JP5020997B2 - Polyolefin molded body, method for reducing carbon dioxide generation during incineration of polyolefin molded body, and masterbatch - Google Patents

Description

  The present invention relates to a polyolefin molded body, a method for reducing the amount of carbon dioxide generated during incineration of a polyolefin molded body, and a masterbatch added to a molding material during molding of a polyolefin molded body.

  In recent years, plastics such as polyolefins have been used in various industrial fields such as containers, packaging, building materials, and electronic parts after being formed into films, plates, pipes, fibers, etc., depending on the intended use. Is increasing further. Along with this, plastic waste is also increasing. Therefore, when plastics after use are disposed of by incineration, which is one of the general waste disposal methods, the generation of carbon dioxide is regarded as a problem due to the increased awareness of environmental conservation. It has become. However, a practical technique for reducing the amount of carbon dioxide generated during the incineration of a polyolefin molded body has not yet been proposed.

  Therefore, in order to reduce the amount of carbon dioxide generated at the time of incineration of a polyolefin molded body, the present inventor replaces a part of the polyolefin constituting the molded body with a powder of an inorganic compound that does not generate carbon dioxide by heating. Recalled independently. Although not intended to reduce the amount of carbon dioxide generated during incineration, there has been a molded body containing an inorganic compound. For example, Patent Document 1 describes the inclusion of barium sulfate as a pigment in order to improve the glossiness of a polyester film. Further, Patent Document 2 describes that talc powder is added to a thermoplastic resin in order to increase the toughness of the plate-shaped molded body. In this case, the affinity between the talc powder and the thermoplastic resin is described. In order to enhance the properties, the treatment with a coupling agent such as a titanate coupling agent or an aluminum coupling agent is described. Such a molded product is not intended to reduce the amount of carbon dioxide generated during incineration, but as a result, compared to a molded product of the same weight that does not contain inorganic compounds, the generation of carbon dioxide during incineration results. The amount is thought to be reduced.

JP 2001-279074 A JP 2006-111822 A

  When an inorganic compound is contained for the purpose of reducing the amount of carbon dioxide generated during incineration, it is desirable to increase the content of the inorganic compound as much as possible in order to enhance the reduction effect. However, when the powder of the inorganic compound is directly contained in the molded body as in Patent Document 1, there is a problem that the strength of the molded body decreases as the content increases. In particular, the problem is likely to be manifested in a thin molded bag-shaped molded article widely used as a shopping bag or a garbage bag, or a film-shaped molded article widely used as a packaging material. Moreover, even if it is a case where the powder of an inorganic compound is processed with a coupling agent and then contained in a molded product as in Patent Document 2, the affinity with the thermoplastic resin is increased and the dispersibility is improved. However, it is still impossible to prevent a decrease in strength of the molded body. Therefore, the reduction of carbon dioxide generation during incineration and the securing of the strength of the molded body are in a trade-off relationship with each other, ensuring the strength of the molded body and reducing the amount of carbon dioxide generated during incineration. It was difficult to increase.

  Accordingly, the problem to be solved by the present invention is to increase the effect of reducing the amount of carbon dioxide generated during incineration of the polyolefin molded product while ensuring the strength of the polyolefin molded product.

  In the present invention, an inorganic compound powder coated with a surface modifier is contained in a polyolefin molded body. The inorganic compound is an inorganic compound that does not generate carbon dioxide by heating. For example, at least one selected from the group consisting of talc, zeolite, metal hydroxide, magnesium sulfate, or barium sulfate can be used. The inorganic compound powder is coated with a first surface modifier that coats the inorganic compound powder and a second surface modifier that coats the first surface modifier and is contained in the polyolefin molded body. ing. The second surface modifier is at least one selected from the group consisting of maleic anhydride-modified polyolefin, a copolymer of maleic anhydride and polyolefin, and a maleic anhydride-modified olefin elastomer, and the first surface The modifier is a coupling agent having an affinity for the inorganic compound powder and the second surface modifier.

  The inorganic compound powder coated with the surface modifier is preferably prepared as a masterbatch containing the inorganic compound powder coated with the surface modifier and the binder resin, and used as a molding material during molding of the polyolefin molded body. Added.

  According to the present invention, an inorganic compound that does not generate carbon dioxide by heating is contained in the polyolefin molded body, and the polyolefin content in the molded body is relatively reduced, thereby reducing the amount of carbon dioxide generated during incineration of the molded body. Can be reduced. In addition, the inorganic compound powder contained in the molded body is coated with the second surface modifier via the first surface modifier, thereby providing the following effects. That is, since the first surface modifier has affinity for the inorganic compound powder and the second surface modifier, the second surface modifier can be more firmly bound to the inorganic compound. The long molecular chain derived from the polyolefin in the second surface modifier is entangled with the polyolefin constituting the molded body and strongly bonded. The strength of the bag-shaped molded product and the film-shaped molded product in a form in which the strength is remarkably lowered by including the powder of the inorganic compound due to the action of the first modifier and the second modifier. It becomes possible to raise content of an inorganic compound, suppressing a fall. As a result, the effect of reducing the amount of carbon dioxide generated during incineration can be enhanced while ensuring the strength of the compact.

  In the present invention, a polyolefin molded body (hereinafter, sometimes abbreviated as a molded body) includes polyolefins such as polyethylene and polypropylene as main constituent materials for forming the molded body. Although the shape is not limited, For example, it shape | molds in various shapes, such as a film form, a bag form, a sheet form, plate shape. For example, it can be suitably used for a file in which a piece of paper such as a document is sandwiched between two sheets. Of course, it also becomes a molded product having a complicated shape. Preferably, it is a film or bag shape. This is because the strength can be ensured even in the case of a thin molded body such as a film or bag, which has been particularly difficult to secure in the past. Therefore, for example, it can be suitably used for shopping bags (shopping bags) and garbage bags. In the present invention, the polyolefin molded body contains an inorganic compound that does not generate carbon dioxide by heating. Thereby, the content of polyolefin that produces carbon dioxide during incineration can be relatively reduced, and the amount of carbon dioxide generated during incineration of the molded body can be reduced by that amount.

  Examples of the inorganic compound that does not generate carbon dioxide by heating include metal hydroxides such as talc, zeolite and magnesium hydroxide, magnesium sulfate, and barium sulfate. The inorganic compound is contained in the molded body in a powder state. The inorganic compound powder is preliminarily coated with a surface modifier described later and molded together with the molding material when the molded body is molded, so that it is uniformly dispersed in the molded body and contained in the molded body. Therefore, barium sulfate is particularly suitable as the inorganic compound of the present invention in consideration of the processability of pulverization, ease of surface modification, convenience of obtaining raw materials, and the like.

  The particle diameter of the inorganic compound powder is preferably as small as possible in order to make it difficult to impair physical properties such as strength of the molded body. For example, the particle diameter is preferably 12 μm or less. More preferably, the particle diameter is 5 μm or less. However, when the particle size of the inorganic compound powder is smaller than 1 μm, the dispersibility is deteriorated. As a result, there is a possibility that problems such as a decrease in physical properties such as the strength of the molded body and an appearance defect may occur. Therefore, most desirably, an inorganic compound powder having a particle size of 1 to 3 μm can be used. The particle diameter of the inorganic compound powder can be measured with a laser particle diameter measuring instrument, and the major axis of the measured particle can be used as the particle diameter.

  As the surface modifier for coating the inorganic compound powder, a first surface modifier for directly coating the inorganic compound powder and a second surface modifier for coating the first surface modifier are used. First, the second surface modifier will be described.

  The second surface modifier is at least one selected from the group consisting of a maleic anhydride-modified polyolefin, a copolymer of maleic anhydride and polyolefin, and a maleic anhydride-modified olefin elastomer. Specific examples of the maleic anhydride-modified polyolefin include maleic anhydride-modified polyethylene and maleic anhydride-modified polypropylene. Specific examples of the copolymer of maleic anhydride and polyolefin include a copolymer of maleic anhydride and polyethylene, a copolymer of maleic anhydride and polypropylene, and the like. For example, DuPont FUSABOND E EC-603D, which is a copolymer of maleic anhydride and polyethylene, can be used effectively. The maleic anhydride-modified olefin elastomer can be obtained by bonding maleic anhydride to a polyolefin elastomer by graft polymerization. These second surface modifiers have a relatively long molecular chain derived from polyolefin and a functional group derived from maleic anhydride.

  As will be described later, the inorganic compound coated with the first surface modifier has a melt index (MI) of 5 to 30 g / 10 min (190 ° C., 2.16 kg). It is preferable because the powder can be efficiently coated. In addition, although the mechanism of action is not necessarily clear, in the second surface modifier, if a large number of functional groups derived from maleic anhydride are introduced into the polyolefin, the second surface modifier is in phase with the first surface modifier. This is preferable because of increased solubility.

  The first surface modifier is a coupling agent having affinity for both the inorganic compound and the second surface modifier. As such a first surface modifier, for example, a titanate coupling agent or an aluminum coupling agent can be used. When the first surface modifier is chemically or physically bonded to the surface of the inorganic compound powder, the affinity with the second surface modifier can be increased. In addition, the inorganic compound powder becomes hydrophobic and the inorganic compound powder is less susceptible to moisture.

  A conventionally well-known thing can be used as said titanate coupling agent. For example, isopropyl triisostearoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, tetraoctyl bis (ditridecyl phosphite) titanate, bis (dioctyl pyrophosphate) oxyacetate titanate and the like can be mentioned. A conventionally well-known thing can be used as said aluminum type coupling agent. For example, aluminum isopropylate, aluminum ethylate, aluminum tris (ethyl acetoacetate), ethyl acetoacetate aluminum diisopropylate and the like can be mentioned.

The ratio of the first surface modifier to the inorganic compound may be a ratio sufficient to cover the entire surface of the inorganic compound powder. Accordingly, the proportion of the first surface modifier can be appropriately set depending on the surface area of the inorganic compound powder. In general, the proportion of the first surface modifier relative to 100 parts by weight of the inorganic compound is 1 part by weight or more and 40 parts by weight. Part or less, preferably 1 part by weight or more and 10 parts by weight or less, more preferably 1 part by weight or more and 5 parts by weight or less.

  The ratio of the second surface modifier to the inorganic compound may be a ratio sufficient to cover the entire surface of the inorganic compound powder coated with the first surface modifier. The ratio of the second surface modifier can be appropriately set depending on the surface area of the inorganic compound powder coated with the first surface modifier, but generally, the ratio of the second surface modifier to 100 parts by weight of the inorganic compound is not limited. The ratio is 2 to 40 parts by weight, preferably 2 to 10 parts by weight, more preferably 2 to 5 parts by weight.

  The inorganic compound powder is first subjected to surface modification through a first step coated with a first surface modifier and a second step coated with a second surface modifier. First, in a 1st process, an inorganic compound powder is coat | covered with a 1st surface modifier by mixing an inorganic compound powder and a 1st surface modifier while heating. The heating temperature at this time is preferably 120 ° C. or higher and 135 ° C. or lower. A temperature lower than 120 ° C. is not preferable because the reaction efficiency is low. If it is 135 ° C. or higher, the first surface modifier may be altered, which is not preferable. Next, in the second step, the inorganic compound powder coated with the first surface modifier obtained in the first step and the second surface modifier are more than the heating temperature in the first step. The outside of the first surface modifier is coated with the second surface modifier by mixing while heating at a high temperature. The heating temperature at this time is preferably 150 ° C. or higher and 160 ° C. or lower. In such a temperature range, the second surface modifier melts and reacts. If the temperature exceeds 160 ° C., the second surface modifier is likely to be decomposed, which causes discoloration and a decrease in reaction efficiency, which is not preferable. The coating mechanism by the second surface modifier is a simple physical coating by the melted second surface modifier, and in addition, an interaction between the functional group derived from maleic anhydride and the first surface modifier occurs. It is presumed that

  The surface-modified inorganic compound powder is uniformly mixed with the molding material and contained in the molded body when the molded body is molded. The surface-modified inorganic compound powder has a relatively long molecular chain entangled with the polyolefin and can suppress a decrease in strength of the molded body. It can be included. From the viewpoint of increasing the effect of reducing the amount of carbon dioxide generated when the molded body is incinerated, it is preferable to increase the content of the inorganic compound in the molded body as much as possible. Therefore, the content of the inorganic compound in the molded body is preferably 10% by weight or more. If the content of the inorganic compound in the molded body is less than 10% by weight, the effect of reducing the amount of carbon dioxide generated when the molded body is incinerated is small, which is not preferable. However, if the content of the inorganic compound exceeds 35% by weight, the moldability decreases. In particular, when molding into a bag shape, the decrease in moldability is remarkable. Therefore, the content of the inorganic compound is preferably 35% by weight or less. In order to secure the effect of reducing the amount of carbon dioxide generated at the time of incineration of the molded body as high as possible while ensuring the physical properties such as moldability and strength of the molded body, the content of the inorganic compound in the molded body is 20 It is more preferable to set it to -30 wt%.

  In adding the surface-modified inorganic compound powder to a molding material such as polyolefin, if the molding material is a powder, it may be added as it is, but if added as a master batch molded into an appropriate shape by a binder resin, Regardless of the form of the molding material, it is preferable because it can be uniformly added and is easy to handle. The master batch can be manufactured through the following first to fourth steps.

[First step]
First, in the first step, the surface of the inorganic compound powder is coated with the first surface modifier by mixing the inorganic compound powder and the first surface modifier while heating. The heating temperature at this time is preferably 120 ° C. or higher and 135 ° C. or lower. The mixing time can be, for example, about 10 minutes.

[Second step]
Next, the inorganic compound powder coated with the first surface modifier obtained in the first step and the second surface modifier are mixed while heating. The heating temperature at this time is preferably 150 ° C. or higher and 160 ° C. or lower. The mixing time can be, for example, about 5 minutes. Thereby, the powder of the inorganic compound coat | covered with the 1st surface modification material and the 2nd surface modification material can be obtained.

Various agitators having a heating function can be used for mixing in the first step and the second step. For example, a jacketed Nauter mixer, ribbon mixer, Henschel mixer, super mixer, etc. can be used and mixed while heating by passing heated oil through the jacket.

[Third step]
Next, in the third step, first, the inorganic compound powder obtained in the second step is cooled to 40 ° C. or lower. Here, the cooling may be active cooling such as flowing cold water through the jacket of the stirrer, or may be allowed to cool. Next, a binder resin and various additives (such as a lubricant, a heat stabilizer, and an antioxidant) are mixed as necessary. Various agitators can be used for mixing.

[Fourth step]
Next, in the fourth step, the mixture obtained in the third step is heated to 90 ° C. or higher and 180 ° C. or lower and formed into a predetermined shape such as a dice shape, a cylindrical shape, a spherical shape, a flat spherical shape, or the like, and a master batch. Get. In the fourth step, various extruders capable of being heat-kneaded can be used. In particular, it is preferable to use a twin screw extruder because a master batch having a good appearance in which inorganic compound powder is uniformly dispersed can be obtained. If it is a twin screw extrusion machine provided with a vacuum function, the volatile component which generate | occur | produces by heating a mixture can be removed, and a masterbatch with a better external appearance can be obtained.

  The proportion of the inorganic compound powder contained in the master batch is preferably 15% by weight or more and 90% by weight or less. When the proportion of the inorganic compound is less than 15% by weight, the proportion of the binder resin is increased more than necessary, and the amount of the master batch added to the molding material is increased. Moreover, since it will become difficult to maintain a shape because the ratio of binder resin reduces if it exceeds 90 weight%, it is unpreferable. From the viewpoint of ensuring shape retention while suppressing the amount of masterbatch added to the molding material, it is more preferably 30% by weight to 80%, and most preferably 60% by weight to 75% by weight.

  The binder resin used in molding the master batch functions as a carrier resin that binds inorganic compounds and other components contained in the master batch to each other. As the binder resin, for example, polyethylene, polypropylene, EVA resin (copolymer of ethylene and vinyl acetate) or the like can be used. More preferably, the same type of resin as the molding material is used as the binder resin.

  In addition to the surface-modified inorganic compound powder and the binder resin, the master batch can contain additives such as a lubricant, a heat stabilizer, and an antioxidant.

  By adding a lubricant, it is possible to stabilize the moldability of the masterbatch and reduce friction with the molding material when the masterbatch is added to the molding material. A conventionally well-known thing can be used as a lubricant. Specific examples of the lubricant used in the present invention include, but are not limited to, the following.

  Examples of the lubricant include hydrocarbon lubricants such as liquid paraffin, paraffin wax and polyethylene wax, fatty acid lubricants such as stearic acid, metal soap lubricants such as calcium stearate, zinc stearate, magnesium stearate and zinc stearate. It can be illustrated. Only one type of lubricant may be used alone, or two or more types may be used in combination. Among these, stearic acid is preferably used because it has excellent compatibility with various thermoplastic resins.

  The ratio of the lubricant contained in the master batch is preferably 15% by weight or less. When the lubricant is contained in an amount of more than 15% by weight, when the masterbatch is formed, the constituent materials of the masterbatch slip each other, so that the moldability is deteriorated. The ratio of the lubricant is more preferably 3% by weight or more and 6% by weight or less. When the ratio of the lubricant is within this range, the lubricity between the constituent materials can be improved and the moldability can be kept good when the master batch is molded. Further, when the masterbatch is added to the plastic material, friction between the masterbatch and the plastic material can be moderated moderately.

  Moreover, a heat stabilizer can be added to a masterbatch, and, thereby, discoloration of the thermoplastic resin by the heating at the time of masterbatch shaping | molding can be prevented. As the heat stabilizer, various heat stabilizers used in plastic molding can be used. Specific examples of the heat stabilizer include, but are not limited to, the following.

  Examples of the heat stabilizer include aliphatic carboxylate lithium stearate, magnesium stearate, calcium laurate, calcium linoleate, calcium stearate, barium ricinoleate, barium stearate, zinc laurate, zinc ricinoleate, and zinc stearate. Aliphatic carboxylate heat stabilizers, dimethyltin bis-2-ethylhexyl thioglycolate, organic tin mercaptides such as mono / dimethyltin stearoxyethyl mercaptide, dibutyltin maleate, dibutyltin bisbutyl maleate, Organic tin maleates such as dibutyltin dilaurate, dibutyltin bis-2-ethylhexylthioglycolate, dibutyltin β-mercaptopropionate, and dioctyltin dilaurate, dioctylus It may be exemplified various organic tin-based heat stabilizers organotin carboxylates such as bis-2-ethylhexyl thioglycolate. Only one type of heat stabilizer may be used alone, or two or more types may be used in combination. The proportion of the heat stabilizer contained in the master batch is preferably 10% by weight or less. More preferably, it is 1 wt% or more and 3 wt% or less.

  Further, an antioxidant can be added to the masterbatch, whereby the thermoplastic resin can be prevented from being oxidized by heating during production of the masterbatch and deteriorating in quality. Any antioxidant can be used as long as it has compatibility with the thermoplastic resin contained in the masterbatch, and various antioxidants generally used for plastic molding can be used. Specific examples of the antioxidant include, but are not limited to, the following.

  Examples of the antioxidant include 2,6-di-t-butyl-4-methylphenol, n-octadecyl-3- (3 ′, 5′-di-t-butyl-4′hydroxyphenyl) propionate, tetrakis- [Methylene-3- (3 ′, 5′-di-t-butyl-4-hydroxyphenyl) propionate] methane, tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, triethylene glycol -Bis- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate], 2,2'-methylenebis- (4-methyl-6-tert-butylphenol), 4,4'-thiobis Phenolic antioxidants such as-(3-methyl-6-t-butylphenol), 4,4'-butylidenebis- (3-methyl-6-t-butylphenol) Agent, dilauryl-3,3′-thiodipropionate, dimyristyl-3,3′-thiocypropionate, distearyl-3,3′-thiodipropionate, pentaerythritol tetrakis (3-laurylthiopropionate ) And the like, trisnonylphenyl phosphite, distearyl pentaerythritol diphosphite, tris (2,4-di-t-butylphenyl) phosphite, tetrakis (2,4-di-t-butyl) And phosphoric acid antioxidants such as phenyl) -4,4′-biphenylene-di-phosphite. Only one type of antioxidant may be used alone, or two or more types may be used in combination. The proportion of the antioxidant contained in the master batch is preferably 15% by weight or less.

  In addition, although the compounding ratio reference | standard of inorganic compound powder, binder resin, and various additives was shown, it cannot be overemphasized that it should prepare within the range which adds them all and becomes 100 weight%. In addition, one kind or plural kinds of additives can be used. However, when plural kinds of additives are used, each additive is used as a whole within a range not inhibiting the action of the inorganic compound powder and the binder resin. The blending ratio of is adjusted.

[Test Example 1]
In Test Example 1, first, a barium sulfate powder having a particle size of 2 μm was used as the inorganic compound and the No. 1 shown in Table 1 was obtained. 1-4 master batches were made. No. In No. 1, a master batch was prepared using aluminum ethylate as the first surface modifier, maleic anhydride-modified polyethylene as the second surface modifier, and polyethylene as the binder resin. No. One master batch contains the inorganic compound powder prepared by sequentially performing the first to fourth steps and coated with the first surface modifier and the second surface modifier. No. The second masterbatch is prepared by omitting the second step, and contains a powder of an inorganic compound that is surface-modified only with the first surface modifier. No. The master batch 3 is prepared by omitting the first step, and contains a powder of an inorganic compound that is surface-modified only with the second surface modifier. No. 4, the second surface modifier is changed to a copolymer of maleic anhydride and polyethylene, and the first surface modifier and the second surface-modified inorganic compound are sequentially subjected to the first to fourth steps. A master batch containing the powder was prepared.

  Next, no. 30 parts by weight of the master batches 1 to 4 were mixed with 70 parts by weight of HDPE (high density polyethylene), respectively, to prepare films 1 to 5 having a thickness of 25 μm and an inorganic compound content of 21% by weight. As a control, an HDPE film 4 having a thickness of 25 μm and containing no inorganic compound powder was prepared.

  In Test Example 1, the film 1 containing the inorganic compound powder coated with the first surface modifier and the second surface modifier is the film 2 containing the inorganic compound powder coated only with the first surface modifier. Higher tensile strength. And although this film 1 was a little lower in tensile strength than the film 5 which does not contain an inorganic compound, it was a grade which is hardly inferior. This is because the compatibility between the inorganic compound powder and the high-density polyethylene was enhanced by entanglement of the long molecular chain of the maleic anhydride-modified polyethylene as the second surface modifier in the film 1 with the high-density polyethylene. It was inferred that there was. However, the film 3 containing the inorganic compound powder coated only with the second surface treatment agent had lower tensile strength than the film 1. As a result, it has been clarified that the tensile strength of the film can be ensured only by covering the powder of the inorganic compound with the second surface modifier via the first surface modifier. This is presumably because the bond between the inorganic compound powder and the high-density polyethylene became stronger by increasing the affinity between the second surface modifier and the inorganic compound by the first surface modifier. It was.

  In addition, when film 1 and film 4 in which the second surface modifier is changed to a copolymer of maleic anhydride and polyethylene are compared, film 4 has higher tensile strength, and the tensile strength is higher than that of inorganic compounds. It was equivalent to the film not containing. Thereby, it became clear that the copolymer of maleic anhydride and polyethylene can be more suitably used as the second surface modifier.

[Test Example 2]
In Test Example 2, No. 1 prepared in Test Example 1 was prepared. An HDPE (High Density Polyethylene) film having an inorganic compound content of 7,14,21% by weight was prepared using 1 masterbatch. About each produced film, 1g of samples were extract | collected and the generation amount of the carbon dioxide was measured on condition of 850 degreeC by the combustion pipe type air method (based on JISK2541-3). The results are shown in Table 3.

  From this result, it was confirmed that the amount of carbon dioxide generated during incineration can be reduced in proportion to the content of the inorganic compound by including the inorganic compound in the film.

Claims (4)

Containing an inorganic compound powder coated with a surface modifier;
The inorganic compound is an inorganic compound that does not generate carbon dioxide by heating,
The inorganic compound powder is coated with a first surface modifier that coats the inorganic compound powder and a second surface modifier that coats the first surface modifier,
The second surface modifier is at least one selected from the group consisting of maleic anhydride-modified polyolefin, a copolymer of maleic anhydride and polyolefin, and a maleic anhydride-modified olefin elastomer,
The first surface modifier is a coupling agent having an affinity for the inorganic compound powder and the second surface modifier, and is a titanate coupling agent or an aluminate coupling agent. Polyolefin molded product. The polyolefin molded body according to claim 1,
The polyolefin molded body, wherein the inorganic compound is at least one selected from the group consisting of talc, zeolite, metal hydroxide, magnesium sulfate or barium sulfate. A polyolefin molded article according to claim 1 or claim 2, wherein
Polyolefin molded product formed into a bag shape, tubular shape, sheet shape or plate shape. A masterbatch added to a molding material when molding a polyolefin molded body,
Contains inorganic compound powder and binder resin coated with a surface modifier,
The inorganic compound is an inorganic compound that does not generate carbon dioxide by heating,
The inorganic compound powder is coated with a first surface modifier that directly coats the inorganic compound powder and a second surface modifier that coats the surface modifier,
The second surface modifier is at least one selected from the group consisting of maleic anhydride-modified polyolefin, a copolymer of maleic anhydride and polyolefin, and a maleic anhydride-modified olefin elastomer,
The first surface modifier is a coupling agent having an affinity for the inorganic compound powder and the second surface modifier, and is a titanate coupling agent or an aluminate coupling agent. A masterbatch characterized by