particularly lowered, which is not preferable. Therefore, the average particle size is preferably in the range of 10 to 40 μm.

(Thermoplastic resin)
As the thermoplastic resin, polyethylene (PE), polypropylene (PP), or polyethylene terephthalate resin is used.
A pigment, titanium oxide, alumina, talc, mica, silica, magnesium carbonate, and metallic glitter can be blended in the thermoplastic resin for the purpose of coloring or gloss.

  While any one of PE, PP and PET resin pellets is in a molten state, a maximum of 70% by weight of spherical glass powder is blended and kneaded, so that the diameter is 3 mm from the nozzle die provided at the discharge port of the extruder. The glass-containing molding pellets in the form of pellets in which spherical glass powders are independently dispersed in the thermoplastic resin can be obtained by extruding into a rod shape, cooling with water, and cutting into a length of about 4 mm with a cutter. The length is not limited to this.

FIG. 4A is an electron micrograph of a glass-containing molding pellet (pellet) produced by the above-described method for producing a glass-containing molding pellet of the present invention. This electron micrograph is a photograph obtained by enlarging a pellet obtained by blending 50% by weight of spherical E glass powder with PP, and by cutting the cut part perpendicularly from the side by 50 times.
FIG. 4B is an electron micrograph taken with the cut portion magnified 100 times.
FIG. 4C is an electron micrograph taken by enlarging the side surface of the pellet 100 times.
From the photograph of the cut portion of the pellet in FIG. 4B, it is observed that the pellet is blended in the individual dispersed state in the PP without aggregation of individual spherical glass powders.
From this, the spherical glass powder is entirely coated with a silane compound by a spraying method, so that the pellets formed by kneading and extruding in an extruder are aggregated into a spherical glass powder. It turned out that it was mix | blended in the state disperse | distributed independently without.

And draw a circle from the middle point of the photograph of FIG. 4A to the position of the upper and lower ends, divide the circle equally into 16 and visually count the number of spherical glass powder blended in each of the 16 sections, The counted results are shown in Table 1.
When spherical glass powder was present on the 16 dividing line, the number of spherical glass powders was calculated as 1/2.

From the measurement results in Table 1, the number of spherical glass powders in each section is in the range of 140 ± 1, indicating that the spherical glass powder is uniformly dispersed in the pellets.
From the above, the glass-containing molding pellets of the present invention obtained by kneading the glass powder and the thermoplastic resin with an extruder and extrusion-molding the glass powder is solid in a spherical shape and has a thickness of 10 to 40 μm. The average particle size, the surface of which is entirely covered with a silane compound, is contained in a thermoplastic resin in a state of being independently and uniformly dispersed at a glass blending ratio in the range of 40 to 70% by weight. Turned out to be.
The photograph of FIG. 4C shows that the side surface of the pellet is covered with a spherical convex portion, and the spherical convex portion is coated with the spherical glass powder with a thermoplastic resin.

(Examples and comparative examples)

  In the following examples, three types of pellet-shaped thermoplastic resins (PE, PP, or PET) are targeted. Among the three types of pellet-shaped resins and spherical E glass powder silanized by the spraying method described above. Four types of resin having a weight blending ratio of 40:60, 50:50, 60:40, and 70:30 are used, and the MFR at the weight blending ratio is shown.

  The MFR is a measure of the fluidity of a polymer in a molten state, and measures the amount flowing out from a nozzle (orifice) having a specified size under a constant pressure and temperature with an extrusion plastometer. And an index expressed in units of g / 10 min. In general, the larger the MFR value, the better the fluidity and workability at the time of melting, and this MFR is used worldwide to represent the flow rate state of the resin.

  The MFR of the above three types of thermoplastic resins is HDPE (hereinafter referred to as “PE”) selected as an example is 0.25, PP is MFR of 10.0, and PET is MFR of 20.0. , MFR of 0.25, 10.0, 20.0 is selected. However, even if the same thermoplastic resin is used, the MFR varies depending on the molecular weight. Three types of thermoplastic resins were selected as the MFRs of the thermoplastic resins having different molecular weights within the range of MFR 0.25 to 20.0 described above.

  The comparative sphere used in Comparative Examples 1 and 2 is a spheroidized E glass fiber that has been silanized by an immersion method, and uses the same spherical glass powder as in the examples. Since the spherical glass powders of the examples are silanized by the spraying method, the spherical glass powders of Comparative Examples 1 and 2 are different from those of the silanizing treatment by the dipping method. No. 2 and No. 2 spherical glass powders are called comparative spheres.

  The immersion method of Comparative Examples 1 and 2 is a method in which a spherical glass powder is immersed in an aqueous solution containing 0.1% by weight of γ-glycidyloxypropylmethyldiethoxysilane for 30 minutes and then filtered. Dried at ℃. As a result of the treatment, a plurality of spherical glass powders come into contact with each other, and the silane compound is coated, filtered, and dried, so that agglomerated glass powder is present in the silanized glass powder.

  As a comparative example, the reason why the examples using glass powders containing various conventional shapes are not compared is that PE pellets and 40% by weight glass powder containing various conventional shapes are used in the first hopper. When trying to knead the mixture, the fluidity suddenly decreases, the frictional resistance against the screw becomes larger than the shearing force of the screw, the screw thread is likely to break, Since it cannot be molded, it was found that experimental data for clarifying the effect of introducing glass powder into the molten thermoplastic resin and the effect of glass powder not in an agglomerated state cannot be obtained compared to the examples. Therefore, a spheroidized E glass fiber was used as a comparative example. Thus, experimental data showing the effect of introducing glass powder into the molten thermoplastic resin and the effect of glass powder not in an agglomerated state could be obtained.

  In Comparative Example 1, one of the three types of resins and the comparative sphere were weighed separately and charged into the extruder. One resin pellet was charged into the first hopper, and the comparative sphere was charged into the second hopper. MFR experimental data showing the fluidity at the weight blending ratio of the comparative example sphere and one resin pellet by weight blending ratio of 20:80, 30:70, 40:60. Are shown in Tables 4, 6 and 8 below.

  In Comparative Example 2, one resin pellet and a comparative example sphere were blended in the first hopper and charged at the same time, and the weight ratio of the comparative example sphere and one resin pellet was 20:80, 30:70, 40:60. MFR experimental data showing the fluidity at the weight blending ratio are shown in Tables 4, 6 and 8 below.

  The conditions for obtaining the three types of molding compositions of Examples and Comparative Examples 1 and 2 described above are the glass particles, the method of silanization treatment, the type of resin, the glass blending ratio, and the first and second hoppers. Table 2 shows 6 items of materials (hereinafter, the conditions of these 6 items are referred to as “6 item conditions”). The “glass blending ratio” is defined as the weight percentage of the spherical glass powder in the thermoplastic resin. In some cases, “glass blending percentage by weight” is indicated by “glass blending percentage%”, but they are used in the same meaning.

By the way, when the glass-containing molding pellets of the examples were molded under the above-mentioned six-item conditions in order to examine what characteristics were compared with the comparative sphere molding compositions of Comparative Examples 1 and 2. The molding composition was melted at the same temperature as the melting temperature at which each resin was melted, and the MFR of the molding composition of each resin was measured. If the MFR of the molding composition is measured at the same temperature as the melting temperature at which each resin is melted, the fluidity when the glass powder is put into the molten region in the molding extruder and kneaded. The state of this can be expressed numerically, whereby the MFR characteristics of the glass-containing molding pellets of the examples are clarified by comparing with the MFR of the comparative sphere molding compositions of Comparative Examples 1 and 2. Is done.
The measurement results are shown in Examples 1 to 3 below.

Example 1
In Example 1, PE is used as the thermoplastic resin, and the weight ratio of the spherical E glass powder silanized by the spray method and PE is 40:60, 50:50, 60:40, 70:30. The thing of the kind standard was used.
HI-ZEX 5100B (trade name: Prime Polymer Product Co., Ltd.) was weighed as PE (high-density polyethylene) from the first hopper of the above-described extruder, and 60% by weight was charged and melted at 230 ° C. Inside, weighed the spherical E glass powder of the above example from the second hopper and put 40% by weight preheated to a temperature equal to or close to the melting temperature of 230 ° C., 230 ° C., screw rotation speed The first level molding composition of Example 1 was obtained by kneading at 200 times / minute, extruding into a 3 mm-diameter rod, water-cooling, cutting into a 4 mm length, and pellets. The preheating temperature is most preferably the same as the melting temperature of 230 ° C., and (230 ° C. ± 10% temperature) is preferred.

Similarly, HI-ZEX 5100B 50 wt%, spherical E glass powder 50 wt% second level molding composition, HI-ZEX 5100 B 40 wt%, spherical E glass powder 60 wt% third level molding. Composition, HI-ZEX 5100B 30% by weight, spherical E glass powder 70% by weight, a fourth level molding composition was obtained.
Next, Comparative Example 1-1 and Comparative Example 1-2 obtained a pellet having a length of 4 mm under the conditions shown in Table 2. The resin used is the same as that of Example 1.

Regarding the other two types of thermoplastic resins (PP, PET) described below, the above six item conditions are also described in the “resin” and “first hopper” items. Since the contents described in the item are the same, it is omitted to represent the six-item conditions in a table for each of the two types of thermoplastic resins.

Table 4 shows the results of measuring the MFR of the pellets at 230 ° C. for each glass blending rate.
In Table 4, the MFR of 100% thermoplastic resin of PE (HI-ZEX 5100B) in Example 1 is 0.25.

FIG. 5 is a graph showing the relationship between the glass blending ratio and MFR, which is created based on the glass blending ratio (% by weight) and MFR data shown in Table 4, as an approximate curve of a second order polynomial.
In this graph, □ indicates the MFR of Example 1, Δ indicates the MFR of Comparative Example 1-1, and x indicates the MFR of Comparative Example 1-2. And each curve of MFR of these Example 1, Comparative example 1-1, and Comparative example 1-2 is 0.25 which is MFR of thermoplastic resin 100% (henceforth "100% MFR"). On the other hand, it shows how each MFR tends to decrease when the blending ratio of the glass powder increases. Then, in order to show the glass blending ratio when the 100% MFR (0.25) of PE is a value of 1/2 (hereinafter referred to as “1/2 MFR”), the intersection with each curve. A vertical line is drawn from X to the X axis.

  In the graphs shown below, □ indicates an example, Δ indicates a comparative example 1, × indicates a comparative example 2, and each curve indicates an MFR of thermoplastic resin 100% (hereinafter, In contrast to “100% MFR”), it shows how each MFR tends to decrease when the blending ratio of the glass powder increases. Is omitted. At the same time, in order to show the glass blending ratio at 1/2 MFR, the description that a perpendicular line is drawn from the intersection with each curve toward the X axis is omitted.

Table 5 shows the glass blending ratios of Comparative Example 1-2, Comparative Example 1-1, and Example 1 at the time of the 1/2 MFR.

(Example 2)
In Example 2, PP is used as the thermoplastic resin, and the weight ratio of the spherical E glass powder silanized by the spray method and PP is 40:60, 50:50, 60:40, and 70:30. The thing of the kind standard was used.
The weight of Novatec PP MA3 (trade name: Nippon Polypro Co., Ltd. product) is weighed as PP from the first hopper of the above-mentioned extruder, and 60% by weight is put into a molten state at 220 ° C. Further, the spherical E glass powder of the above example was weighed and charged with 40% by weight preheated to a temperature equal to or close to the melting temperature of 220 ° C., and kneaded at 220 ° C. with a screw speed of 200 times / minute. Then, it was extruded into a rod shape having a diameter of 3 mm, cooled with water and cut into a length of 4 mm to obtain a pellet-like shape, and the first level molding composition of Example 2 was obtained. The preheating temperature is most preferably the same as the melting temperature 220 ° C., and (220 ° C. ± 10% temperature) is preferred.

Hereinafter, similarly, Novatec PP MA3 50 wt%, spherical E glass powder 50 wt% second level molding composition, Novatec PP MA3 40 wt%, spherical E glass powder 60 wt% third level molding. Composition, Novatec PP MA3 30% by weight, spherical E glass powder 70% by weight, a fourth level molding composition was obtained.
Next, Comparative Example 2-1 and Comparative Example 2-2 obtained pellets having a length of 4 mm under the conditions shown in Table 2. The resin used is the same as the resin of Example 2.

Table 6 shows the results of measuring the MFR of the PP pellets at 220 ° C. for each glass blending ratio.
In Table 6, the MFR of 100% thermoplastic resin of PP (Novatech PP MA3) in Example 2 is 10.0.

FIG. 6 is a graph showing the relationship between the glass blending ratio and MFR, which is created based on the glass blending ratio (% by weight) and MFR data shown in Table 6, as an approximate curve of a second order polynomial.
Table 7 shows glass blending ratios of Comparative Example 2-2, Comparative Example 2-1, and Example 2 at the time of 1/2 MFR.

Example 3
In Example 3, PET is used as the thermoplastic resin, and the weight ratio of the spherical E glass powder silanized by the spray method and the PET is 40:60, 50:50, 60:40, and 70:30. The thing of the kind standard was used.
Byron FN305 (trade name; product of Toyobo Co., Ltd.) was weighed as PET from the first hopper of the above-described extruder, and 60% by weight was put into a molten state at 250 ° C. The spherical E glass powder of the example was weighed and charged with 40% by weight preheated to a temperature equal to or close to the melting temperature of 250 ° C., and kneaded at 250 ° C. at a screw speed of 200 times / min. Extruded into a 3 mm diameter rod shape, water cooled and cut to 4 mm length to give a pellet shape, the first level molding composition of Example 3 was obtained. The preheating temperature is most preferably the same as the melting temperature 250 ° C., and (250 ° C. ± 10% temperature) is preferred.

Similarly, the second level molding composition of Byron FN305 50% by weight and spherical E glass powder 50% by weight, the third level molding composition of Byron FN305 40% by weight and spherical E glass powder 60% by weight. The fourth level molding composition of Byron FN305 30% by weight and spherical E glass powder 70% by weight was obtained.
Next, Comparative Example 3-1 and Comparative Example 3-2 obtained pellets having a length of 4 mm under the conditions shown in Table 2. The resin used is the same as that of Example 3.

Table 8 shows the results of measuring the MFR of the pellets at 250 ° C for each glass blending rate. In Table 8, the MFR of 100% thermoplastic resin of Byron FN305 of Example 3 is 20.0.

FIG. 7 is a graph showing the relationship between the glass blending ratio and MFR, which is created based on the glass blending ratio (wt%) and MFR data shown in Table 8, as an approximate curve of a second order polynomial.
Table 9 shows the glass blending ratios of Comparative Example 3-2, Comparative Example 3-1, and Example 3 at the time of 1/2 MFR.

  In the above-mentioned example, the example of the best mode in which the spherical glass powder charged into the extruder is preheated to a temperature equal to or close to the melting temperature is shown, but the present invention is limited to this example. For example, instead of preheating the spherical glass powder charged into the extruder to a temperature equal to or close to the melting temperature, the spherical glass powder may be charged without preheating to the second hopper. In that case, the melting temperature (heating, cooling) used for conventional pellet molding, such as increasing the melting temperature so that the melting temperature does not rapidly drop due to the introduction of a large amount of spherical glass powder, The glass-containing molding pellets obtained by kneading and extruding under the control of the screw speed and the like are also included in the glass-containing molding pellets of the present invention.

Next, MFR, which is a characteristic of the three types of embodiments, will be described.
Examples of compositions containing three types of spherical E glass powders and comparative examples of compositions containing comparative spheres, and the relationship between the glass blending ratio and MFR of these both in the graphs of FIGS. As shown in the graph, the graphs of the three examples show a parabola with the MFR at the top of the MFR of 100% thermoplastic resin as the glass blending ratio increases, and 100% While the value of 1/2 of the MFR is in the range of 50 to 60% by weight of the glass blending ratio, the graphs of the three types of Comparative Examples 1 and 2 show that the MFR is the thermoplastic resin 100 as the glass blending ratio increases. % Of the MFR of the thermoplastic resin of Comparative Example 1 and Comparative Example 2 is half the value of the MFR of Comparative Example 1 and Comparative Example 1 is a glass blending ratio of 30 to 30%. In the range of 40 wt%, in Comparative Example 2 Shows that in the range of glass load ratio of 20 to 30 wt%.

  Accordingly, in the three examples, the MFR shows a parabola with the MFR of the thermoplastic resin 100% at the top as the glass blending ratio increases, and in the range of 40-50 wt% glass blending ratio, 100% It is a value of 1/2 or more of MFR, and shows that the value changes from 1/2 of 100% MFR to a value of 1/2 or less in the range of 50 to 60% by weight of glass.

  Comparative Example 1 shows an almost straight line in which the MFR slopes downward with the MFR of the thermoplastic resin 100% as the apex as the glass blending ratio increases, and is 100% in the range of 30-40 wt% glass blending ratio. It shows that the MFR changes from a value of 1/2 or more to a value of 1/2 or less. In Comparative Example 2, the MFR is inclined downward with the MFR of 100% thermoplastic resin as the apex as the glass blending ratio increases. It shows a substantially straight line, and shows a change from a value of 1/2 or more to 100% MFR to a value of 1/2 or less in a range of 20 to 30% by weight of glass.

  The graphs of Examples 1 to 3 show that the lowering behavior of MFR with the increase in the glass blending ratio is more gradual than the graph of the comparative example, and this indicates that the blending amount of the spherical glass powder is temporarily in the manufacturing process. Even if it fluctuates, it turns out that the fluctuation | variation of MFR resulting from it is small. Therefore, these graphs show that it is advantageous in terms of quality control in the manufacturing process of glass-containing molding pellets.

Next, Table 10 shows the glass blending ratios of Comparative Example 2, Comparative Example 1 and Example at 1/2 MFR for each thermoplastic resin shown in Examples 1 to 3 for three types of thermoplastic resins. .
From the MFR of the comparative examples and examples shown in Table 10, the glass blending ratio of Comparative Example 2 at 1/2 MFR is in the range of 25-26 wt%, and the glass blending ratio of Comparative Example 1 at that time is 32- Since the glass blending ratio of the example at that time is in the range of 54 to 57% by weight, the difference between the maximum and the minimum is 1% in Comparative Example 2 and in Comparative Example 1 4% and 3% in the examples. Examples 1 to 3 contain a large amount of glass in about 2 times that of Comparative Example 2 and 1.6 times that of Comparative Example 1. Even then, it was found to be 1/2 MFR.
The above-mentioned 1/2 MFR of the thermoplastic resin is useful for grasping the MFR characteristics of the glass-containing molding pellets accompanying the increase in the glass blending ratio.

Table 11 shows five-point MFRs of 100% MFR thermoplastic resins of Examples 1 to 3, glass blending ratios of 40, 50, 60, and 70% by weight. FIG. 8 shows an approximate curve of a quadratic polynomial calculated based on the five-point data in Table 11, and is a graph showing the relationship between the glass blending ratio and MFR in the glass-containing molding pellets of Examples 1 to 3. . This graph shows a tendency that the MFR of each thermoplastic resin 100% gradually decreases as the glass blending ratio increases.
In the marks shown in FIG. 8, PE indicates a ◇ mark, PP indicates a □ mark, and PET indicates a △ mark.

  In Examples 1 to 3, it can be seen from the graph of FIG. 8 that the MFR that gradually decreases with an increase in the glass blending ratio shows values on a parabola, but the glass blending ratios of 40, 50, 60, and 70 wt% With each increase, the reduction rate of MFR as a quantitative value indicating how much the MFR is reduced with respect to the MFR of 100% thermoplastic resin is, for example, a glass having a glass blending ratio of 70% by weight. If the reduction rate of MFR of contained pellets is required, if the extruder continues to run for a long time, how much of the reduction rate of MFR can prevent troubles such as screw breakage? Know in advance.

Moreover, in order to solve the global warming problem and the problem of depletion of petroleum resources, it is more effective to add a large amount of spherical glass powder, but glass-containing molding pellets are blow molded, injection molded, Considering mass production of molded products molded by an extrusion molding method or the like, it is necessary to examine a glass blending ratio that can be easily molded by any molding method by obtaining a reduction ratio of MFR.
And if the mutual relationship between the value of the glass blending rate and the rate of decrease in MFR is known, the glass blending rate can be easily determined according to the MFR of the selected thermoplastic resin. For example, when molding a glass-containing molding pellet by selecting PE, the MFR of PE100% is a small value of 0.25, so the glass necessary for molding with the MFR reduction rate suppressed to 60% It would be convenient if the value of the blending ratio could be easily determined.

Therefore, first, a method for obtaining the MFR reduction ratio with an increase in the glass blending ratio relative to the thermoplastic resin will be described.
As described above, Table 10 shows the glass blending ratios of Comparative Example 2, Comparative Example 1, and Examples at 1/2 MFR for each thermoplastic resin shown in Examples 1 to 3 above. The 1/2 MFR of the plastic resin indicates a glass blending ratio in which the MFR of the glass-containing molding pellets becomes a half value of 100% of the thermoplastic resin due to an increase in the spherical glass to be blended with 100% of the thermoplastic resin. . For example, when PE is 57% by weight and PP is 54% by weight of glass, the value is 1/2 of 100% of the thermoplastic resin. From this, the value obtained by dividing the MFR of 40, 50, 60, and 70% by weight of the glass composition of Examples 1 to 3 shown in Table 12 below by the MFR of 100% of the thermoplastic resin, that is, an increase in the glass composition ratio. Means the reduction rate of MFR indicating how much the MFR of 100% thermoplastic resin is reduced.

Therefore, the value obtained by dividing the MFR of 40, 50, 60, and 70% by weight of the glass blending ratio of Examples 1 to 3 shown in Table 11 by the MFR of 100% of the thermoplastic resin is referred to as “melt flow rate reduction ratio” (hereinafter, It was defined as “MFR reduction ratio”) and the value was obtained. The obtained results are shown in Table 12. Table 10 shows the value of the glass blending ratio shown at 1/2 MFR, but Table 12 shows the value of the MFR reduction ratio shown when the glass blending ratio is 40, 50, 60, and 70% by weight. It should be noted that the MFR reduction ratio shows a different range for each glass blending ratio.

FIG. 9A shows approximate curves of second-order polynomials of MFR reduction ratios for the three types of Examples 1 to 3 calculated based on the five-point data in Table 12, so-called parabolas. It is the graph which showed the relationship between the MFR fall rate in the pellet for glass, and a glass compounding rate. PE is y = −1.31x ² −0.22x + 1.00, PP is y = −1.11x ² −0.24x + 1.00, and PET is y = −1.52x ² −0.03x + 1.00 These formulas represent parabolas. In the graph of FIG. 9A, the x-axis indicates the glass blending ratio (% by weight), and the y-axis indicates the MFR reduction rate. In the three types of Examples 1 to 3, the MFR at 100% has three types of unique values (0.25, 10.0, 20.0). However, as shown in FIG. 9A, the MFR reduction rate continues to decrease gradually as the glass blending rate increases, and the maximum and minimum values of the MFR reduction rate of each glass blending rate based on Table 12 When the glass blending ratio is 40% by weight, the maximum value is 0.75 and the minimum value is 0.70, the difference is 0.05, and the maximum value of the glass blending ratio of 50% by weight is 0.62. The minimum value is 0.56, the difference is 0.06, the maximum value of 60% by weight of glass is 0.48, the minimum value is 0.40, the difference is 0.08, and The maximum value of the glass blending ratio of 70% by weight is 0.28, the minimum value is 0.20, and the difference is 0.08. This indicates that the experimental data exists in a narrow range of 0.05 to 0.08 without dispersion of the three types of MFR reduction ratios shown for each glass blending ratio.
The three types of parabola shown in FIG. 9A are considered to gradually decrease with the same gradient as the glass composition ratio increases, considering the error that the experimental data has, and therefore, for each glass composition ratio shown in Table 12. The maximum value and the minimum value of the MFR reduction ratio are obtained, and the equation (1) obtained from the maximum value is y = −1.34x ² −0.08x + 1.00, and the equation (2) obtained from the minimum value is obtained. was y ⁼ -1.31x 2 -0.22x + 1.00.
The coefficients and constants of this equation are shown below as equations (1) and (2) obtained by rounding off the third decimal place.
y = −1.34x ² −0.08x + 1.00 (1)
y = −1.31x ² −0.22x + 1.00 (2)
Here, x indicates the required amount of the glass blending ratio (40 ≦ x ≦ 70), and y indicates the MFR reduction rate.
Table 13 is a table showing the maximum value and the minimum value of the MFR reduction ratio with respect to the glass blending ratio of 40%, 50%, 60%, and 70% by weight of Table 12 described above.

  FIG. 9B is a graph of an equation showing the relationship between the glass blending ratio and the MFR reduction rate. Since this formula shows the relationship between the glass blending rate and the MFR reduction rate, the flow characteristics of the glass-containing molding pellets can be grasped uniformly, and if the required MFR reduction rate is selected, the spherical shape to be blended in the resin If the glass blending ratio of the glass powder is predicted, or the glass blending ratio is selected, the rate of decrease in the melt flow rate of the glass-containing molding pellets can be predicted, and operations during molding of glass-containing molding pellets and glass-containing blow containers are possible. It is possible to improve the performance.

  Next, a glass-containing blow container formed by a conventional blow molding method using pellets containing 40% by weight or more of glass powder in PE, PP, and PET, which are versatile resins, has excellent physical properties. Reducing the incineration energy, which is one of the above, and also showing the relationship between the glass blending ratio of the blow container and the incineration energy, the incineration energy can be significantly reduced with the increase in glass powder, and the cost is low What can be manufactured will be described below. The conventional blow molding method is mainly applied to the production of containers for food, beverages, liquid detergents, toiletries, cosmetics, pharmaceuticals, etc., but is also used for molding automotive parts that are industrial products.

Various resins can be used to mold the thermoplastic resin by the blow molding method. As described above, the thermoplastic resins used in a large amount in the blow container include PE, PP and PET. The glass-containing blow container of the present invention is intended for these three types of resins.
And the glass-containing molding pellets used in the glass-containing blow container of the present invention are not limited to those molded by the manufacturing method in which spherical glass powder preheated in the second hopper is used, but as described above. In addition, when spherical glass powder is put into the second hopper without preheating, it is kneaded and extruded under the control of the melting temperature (heating, cooling), screw speed, etc., used in conventional pellet molding. The obtained glass-containing molding pellets contain spherical glass powder in a glass compounding ratio in the range of 40 to 70% by weight in the thermoplastic resin, and the melt flow rate reduction ratio is the above formula (1) and formula (2). It should be noted that this includes those in the range of

(Blow molding method)
A parison or preform melted and formed by an extruder, an injection device, etc. is sandwiched in a mold, a gas is blown inside, and the outer surface of the parison or preform is pressed against the inner surface of the mold by that pressure to form a hollow body. This is a molding method comprising a forming step. The blow molding method is a two-stage molding method in which a parison is first molded, and an extrusion blow molding machine and an injection blow molding machine are generally applied to the parison molding. In addition, a compression molding machine is also applicable. Thus, there are various types of blow molding methods.

  In the direct blow method using the extrusion blow molding machine (also referred to as “direct blow”), a parison is supplied into a mold by an extruder and a head, and blow molding is performed. A tube is formed by heating and melting a molding material. This is a molding method comprising a process of forming a blow container by extruding it into a shape, sandwiching it with a mold, and blowing high-pressure air into the inside, and in contrast to this, an injection using the injection blow molding machine (also referred to as “injection blow”). The blow method is a molding method that consists of the process of forming a preform and then directly blow-molding it with a single molding machine composed of an injection device and a blow mechanism. Form a bottomed parison with a smooth bottom with no joining marks with the device, then move it into a hollow die, Therefore, a blow molding mechanism blows air to form a hollow mold. The molding method includes a process in which a molding material is melted by heating and injected and filled in a previously closed mold, and then solidified or cured. The injection blow method includes a hot parison method and a cold parison method, and the hot parison method introduces a parison in a high temperature state immediately after injection molding into a split mold and immediately blows air into the parison, or After adjusting the temperature of the parison, air is blown into the parison and blow molded. In the cold parison method, the injection-molded parison is once cooled and solidified, and the parison is heated by heating means in a separate process, and then inside the split mold. And blow-molding by blowing air into the parison.

(Method for producing glass-containing blow container)
Various resins can be used to mold the thermoplastic resin by blow molding, and examples of the thermoplastic resin used in a large amount in the bottle include PE, PP, and PET.
The experimental data of the examples and comparative examples shown below are for three types of resins, PE, PP and PET. In the examples, four types of weight blending ratios of 40:60, 50:50, 60:40, and 70:30 of one of the three types of resins and the spherical E glass powder silanized by the spraying method described above are used. The incineration energy experimental data at the weight blending ratio is shown below.

  Examples of PE resin in Example 11, PP in Example 21, and PET resin in Example 31 will be described below. The glass-containing molding pellets of these resins are as described above. Therefore, description of the manufacturing method of the pellet is abbreviate | omitted. As a blow molding method, Example 11 was a direct blow method, Example 21 was a hot parison method, and Example 31 was a cold parison method to produce a blow container.

The blow container was created using three different blow molding methods in this way, using conventional blow molding machines using various types of existing blow molding machines, using pellets with a glass compounding ratio of 40 to 70% by weight. This is to verify whether a large quantity of blow containers can be produced industrially under the same conditions as the law.
In general, blow containers made of the same resin using different blow molding methods are known to have the same physical property characteristics. Producing a blow container prototype using different types of blow molding methods and measuring the total light transmittance, thermal conductivity, and Rockwell hardness, the results were the same. PE, PP and PET pellets A blow container was prepared using three different blow molding methods, and the total light transmittance was measured.

(Measurement specimen)
In Example 11, a 120 ml bottle having a thickness of 1.1 mm was prepared in Example 11, a 500 ml bottle having the same thickness in Example 21, and a 1000 ml bottle having the same thickness in Example 31. The physical properties were measured using a bottle having a width of 20 mm × 30 mm and a thickness of 1.1 mm cut from each bottle.
(Measurement of total light transmittance and haze)
Using a Shimadzu UV-visible spectrophotometer UV-3100B and integrating sphere ISR-3100, based on JISK7105, total light transmittance% (T.) and diffuse transmittance% (T ₁ ) at a measurement wavelength of 380 to 780 nm were measured. . And T measured. The haze% (H) was determined from T ₁ by the following formula. The haze means a value defined by JIS K 7105, and is obtained by the following formula.
H = T ₁ / T. × 100

(Example 11)
A glass-containing blow container for PE-containing glass-containing molding pellets (hereinafter referred to as “pellets”) was produced by the direct blow method as follows.
After pellets with a spherical glass powder and PE weight ratio of 40:60, 50:50, 60:40, and 70:30 were dried at 100 ° C. for 4 hours, the pellets were charged from the hopper of an extrusion blow molding machine. The direct blow method was performed under the conditions of a rear temperature of 215 ° C., a front temperature of 220 ° C., a screw speed of 100 times / minute, an injection pressure of 100 kg / cm ² , and a mold temperature of 70 ° C., and a cooling time of 18 In 120 seconds, a glass-containing blow container of 120 ml could be formed.

In addition, by using the above pellets having a spherical glass powder and PE weight ratio of 50:50, the rear temperature is 235 ° C., the front temperature is 242 ° C., and the screw rotation speed is 100 times / min. A parison was formed under an injection pressure of 100 kg / cm ² to form a 150 ml glass-containing blow container. The cooling time required at that time is 22 seconds. A 150 ml glass-containing blow container could be formed from pellets of PE 100% containing no spherical glass powder using an injection blow molding machine by the injection blow method. The glass-containing blow container can be produced without changing the control method that has been conventionally performed, and no trouble occurred during molding.
Furthermore, it turned out that the blow container of PE containing 40 to 70 weight% of glass compounding ratio is provided with the texture of the appearance of the frosted glass.

(Example 21)
A glass-containing blow container was produced from the PP pellets by the hot parison method as follows.
Pellets with a spherical glass powder and PP weight ratio of 40:60, 50:50, 60:40, 70:30 are dried at 100 ° C. for 4 hours, and the dried pellets are charged from the hopper of an injection blow molding machine. Then, melt at 240 ° C. and stir at 150 times / minute, make pressure (1); 80 kg, pressure (2); 25 kg, injection pressure; 6 seconds later, blowing was performed for 6 seconds, and a glass-containing blow container of 500 ml could be formed with a hot parison.
Moreover, it turned out that the blow container of PP containing 40 to 70 weight% of glass compounding ratio is provided with the texture of the appearance of the frosted glass.

(Example 31)
A glass-containing blow container was produced from the PET pellets by the cold parison method as follows.
Pellets with a spherical glass powder and PET weight ratio of 40:60, 50:50, 60:40, 70:30 are dried at 130 ° C. for 4 hours, and the dried pellets are charged from the hopper of an injection blow molding machine. Then, melt at 270 ° C. and stir at 150 times / min., Pressure (1); 80 kg, pressure (2); 25 kg, injection pressure is 10 kg, make a parison by 8 seconds injection, take out at room temperature I left the parison. The parison was transferred to a blow mechanism, heated and softened to 270 ° C., and blown for 8 seconds, whereby a 1000 ml glass-containing blow container could be formed by the cold parison method.
Moreover, it turned out that the blow container of PET containing 40 to 70 weight% of glass compounding ratio is provided with the texture of the earthenware appearance.

(Production of glass-containing blow containers)
By the way, since Example 11-31 did not generate | occur | produce a trouble when shape | molding a blow container using the pellet containing glass containing 40-70 weight% of glass containing ratio, the blow container of Examples 11-31 Is a conventional blow molding method such as the conventional direct blow method, hot parison method or cold parison method, and can produce a blow container with a glass blending ratio of 40 to 70% by weight, which causes trouble during molding. It can be said that there is no risk of occurrence.
Therefore, it can be said that the glass-containing blow container can be commercialized without any trouble as long as pellets having a glass blending ratio of 40 to 70% by weight are used in the three conventional blow molding methods.
Moreover, the blow container of PE or PP containing 40 to 70% by weight of the glass is provided with a texture of a polished glass-like appearance, and the blow container of PET containing 40 to 70% by weight of the glass is made of ceramic. It was found to have a texture of appearance.

(Comparative example)
In the comparative example, the above-mentioned three types of PE, PP and PET thermoplastic resin 100% blow containers (hereinafter referred to as “resin 100% blow containers”) were used.
PE, PP, and PET were molded by the method for producing glass-containing molding pellets shown in Examples 11 to 31 above, and the resin 100 was manufactured in the same manner as the method for producing the glass-containing blow containers in Examples 11 to 31 described above. % Blow container was molded to obtain three types of Comparative Examples 1-3.
As the physical properties of the glass-containing blow containers of Examples 11 to 31 and the resin 100% blow containers of Comparative Examples 1 to 3, the total light transmittance was measured as follows. And the test piece of the measurement cut | disconnected the thing whose width is 20 mm x 30 mm, and the thickness is 1.1 mm from the glass containing blow container whose comparative example 1 is 120m1, comparative example 2 is 150m1, and comparative example 3 is 1000m1. The total light transmittance and the diffuse transmittance were measured using a sample.

As the physical properties of the blow containers of Comparative Examples 1 to 3 (100% resin blow container) and Examples 11 to 31 (PE, PP and PET), the measurement results of the total light transmittance are shown in Tables 14, 20 and 20 below. 30. In these tables, the glass blending ratios 0, 40, 50, 60 and 70% by weight are arranged in the horizontal column, and PE, PP and PET of Examples 11 to 31 are arranged in the vertical column. The transmittance measurement results are shown.
The following experimental data of total light transmittance and diffuse transmittance were obtained by acquiring four data as the number of experimental data in order to reduce the error, and the four data were totaled and divided by four. Average values are shown.

(Total light transmittance, diffuse transmittance and haze)
Next, from the total light transmittance and diffuse transmittance of Comparative Example 1 of PE having a glass blending rate of 0% by weight, Example 11 having a glass blending rate of 40, 50, 60 and 70% by weight of PE and the measurement results thereof. The haze obtained by the calculation is as shown in Table 16.
As another comparative example, a blow container containing 50 or 60% by weight of titanium oxide in PE was prepared, and the total light transmittance and diffuse transmittance were measured to measure the total light transmittance, diffuse transmittance and The haze is shown in Table 16. Titanium oxide is known as a light-shielding pigment, and it is generally carried out to contain about 5% by weight in a thermoplastic resin in order to prevent light transmission. Here, as a comparative example for comparison with the example, a blow container containing 50 or 60% by weight of titanium oxide was prepared as a test.

Table 17 shows the total light transmittance, diffuse transmittance and haze of Comparative Example 2 in which the glass blending ratio is 0% by weight and Example 21 in which the PP glass blending ratio is 40, 50, 60 and 70% by weight. It is.

Table 18 shows the total light transmittance, diffuse transmittance, and haze of Comparative Example 2 in which the glass blending ratio is 0% by weight and Example 21 in which the PET glass blending ratio is 40, 50, 60, and 70% by weight. It is.

The graphs of Examples 11 to 31 represented by the approximate expression of the straight line in FIG. 10 show that the intrinsic total light transmittance of the resin 100% blow container is large and decreases without crossing each straight line in the order of PE, PP, and PET. Therefore, the graphs of the straight lines of Examples 11 to 31 show that the values of the intrinsic total light transmittance values are 68.1 for PE, 73.6 for PP, and 89.4 for PET. In order to examine whether the slope of the straight line is affected, a glass-containing blow container having a molded glass composition ratio of 40 to 70% by weight is compared with the resin 100% blow container in the above-mentioned intrinsic total light beam. In order to make it easier to understand how much the transmittance increases, the total light transmittance of the glass-containing blow containers of Examples 11 to 31 is divided by the specific total light transmittance of the 100% resin blow container. The value was obtained. Table 19 shows the values obtained by the calculation.

Here, a value obtained by dividing the total light transmittance of the glass-containing blow containers of Examples 11 to 31 by the total light transmittance of the resin 100% blow container is defined as a “total light transmittance improvement index”. Since the glass-containing blow containers of Examples 11 to 31 become opaque as the glass blending rate increases and the appearance is polished and changed to a glass-like tone, the total light transmittance is improved. Used in meaning.
FIG. 11A is a graph showing the relationship between the glass blending ratio of the glass-containing blow containers of Examples 11 to 31 and the total light transmittance improvement index.
It was obtained by plotting the glass blending ratio (% by weight) of the glass-containing blow containers of Comparative Examples 1 to 3 and Examples 11 to 31 shown in Table 19 on the x-axis and the total light transmittance improvement index on the y-axis. When an approximate expression was obtained based on 5 points, an approximate expression of a straight line was obtained, and the approximate expression of the straight line was that the index for improving the total light transmittance of the glass-containing blow containers of Examples 11 to 31 was that of a resin 100% blow container. In contrast to the total light transmittance improvement index, the total light transmittance improvement index gradually decreases along this straight line as the glass blending ratio increases, and the expression of PE in Example 11 is y = −0. 0087x + 0.9964, the PP equation of Example 21 is y = −0.0086x + 0.9945, and the PET equation of Example 31 is y = −0.0086x + 0.996, so Examples 11-31 The formula of the total light transmittance improvement index Tendency to decrease indicates that it is the same.

Therefore, it is considered that the approximation formulas of these straight lines gradually decrease with the same gradient as the glass blending ratio increases, considering the error of the experimental data. The average value was obtained by adding the values of the total light transmittance improvement index, and the formula obtained from the obtained average value of 5 points was y = −0.0087x + 0.9975. The coefficient and constant of this formula are shown below as formula (4) obtained by rounding off the fourth decimal place.
y = −0.009x + 0.998 (4)
Here, x is a necessary amount of the glass blending ratio (40 ≦ x ≦ 70), and y is a total light transmittance improvement index.
FIG. 11B is a graph showing the relationship between the glass blending ratio of the glass-containing blow containers of Examples 11 to 31 and the average value of the total light transmittance improvement index, which is expressed by equation (4) (hereinafter, “average value equation (4)”. "). This average value formula (4) indicates that the glass-containing blow container is composed of glass regardless of PE, PP and PET resins, and regardless of the blow molding method of direct blow method, hot parison method or cold parison method. It is shown that the total light transmittance improvement index is gradually decreasing as the rate increases. In addition, X mark has shown PE containing 50 or 60 weight% titanium oxide.

Since the blow containers of Comparative Examples 1 to 3 have a total light transmittance improvement index of 1, the average value formula (4) indicates that the glass-containing blow container is compared with the resin 100% blow container as the glass blending ratio increases. Thus, it can be understood at what rate the total light transmittance gradually decreases. In other words, the graph showing the total light transmittance improvement index of FIG. 11A shows the total light transmittance of the glass-containing blow container if the glass blending ratio of the glass-containing blow container is known as compared to the resin 100% blow container. It shows how much it can be reduced as compared with a 100% resin blow container, and the rate at which the total light transmittance can be reduced can be easily determined. On the contrary, when the total light transmittance required for the product to be manufactured is determined, the graph shows the necessary glass blending ratio of the glass-containing molding pellets from the determined total light transmittance. Therefore, the required amount of the glass blending ratio can be easily determined.
When the calculation is performed by substituting the minimum value 40 and the maximum value 70% by weight of x into the average value x in the formula (4), the total light transmittance improvement index becomes 0.1 as the glass content increases. It can be seen that the improvement is gradually reduced from 64 to 0.37.

And, the value of the total light transmittance improvement index in Table 19 is the total light transmittance improvement obtained by substituting the glass blending ratio for x in the above equation (4) because of the error of the experimental data. Although a value different from the index is shown, it was calculated how much the error range of this experimental data was every 40, 50, 60 and 70% by weight of the glass blending ratio. The error is -1.5% at a glass compounding ratio of 40% by weight, the error is ± 1.8% at 50% by weight, the error is 0% at 60% by weight, and the error is + 2.5% at 70% by weight. From this, it was found that the index for improving the total light transmittance of the glass-containing blow container obtained by the experiment was in the range of +2.5 to -1.8% error.
In other words, it is shown that the value indicated by the total light transmittance improvement index is gradually reduced and improved along with the above average value expression (4) as the glass blending ratio increases. Therefore, the term “gradually decreasing along equation (4) of the average value” is defined and used as a value including an error. Therefore, when the term is used below, it means a value including an error. Please note that.

  Furthermore, the total light transmittance improvement index of glass blending ratio 50 or 60 wt% PE, PP and PET shown in FIG. 11B and Table 19 is 0.22 or 0.21 for comparative examples containing 50 or 60 wt% titanium oxide. On the other hand, since the value is 2 to 3 times, the total light transmittance improvement index of Examples 11 to 13 is much larger than that of the comparative example. . This indicates that about 80% of the linear light is blocked in the comparative example, whereas about 60% of the linear light is blocked in the example.

FIG. 12 is a graph showing the relationship between the glass blending ratio and haze.
The graphs are drawn with approximate equations of curves by plotting the glass blending ratios of PE, PP, and PET shown in Tables 16 to 18 on the x-axis and haze on the y-axis.
As described above, the mark ◇ is PE, the triangle mark is PET, and the square mark is PP. The approximate expression of the curve is that PE is y = −0.0072x ² + 0.7498x + 76.686, and PP is y = −0. 0058x ² + 0.7763x + 72.232, and PET is y = −0.0179x ² + 2.635x + 0.7399. FIG. 12 shows that haze increases with an increase in the glass blending ratio, and that 90 or more when the glass blending ratio is 50 wt% or more.
On the other hand, the glass-containing blow container having a glass compounding ratio of 50 or 60% by weight PE has a haze of 96.8 or 91.0, whereas the comparative example of titanium oxide 50 or 60% by weight PE has a haze of 80. .9 or 86.4, the glass-containing blow container of Examples 11 to 31 having a glass compounding ratio of 50 to 70% by weight shows that the haze is larger than that of the comparative example containing titanium oxide.

  From the graph shown in FIG. 12, the glass-containing blow containers of PE and PP change on the approximate expression of the curve in which the haze approximates as the glass content increases, whereas the glass-containing blow container of PET It can be seen that the blow container changes on the approximate expression of the curve indicating a lower haze value than the approximate expression of the PE and PP curves.

As described above, the haze% (H) is a value obtained by dividing the diffuse transmittance% (T ₁ ) by the measurement wavelength of 380 to 780 nm by the total light transmittance% (T.). The graph which shows the relationship between a glass compounding rate, a total light transmittance, and a diffuse transmittance is shown to FIG.
FIG. 13A is a graph showing the relationship between the glass blending rate of PE, the total light transmittance, and the diffuse transmittance. X represents the total light transmittance of the comparative example (PE blow container containing 50 or 60 wt% titanium oxide), and * represents the diffuse transmittance of the comparative example. FIG. 13B is a graph showing the relationship between PP glass blending rate, total light transmittance and diffuse transmittance, and FIG. 13C is a graph showing the relationship between PET glass blending rate, total light transmittance and diffuse transmittance. is there.
From these graphs, it can be seen that when the glass blending ratio is 50% by weight or more, the total light transmittance and the diffuse transmittance are almost the same as the glass blending ratio is increased. Examples 1 and 2 have a haze of 90% or more in the range of 40 to 70% by weight of glass, and Example 31 has a haze of 90% or more in the range of 50 to 70% by weight of glass. It shows that it becomes.

By the way, according to Patent Document 4, the multilayer blow-molded product has a haze of 80 to 95% and a total light transmittance of 60 to 90% because the contents and the inner solution can be seen with an opaque feeling like a frosted glass container. If so, it is described that it is more preferable.
However, although the haze of Examples 11 and 21 is 90% or more, the total light transmittance is different in the range of 45 to 27%. Therefore, in order to verify whether or not the contents liquid can be seen, bottles of 60, 70% by weight glass-containing blow containers with PE, PP, and PET, and bottles of blow containers, containing 50 and 60% by weight titanium oxide, are used. A liquid was injected into the liquid, and the appearance of whether or not the liquid level could be identified was observed. The bottles of the blow containers containing 50 and 60 wt% titanium cannot be identified in the liquid level, but the glass-containing blow containers have been found to be able to identify the liquid level of the bottle.
In addition, since the index for improving the total light transmittance of the glass-containing blow container when the glass blending ratio is 70% by weight is 0.37 based on the average value formula (4), this means that the total light transmittance is If the rate improvement index is 0.37 or more, it means that the liquid level in the bottle can be identified.

(Appearance of glass-containing blow container)
By the way, the blown container of the thermoplastic resin is required to have a polished glass-like surface texture depending on the intended use. For example, although the production amount of PET bottles tends to increase every year, the haze of PET bottles is as small as 1.2% and easily transmits light, so that a polished glass-like surface texture is required of PET. Therefore, a method of blending and extruding by mixing inorganic fine powders such as calcium carbonate and mycal into PET has been performed, but in that case, the decrease in total light transmittance and transparency are impaired, which is disadvantageous. . However, PET bottles, which are blow containers containing 40 to 70% by weight of glass, have a ceramic-like appearance, and PE or PP bottles have a polished-glass appearance. As described above. And as the glass blending ratio increases, the texture of the appearance increases, and a feeling of weight and luxury are felt.
As described above, since the total light transmittance improvement index is 0.37 or more, the glass-containing blow container of the present invention can identify the liquid level in the bottle, and the PE or PP bottle has a polished glass-like appearance. The PET bottle has a ceramic-like appearance, and as the blending ratio of the glass increases, the appearance increases, giving it a sense of weight and luxury. ing. And the food container and cosmetics container provided with these characteristics are excellent in convenience because the position of the liquid surface storing the liquid is known.

  The glass-containing blow container of the present invention may have various shapes depending on the application, and is used for the shape of bottles, tubes, cups, trays, and the like. As specific applications, the bottle is a beverage container, a cosmetic container, A shampoo container, a rinse container, and a body soap container, the tube is a cosmetic container and a pharmaceutical container, the cup is a food container, and the tray is used as a lunch box and a fresh food container.

Claims (9)

A glass-containing blow container formed by a blow molding method using glass-containing molding pellets containing glass powder in a thermoplastic resin,
The solid spherical glass powder, which is the glass powder, is incorporated into a kind of resin selected from the group consisting of polyethylene resin, polypropylene resin and polyethylene terephthalate resin, in which the glass-containing molding pellets are the thermoplastic resin. It is contained in a range of ˜70% by weight, and the total light transmittance improvement index of the glass-containing blow container is gradually reduced according to the following formula as the glass content increases, and is improved. A glass-containing blow container.
y = −0.009x + 0.998
(X: glass blending ratio, y: total light transmittance improvement index)   2. The glass-containing blow container according to claim 1, wherein the total light transmittance improvement index is gradually reduced from 0.64 to 0.37 as the glass content increases.   The glass-containing blow container of the polyethylene resin or polypropylene resin has a haze value of 90% or more.   The glass-containing blow container according to claim 3, wherein the appearance of the glass-containing blow container has a polished glass-like texture.   The glass-containing blow container of the polyethylene terephthalate resin contains the glass content in the range of 40 to 70% by weight, and the total light transmittance improvement index increases from 0.55 to 0 as the glass content increases. The glass-containing blow container according to claim 2, wherein the glass-containing blow container is improved by gradually decreasing to 37, and the haze exhibits a value of 90% or more.   The glass-containing blow container according to claim 5, wherein an appearance of the glass-containing blow container has a ceramic-like texture.   The glass-containing blow container according to claim 3 or 5, wherein the liquid level of the glass-containing blow container can be identified.   The glass-containing blow container according to claim 3 or 5, wherein the glass-containing blow container has a shape of a bottle, a tube, a cup and / or a tray.   The glass-containing blow container is a beverage container, a cosmetic container, a shampoo container, a rinse container, a body soap container, the tube is a cosmetic container, a pharmaceutical container, the cup is a food container, the tray is a lunch box, a fresh food container It is a food container, The glass containing blow container of Claim 3 or 5 characterized by the above-mentioned.