JP6954705B1 - Resin composition and molded product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin in which calcium carbonate is highly filled, a small amount of elution under acidic conditions, good moldability, and excellent physical properties such as mechanical strength, particularly a food packaging container. And a resin composition suitable for tableware, and a molded product composed of such a resin composition. SOLUTION: In a resin composition containing a thermoplastic resin and an inorganic substance powder in a mass ratio of 50:50 to 10:90, the inorganic substance powder is surface-treated with a surface treatment agent containing a phosphoric acid ester. It is a resin composition characterized by being an esterified calcium carbonate. The phosphoric acid ester is preferably polyoxyethylene lauryl ether phosphoric acid. [Selection diagram] None

Description

The present invention relates to resin compositions and molded articles. More specifically, the present invention has a small amount of elution under acidic conditions, good moldability, and excellent physical properties such as mechanical strength, despite the fact that the thermoplastic resin is highly filled with calcium carbonate. The present invention relates to a resin composition and an article comprising such a resin composition, particularly a food packaging container and a tableware.

Conventionally, as a food packaging container, a container formed by using paper, polyester, polypropylene, expanded polystyrene or the like as a base material has been widely used. However, now that environmental protection has become an international issue, reducing the consumption of synthetic resins and paper materials has been greatly studied, and from this point of view, inorganic substance powder is highly contained in thermoplastic resins. A filled resin composition has been proposed (see, for example, Patent Document 1 and the like), and is expected to be applied in the field of food packaging containers. Among the inorganic substance powders, calcium carbonate is not harmful to the human body and is abundantly produced in Japan. Therefore, the resin composition filled with it is useful for food packaging containers and tableware.

However, in the food packaging container formed of the resin composition as described above, the inorganic substance powder may fall off during use, or the inorganic substance powder may be added to foods, particularly liquid foods such as strongly acidic beverages. There is a problem that calcium carbonate used as a food material may be eluted. For example, a resin container used for foods having a pH of 5 or less is required to have a small amount of elution into warm acetic acid, but a resin composition containing a large amount of calcium carbonate tends to have a large amount of elution. In addition, since the thermoplastic resin is highly filled with the inorganic substance powder, minute voids are likely to be generated in the packaging container, so that the gas barrier property is poor, and there are problems in terms of moisture, odor transfer, and maintenance of product freshness. And the oil resistance was not sufficient.

Therefore, when a resin composition containing an inorganic substance powder is used in a food packaging container, it generally has a two-layer or three-layer structure in which the resin is laminated on the side or both sides in contact with the food. For example, Patent Document 2 discloses a sheet-like laminate in which an outer layer of a thermoplastic resin is laminated on both sides of an inner layer containing an inorganic filler in an amount of more than 50% by mass.

Further, as a method of suppressing the generation of voids in the resin composition and improving the mechanical strength, a technique of surface-treating an inorganic substance powder is known. Patent Document 2 also describes a technique for treating the surface of calcium carbonate particles with a silane coupling agent or metal soap. Here, the surface treatment technique itself is known, and for example, calcium carbonate surface-treated with a resin acid, a silane, a phosphoric acid ester, or the like in addition to a fatty acid is described in Non-Patent Documents 1 and Patent Documents 3 and 4.

International Publication No. WO2014 / 109267 Japanese Patent No. 6857428 Special Table 2016-513159 Japanese Unexamined Patent Publication No. 11-355790

Tsutsui, Journal of the Japan Rubber Association, Vol. 78, p. 218 (2005)

A laminated body as described in Patent Document 2 has a drawback in terms of productivity because a laminating process is indispensable at the time of manufacturing. Since it is difficult to provide a surface layer at the end of a container or the like, good evaluation results may not be obtained in the acetic acid elution test. The cost of the resin laminate tends to be high, and it is difficult to contribute to environmental protection by reducing the consumption of synthetic resin. There is a demand for a technique for suppressing elution from an inorganic substance powder-filled resin composition without laminating resin layers.

Patent Document 2 also describes that surface treatment with calcium stearate or the like can suppress the generation of voids at the interface between the calcium carbonate particles and the thermoplastic resin, and can improve the moldability of the laminate. However, as shown in Examples described later, if the surface treatment agent is improperly selected, the moldability and mechanical properties of the resin composition may rather deteriorate.

Most of the conventional surface treatment methods have been studied in a system in which the amount of calcium carbonate blended is smaller than that of a thermoplastic resin or the like, for example, as in Non-Patent Document 1. Patent Document 3 also describes a polymer composition containing up to 95% by weight of a surface-treated inorganic substance. However, the relationship between the mechanical properties of the molded product and the surface treatment method has actually been studied only for compositions having an inorganic substance content of 20% by weight or less. Although Patent Document 4 describes an electric wire sheath layer based on a composition filled with a large amount of silane-treated calcium carbonate or the like, its physical properties such as mechanical strength have not been evaluated. As described above, for resin compositions filled with a large amount of inorganic substance powder, particularly for resin compositions for foods, the relationship between the surface treatment method and moldability and mechanical properties has not been studied at present. ..

The present invention has been made in view of the above circumstances, and despite the fact that the thermoplastic resin is highly filled with calcium carbonate, the amount of elution under acidic conditions is small, the moldability is good, and the machine is mechanical. An object of the present invention is to provide a resin composition having excellent physical properties such as physical strength, particularly suitable for food packaging containers and tableware, and a molded product made of such a resin composition.

As a result of diligent studies, the present inventors have made carbonic acid with a surface treatment agent containing phosphoric acid esters, particularly a surface treatment agent containing phosphoric acid esters having a specific structure as a main component, in a resin composition filled with a large amount of calcium carbonate. It has been found that by treating the calcium surface, the moldability can be improved without deteriorating the physical properties of the resin composition, and the amount of elution into acetic acid or the like can be reduced, and the present invention has been reached.

That is, the present invention that solves the above problems is a resin composition containing a thermoplastic resin and an inorganic substance powder in a mass ratio of 50:50 to 10:90, wherein the inorganic substance powder contains a phosphoric acid ester. It is a resin composition characterized by being calcium carbonate surface-treated with a surface-treating agent.

In one embodiment of the resin composition of the present invention, a resin composition in which the phosphoric acid ester is polyoxyethylene lauryl ether phosphoric acid is shown.

In one embodiment of the resin composition of the present invention, the average particle size calculated from the measurement result of the specific surface area of the calcium carbonate particles by the air permeation method according to JIS M-8511 is 0.7 μm or more and 6.0 μm or less. The resin composition is shown.

In one embodiment of the resin composition of the present invention, the resin composition in which the calcium carbonate is heavy calcium carbonate is shown.

In one embodiment of the resin composition of the present invention, a resin composition in which the thermoplastic resin is a polyolefin-based resin is shown.

In one embodiment of the resin composition of the present invention, a resin composition in which the polyolefin-based resin is composed of a polyethylene-based resin and / or a polypropylene-based resin is shown.

In one embodiment of the resin composition of the present invention, a molded product made of any of the above resin compositions is shown.

In one embodiment of the resin composition of the present invention, a food packaging container made of any of the above resin compositions is shown.

According to the present invention, despite the fact that the thermoplastic resin is highly filled with calcium carbonate, the resin composition has a small amount of elution under acidic conditions, good moldability, and excellent physical properties such as mechanical strength. Things are provided. Molded articles based on the resin composition of the present invention are particularly suitable for food packaging containers and tableware.

Hereinafter, the present invention will be described in detail based on the embodiments.

The resin composition of the present invention contains a thermoplastic resin and calcium carbonate surface-treated with a surface treatment agent containing a phosphoric acid ester in a mass ratio of 50:50 to 10:90. Hereinafter, these components in the resin composition will be described.

≪Thermoplastic resin≫
In the resin composition of the present invention, the type of thermoplastic resin is not particularly limited. For example, polyolefin resins such as polyethylene resins, polypropylene resins, polymethyl-1-pentene, and ethylene-cyclic olefin copolymers; ethylene-vinyl acetate copolymers, ethylene-acrylic acid copolymers, ethylene-methacrylic acid. Copolymer, metal salt (ionomer) of ethylene- (meth) acrylic acid copolymer, ethylene-acrylic acid alkyl ester copolymer, ethylene-methacrylic acid alkyl ester copolymer, maleic acid-modified polyethylene, maleic acid-modified polypropylene Functional group-containing polyolefin resins such as Nylon-6, Nylon-6,6, Nylon-6,10, Nylon-6,12 and other polyamide resins; Polyethylene terephthalate and its copolymers, polyethylene naphthalate, polybutylene, etc. Aromatic polyester resins such as terephthalate, thermoplastic polyester resins such as aliphatic polyester resins such as polyvinyl acetate, polybutylene succinate and polylactic acid; acrylics such as poly (meth) acrylic acid (ester) and polyacrylonitrile Based resin; Polycarbonate resin such as aromatic polycarbonate and aliphatic polycarbonate; Polystyrene resin such as atactic polystyrene, syndiotactic polystyrene, acrylonitrile-styrene (AS) copolymer, acrylonitrile-butadiene-styrene (ABS) copolymer, etc. ; Polyvinyl chloride resin such as polyvinyl chloride and polyvinylidene chloride; Polyphenylene sulfide; Polyether resin such as polyether sulfone, polyether ketone, polyether ether ketone; Further, polyvinyl alcohol, petroleum hydrocarbon resin, kumaron Various known thermoplastic resins such as inden resins can be mentioned, but are not limited thereto. A plurality of types of thermoplastic resins can also be used in combination. It also contains elastomeric components such as styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-butadiene-ethylene copolymer, styrene-isoprene-ethylene copolymer, acrylonitrile-butadiene copolymer, and fluoroelastomer. You may do it.

Among these thermoplastic resins, polyolefin-based resins are preferable from the viewpoints of ease of molding, performance, economy, and the like.

<Polyolefin resin>
Here, the polyolefin-based resin is a polyolefin-based resin containing an olefin component unit as a main component, and specifically, as described above, a polypropylene-based resin, a polyethylene-based resin, and other polymethyl-1-pentene and ethylene-. Examples thereof include cyclic olefin copolymers and the like, as well as mixtures of two or more of them. The above-mentioned "main component" means that the polyolefin component unit contains 50% by mass or more of the olefin component unit, and the content thereof is preferably 75% by mass or more, more preferably 85% by mass. % Or more, more preferably 90% by mass or more. In particular, a polyolefin homopolymer is preferable. The method for producing the polyolefin resin used in the present invention is not particularly limited, and can be obtained by any of a method using a Ziegler-Natta catalyst, a metallocene catalyst, a radical initiator such as oxygen or peroxide, or the like. It may be a catalyst.

The resin composition of the present invention preferably contains a polyethylene-based resin and / or a polypropylene-based resin as these polyolefin-based resins. More preferably, the thermoplastic resin is substantially composed of a polyethylene-based resin and / or a polypropylene-based resin. These resins are particularly excellent in the balance between physical properties, moldability, and cost, and are suitable as thermoplastic resin components in the resin composition of the present invention. In particular, polypropylene-based resins are preferably used because they are particularly excellent in the balance between mechanical strength and heat resistance.

Examples of the polypropylene-based resin include resins having a propylene component unit of 50% by mass or more, and examples thereof include propylene homopolymers and copolymers with other monomers copolymerizable with propylene. The propylene homopolymer includes any of isotactics, syndiotactics, atactics, hemiisotactics and linear or branched polypropylenes exhibiting various stereoregularities. Further, the above-mentioned copolymer may be a random copolymer or a block copolymer, and may be not only a binary copolymer but also a ternary copolymer. Examples of the copolymerization component (other monomers) include ethylene, 1-butene, isobutylene, 1-pentene, 3-methyl-1-butene, 1-hexene, 3,4-dimethyl-1-butene, 1-hexene, and the like. Α-olefins having 4 to 10 carbon atoms such as 3-methyl-1-hexene; and further, but not limited to, tetrafluoroethylene and vinyl acetate. In the present invention, a homopolymer or a resin in which a small amount of other monomers is copolymerized, for example, less than 5% by mass is used. In addition, even in the homopolymer of propylene, a structure as if α-olefin such as hexene is copolymerized as a result of the polymerization may be partially contained, but in the present invention, such a polymer is also included. , Widely included as a propylene homopolymer. These polypropylene-based resins can be used alone or in admixture of two or more.

Examples of the polyethylene-based resin include resins having an ethylene component unit of 50% by mass or more, and examples thereof include high-density polyethylene (HDPE), low-density polyethylene (LDPE), medium-density polyethylene, and linear low-density polyethylene (straight-line low-density polyethylene). LLDPE), ethylene-vinyl acetate copolymer, ethylene-propylene copolymer, ethylene-propylene-butene 1 copolymer, ethylene-butene 1 copolymer, ethylene-hexene 1 copolymer, ethylene-4 methylpentene 1 Examples thereof include a copolymer, a polyethylene-octene 1 copolymer, and a mixture of two or more thereof.

≪Inorganic substance powder≫
The inorganic substance powder contained in the resin composition of the present invention is calcium carbonate surface-treated with a surface treatment agent containing a phosphoric acid ester.

<Calcium carbonate>
Calcium carbonate includes those prepared by a synthetic method (so-called light calcium carbonate) and _{those obtained by mechanically crushing and classifying natural raw materials such as limestone containing CaCO 3} as a main component (so-called heavy calcium carbonate). Any of these may be used, and these may be used in combination. The shape is not particularly limited, and may be in the form of particles, flakes, granules, fibers, or the like. Further, it may be in the form of particles, which may be spherical as generally obtained by a synthetic method, or may have an indefinite shape as obtained by pulverizing the collected natural minerals. ..

The calcium carbonate is not particularly limited, but its average particle size is preferably 0.7 μm or more and 6.0 μm or less, more preferably 0.8 μm or more and 5.0 μm or less, and even more preferably 1.0 μm. It is 4.0 μm or less. The average particle size of the inorganic substance powder such as calcium carbonate described in the present specification refers to a value calculated from the measurement result of the specific surface area by the air permeation method according to JIS M-8511. As the measuring device, for example, a specific surface area measuring device SS-100 manufactured by Shimadzu Corporation can be preferably used. When the average particle size is larger than 6.0 μm, for example, when a sheet-shaped molded product is formed, the inorganic substance powder protrudes from the surface of the molded product and falls off, depending on the layer thickness of the molded product. There is a risk of damage to the surface properties and mechanical strength. In particular, it is preferable that the particle size distribution does not contain particles having a particle size of 45 μm or more. On the other hand, if the particles become too fine, the viscosity may increase remarkably when kneaded with the above-mentioned resin, which may make it difficult to manufacture a molded product. Such a problem can be prevented by setting the average particle size of the inorganic substance powder to 0.7 μm or more, particularly 0.8 μm or more and 6.0 μm or less.

In the present invention, calcium carbonate is the first calcium carbonate having an average particle size of 0.7 μm or more and less than 2.0 μm, particularly 0.8 μm or more and less than 2.0 μm, measured by the air permeation method according to JIS M-8511, and JIS. It may contain a second calcium carbonate having an average particle size of 2.0 μm or more and 6.0 μm or less, particularly 2.0 μm or more and 5.0 μm or less, as measured by the air permeation method by M-8511. This makes it possible to improve the surface properties of the molded product and the physical properties such as printability and blocking property. In addition, uneven distribution of calcium carbonate is suppressed, a molded product having good appearance and mechanical properties such as elongation at break can be obtained, and it is possible to reduce the loss of calcium carbonate from the molded product of the resin composition. .. Although not particularly limited, when the average particle size of the first calcium carbonate is a and the average particle size of the second calcium carbonate is b, the a / b ratio is more preferably 0.85 or less. It is desirable that the particles can be roughly classified into 0.10 to 0.70, more preferably 0.10 to 0.50. This is because a particularly excellent effect can be expected by using those having a certain difference in average particle size in combination. Further, it is desirable that the coefficient of variation (Cv) of the distribution of the particle size (μm) of each of the first calcium carbonate and the second calcium carbonate is about 0.01 to 0.10. It is desirable that it is about 0.08. If the variation in particle size defined by the coefficient of variation (Cv) is about this level, it is considered that each powder group can give a more complementary effect. The mass ratio of the first calcium carbonate to the second calcium carbonate is preferably 90: 10 to 98: 2, particularly about 92: 8 to 95: 5. Three or more calcium carbonate groups having different average particle size distributions may be used.

In the present invention, calcium carbonate preferably contains heavy calcium carbonate. More preferably, the heavy calcium carbonate and its unavoidable impurities constitute the inorganic substance powder in the resin composition of the present invention. Here, heavy calcium carbonate is obtained by mechanically crushing and processing natural limestone or the like, and is clearly distinguished from synthetic calcium carbonate produced by a chemical precipitation reaction or the like. The pulverization method includes a dry method and a wet method, and the dry method is preferable.

Unlike light calcium carbonate produced by a synthetic method, heavy calcium carbonate is characterized by surface irregularity and a large specific surface area due to particle formation performed by a pulverization treatment. Since heavy calcium carbonate has such irregular shape and large specific surface area, heavy calcium carbonate has more contact interfaces with the thermoplastic resin when blended in the thermoplastic resin. , Effective for uniform dispersion.

Although not particularly limited, the specific surface area of the calcium carbonate ^{is preferably about 3,000 cm 2} / g or more and 35,000 cm ² / g or less, although it depends on the average particle size thereof. .. The specific surface area referred to here is based on the air permeation method. When the specific surface area is within this range, the deterioration of workability of the obtained molded product tends to be suppressed.

Further, the indeterminate form of the calcium carbonate particles can be expressed by the low degree of spheroidization of the particle shape, and is not particularly limited, but specifically, the roundness is 0.50 or more and 0. It is .95 or less, more preferably 0.55 or more and 0.93 or less, and further preferably 0.60 or more and 0.90 or less. When the roundness of the calcium carbonate particles is within this range, the strength and moldability of the molded product are also appropriate. Here, the roundness can be expressed by (projected area of particles) / (area of a circle having the same perimeter as the projected perimeter of particles). The method for measuring the roundness is not particularly limited, and for example, the projected area of the particles and the projected peripheral length of the particles may be measured from a micrograph, or a generally commercially available image analysis software may be used.

<Surface treatment>
In the present invention, calcium carbonate as described above is a surface treatment agent containing a phosphoric acid ester, and at least a part thereof is surface-treated. By such surface treatment (surface modification), the dispersibility and reactivity of calcium carbonate can be enhanced, and the physical properties and moldability of the resin composition can be improved. Moreover, unlike calcium carbonate modified with a general-purpose surface treatment agent such as fatty acid, even if it is highly filled in a thermoplastic resin, it has excellent mechanical properties and physical properties such as elution under acidic conditions, and is a food product. A resin composition suitable for packaging containers and tableware is provided.

<Phosphate ester surface treatment agent>
In the present invention, the "surface treatment agent containing a phosphoric acid ester" includes all surface treatment agents containing a phosphoric acid-based ester. Examples of phosphate-based esters are phosphate-alcohol monoesters, diesters, triesters; phosphate-phenol monoesters, diesters, triesters; phosphate-alkylphenol monoesters, diesters, triesters. A monoester, diester, or triester of phosphoric acid, alcohol, and alkylene oxide, for example, a phosphoric acid ester having a structure in which an alkyloxy group, an alkyloxyalkyleneoxy group, and a hydroxy group are bonded to a phosphorus atom; a carboxy group or a carbonyl group. A phosphate ester having a structure of; and salts thereof, such as sodium salt, potassium salt, ammonium salt and the like, but are not limited thereto. A plurality of types of these phosphoric acid esters can also be used in combination. Further, a surface treatment agent containing a fatty acid, a resin acid, an anhydrous fatty acid-modified resin, or the like may be used together with these phosphoric acid esters.

<Phosphate ester>
In the present invention, the phosphoric acid ester is preferably a monoester, a diester, a salt thereof, or a mixture of two or three or more thereof. Generally, a surface treatment agent containing a monoester or a diester has a large effect of modifying the surface of calcium carbonate. The present invention is not limited to a specific theory, but monoesters and diesters strongly react or adsorb to the surface of calcium carbonate via> P (= O) -O- groups in the molecule. Conceivable. Further, in general, the longer the aliphatic hydrocarbon chain length tends to be more compatible with the thermoplastic resin, and the effect of the present invention becomes particularly remarkable. Therefore, a phosphate ester having a long-chain aliphatic hydrocarbon group in the molecule, for example, a monoester, a diester, or a triester of a phosphoric acid and a long-chain alcohol; a monoester, a diester, or a triester of a phosphoric acid and a long-chain alkylphenol. A surface treatment agent containing one or more phosphoric acid esters selected from monoesters, diesters and triesters of phosphoric acid, long-chain alcohol and alkylene oxide; and salts thereof is preferable. More preferably, it is a monoester and diester of phosphoric acid and long-chain alcohol, a monoester and diester of phosphoric acid and long-chain alcohol and alkylene oxide, and one or more phosphoric acid esters selected from salts thereof. ..

The aliphatic hydrocarbon group in the phosphoric acid ester is not particularly limited, and includes all saturated or unsaturated linear, branched, or cyclic aliphatic hydrocarbon groups. It may be substituted with a hydroxy group, an alkoxy group, an amino group, a nitro group, a cyano group or the like. Examples are isopropyl group, butyl group, hexyl group, n-octyl group, isooctyl group, decyl group, dodecyl group (lauryl group), pentadecyl group (myristyl group), tetradecyl group (myristyl group), hexadecyl group (palmityl group). , Octadesyl group (stearyl group), hexadecenyl group (palmitrail group), octadecenyl group (oleyl group), octadecadienyl group (linoleyl group, elelide linolenyl group), octadecatrienyl group (linolenyl group), hydroxy Examples thereof include, but are not limited to, an octadecenyl group (linoleyl group). The number of carbon atoms of the aliphatic hydrocarbon group is also not particularly limited, and may be, for example, an aliphatic hydrocarbon group having 3 to 20 carbon atoms, particularly 8 to 18, particularly 10 to 14 carbon atoms.

In the present invention, the phosphoric acid ester is particularly preferably a monoester of phosphoric acid, an alcohol and an alkylene oxide, a diester, and / or a salt thereof. For example, a compound such as formula 1: [C _x H _{2x + 1} O (C _y H _2y O) _z ] _n P (= O) (OH) _m or a salt thereof (in formula 1, x, y, and z are 1). The above integers; n and m are 1 or 2 and n + m = 3), but are not limited thereto. The hydrocarbon group ( _{corresponding to C x} H _{2x + 1} ) of the phosphoric acid ester may have, for example, an unsaturated bond or a cyclic structure and have a hydrogen atom number of 2x-1 or less, a branched structure, a hydroxy group, or the like. It may have a substituent of. According to such a phosphoric acid ester, the surface of calcium carbonate can be modified particularly effectively, the amount of elution under acidic conditions is small, and it is possible to obtain a resin composition having good physical properties such as mechanical strength. Become. The present invention is not limited by any particular theory, but the presence of alkylene oxide units in the molecule allows the aliphatic hydrocarbon groups to spread more widely from the phosphate ester on the surface of calcium carbonate, resulting in a surface. It is considered that the compatibility between the treated calcium carbonate and the thermoplastic resin is good.

Even in the above-mentioned phosphoric acid ester, the number of carbon atoms of the aliphatic hydrocarbon group (for example, x in the above formula 1) is not particularly limited, but is 3 to 20, particularly 8 to 18, particularly 10 to 14. Is preferable. More preferably, polyoxyethylene lauryl ether phosphoric acid or a salt thereof is used. The type of alkylene oxide is not particularly limited, but ethylene oxide, propylene oxide, and butylene oxide are particularly preferable, and ethylene oxide (y = 2 in the above formula 1) is particularly preferable. The number of alkylene oxide units (z in Formula 1) is also not particularly limited. For example, 1 to 12 alkylene oxide units, particularly 1 to 4 alkylene oxide units, are provided between each aliphatic hydrocarbon group as described above and a phosphorus atom. It is preferable to have one. More preferably, polyoxyethylene (1-4) lauryl ether phosphoric acid and / or a salt thereof, particularly preferably monopolyoxyethylene (2) lauryl ether phosphoric acid, dipolyoxyethylene (2) lauryl ether phosphoric acid, And one or more phosphate esters selected from their salts.

<Surface treatment method>
The surface treatment method for calcium carbonate with a phosphoric acid ester as described above is not particularly limited, and various known surface treatment methods can be incorporated. For example, a method of adding a phosphoric acid ester to a calcium carbonate slurry and stirring it (wet method), a method of putting calcium carbonate and a phosphoric acid ester in a crusher or a mixer, and stirring while heating as desired (dry method). Further, a method of stirring the hydrous cake containing calcium carbonate and the phosphoric acid ester while heating in a mixer can be mentioned, but the method is not limited thereto. Although it depends on the type of phosphate ester used as the surface treatment agent, it is generally preferable that the surface treatment of light calcium carbonate is performed by a wet method and the surface treatment of heavy calcium carbonate is performed by a dry method.

There is no particular limitation on the ratio of the amount of phosphoric acid ester to calcium carbonate during surface treatment. However, the amount of the phosphoric acid ester is preferably 0.2 to 10 parts by mass, particularly 0.5 to 5 parts by mass, and particularly preferably about 1 to 3 parts by mass with respect to 100 parts by mass of calcium carbonate. With such an amount of phosphoric acid ester, it becomes easy to uniformly modify the surface of calcium carbonate, and the risk of excess phosphoric acid ester elution during use can be reduced. The amount of phosphoric acid ester on the surface of calcium carbonate can be quantified by a known analysis method such as solvent extraction or thermal decomposition GC / MS.

When the surface is treated by the wet method, the concentration of calcium carbonate in the slurry and the type of solvent are not particularly limited. A water-based slurry having a calcium carbonate concentration of 10 to 300 g / L, particularly about 25 to 200 g / L is preferable. At such a concentration, the productivity of the surface treatment is increased, and the viscosity is not increased to reduce the workability. By using an aqueous solvent, surface treatment can be performed easily and at low cost, and safety can be maintained even if the treatment temperature is raised. The slurry temperature in the wet method is preferably 20 to 98 ° C, more preferably 40 to 90 ° C, and even more preferably 60 to 80 ° C. By performing the surface treatment at 20 ° C. or higher, the surface treatment agent can be uniformly adsorbed and bonded on calcium carbonate, and the surface treatment can be performed uniformly. Further, if the slurry temperature is 98 ° C. or lower, there is no risk of bumping or the like, and a pressure-resistant device is not required. In the surface treatment by the wet method, a surfactant may be contained in the slurry.

The surface treatment by the dry method can be performed by kneading calcium carbonate and a phosphoric acid ester in a kneader such as a Henschel mixer, a kneader, or an extrusion kneader. In particular, when heavy calcium carbonate is used, a desired phosphoric acid ester can be added to the crusher, and the surface treatment can be performed at the same time as adjusting the particle size of calcium carbonate. Here, the temperature at the time of surface treatment can be arbitrarily set according to the type of phosphoric acid ester used, but is generally 20 to 150 ° C., particularly 40 to 130 ° C., and further about 60 to 120 ° C. Is preferable. By performing the surface treatment at 20 ° C. or higher, the surface treatment agent can be uniformly adsorbed and bonded on calcium carbonate, and the surface treatment can be performed uniformly. Further, when the treatment temperature is about 150 ° C. or lower, the risk of thermal deterioration and deterioration of the surface treatment agent can be reduced. More preferably, it is treated at a temperature equal to or higher than the melting point of the phosphoric acid ester used. As a result, the surface treatment agent can be more uniformly adsorbed and bonded on the calcium carbonate. For example, since polyoxyethylene lauryl ether phosphoric acid and the like are liquid at room temperature, the surface treatment can be performed at room temperature. When polyoxyethylene stearyl ether phosphoric acid or the like is used, kneading may be performed at a temperature of about 50 to 150 ° C. In the dry method, a small amount of solvent can be used in combination. For example, an aqueous solution of a phosphoric acid ester, particularly a salt-type phosphoric acid ester, may be added to calcium carbonate and kneaded or pulverized as described above.

In the surface treatment using the water-containing cake of calcium carbonate, the same conditions as the dry method can be adopted, but the temperature at the time of treatment is preferably 20 to 150 ° C., particularly about 40 to 98 ° C. This makes it possible to reduce the risk of non-uniform adsorption and bumping of the surface treatment agent.

In the resin composition of the present invention, the inorganic substance powder is calcium carbonate surface-treated with a surface treatment agent containing a phosphoric acid ester as described above, but may further contain an inorganic substance powder other than these. Examples include powders of carbonates such as calcium, magnesium, aluminum, titanium, iron, zinc, sulfates, silicates, phosphates, borates, oxides, or hydrates thereof. Specifically, for example, non-surface treated calcium carbonate, magnesium carbonate, zinc oxide, titanium oxide, silica, alumina, clay, talc, kaolin, aluminum hydroxide, magnesium hydroxide, aluminum silicate, magnesium silicate, silicic acid. Calcium, aluminum sulfate, magnesium sulfate, calcium sulfate, magnesium phosphate, barium sulfate, silica sand, carbon black, zeolite, molybdenum, diatomaceous soil, cericite, silas, calcium sulfite, sodium sulfate, potassium titanate, bentonite, wollastonite, Examples thereof include dolomite and graphite. These may be synthetic or derived from natural minerals, and they may be contained alone or in combination of two or more. However, in consideration of dispersibility in the thermoplastic resin, elution from the resin composition, and the like, the inorganic substance powder in the resin composition of the present invention is preferably 90% by mass or more, more preferably 95% by mass or more, particularly preferably. It is preferable that substantially the entire amount excluding the unavoidable impurities consists of the above-mentioned surface-treated calcium carbonate powder.

≪Resin composition≫
In the resin composition of the present invention, the above-mentioned thermoplastic resin and inorganic substance powder are contained in a mass ratio of 50:50 to 10:90. This is because if the content of the inorganic substance powder is small, it is difficult to obtain physical properties such as the texture and strength of the resin composition, and if it is too large, kneading and molding processing become difficult, and the flexibility becomes insufficient. The ratio of the inorganic substance powder to the total mass of the thermoplastic resin and the inorganic substance powder is preferably 52% by mass or more, more preferably 55% by mass or more. The upper limit of the ratio is preferably 80% by mass or less, more preferably 75% by mass or less, and particularly preferably 70% by mass or less.

<Other additives>
If necessary, other additives may be added to the resin composition according to the present invention as an auxiliary agent. Other additives include, for example, colorants, lubricants, coupling agents, fluidity improvers (fluidity modifiers), crosslinkers, dispersants, antioxidants, UV absorbers, flame retardants, stabilizers, and antistatic agents. An inhibitor, a foaming agent, a plasticizer and the like may be blended. These additives may be used alone or in combination of two or more. Further, these may be blended in the kneading step described later, or may be blended in the raw material components in advance before the kneading step.

In the resin composition according to the present invention, the amount of these other additives added is not particularly limited as long as it does not impair the desired physical properties and processability, but the total mass of the resin composition is 100%. In this case, each of these other additives is blended in a proportion of about 0 to 10% by mass, particularly about 0.04 to 5% by mass, and the total amount of the other additives is 10% by mass or less. Is desired. For example, in 100% by mass of the total resin composition, 10 to 45% by mass, particularly 20 to 25% by mass of thermoplastic resin; 90 to 45% by mass, especially 75 to 55% by mass of surface-modified calcium carbonate; The additive may be contained in an amount of 0 to 10% by mass, particularly 0.04 to 5% by mass.

Hereinafter, among these additives, those considered to be important will be described with examples, but the present invention is not limited to these.

Examples of the plasticizer include triethyl citrate, acetyl triethyl citrate, dibutyl phthalate, diaryl phthalate, dimethyl phthalate, diethyl phthalate, di-2-methoxyethyl phthalate, dibutyl tartrate, and o-benzoyl benzoic acid. Examples include esters, diacetin, epoxidized soybean oil and the like. These plasticizers are usually blended in an amount of about several mass% with respect to the thermoplastic resin, but the amount is not limited to these ranges, and depending on the use of the resin composition, about 20 to 50 parts by mass of epoxidized soybean oil or the like is added. It is also possible to mix. However, in the resin composition of the present invention, the blending amount thereof is preferably 0.5 to 10 parts by mass, particularly about 1 to 5 parts by mass with respect to 100 parts by mass of the thermoplastic resin.

As the colorant, any known organic pigment, inorganic pigment or dye can be used. Specifically, organic pigments such as azo-based, anthraquinone-based, phthalocyanine-based, quinacridone-based, isoindoleinone-based, geoosazine-based, perinone-based, quinophthalone-based, and perylene-based pigments, ultramarine blue, titanium oxide, titanium yellow, and iron oxide. (Valve handle), chrome oxide, zinc flower, carbon black and other inorganic pigments can be mentioned.

Examples of the lubricant include fatty acid-based lubricants such as stearic acid, hydroxystearic acid, composite stearic acid, and oleic acid; aliphatic alcohol-based lubricants; stearoamide, oxystearoamide, oleylamide, elcilamide, ricinolamide, behenamide, and methylol. An aliphatic amide lubricant such as amide, methylene bisstearoamide, methylene bisstearobehenamide, higher fatty acid bisamide acid, complex amide; stearic acid-n-butyl, methyl hydroxystearate, polyhydric alcohol fatty acid ester, Fatty acid ester-based lubricants such as saturated fatty acid esters and ester-based waxes; fatty acid metal soap-based lubricants such as zinc stearate and magnesium stearate can be mentioned.

As the antioxidant, a phosphorus-based antioxidant, a phenol-based antioxidant, and a pentaerythritol-based antioxidant can be used. Phosphorus-based, more specifically, phosphorus-based antioxidants such as phosphite ester and phosphoric acid ester are preferably used. Examples of the phosphorous acid ester include triphenyl phosphite, trisnonylphenyl phosphite, tris (2,4-di-t-butylphenyl) phosphite, and other phosphorous acid triesters, diesters, and monoesters. Can be mentioned.

Examples of the phosphoric acid ester include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, triphenyl phosphate, tricresyl phosphate, tris (nonylphenyl) phosphate, 2-ethylphenyldiphenyl phosphate and the like. These phosphorus-based antioxidants may be used alone or in combination of two or more.

Examples of phenolic antioxidants include α-tocopherol, butylhydroxytoluene, cinapyl alcohol, vitamin E, n-octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2-. t-Butyl-6- (3'-t-butyl-5'-methyl-2'-hydroxybenzyl) -4-methylphenylacrylate, 2,6-di-t-butyl-4- (N, N-dimethyl) Aminomethyl) phenol, 3,5-di-t-butyl-4-hydroxybenzylphosphonate diethyl ester, and tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxymethyl] methane Etc. are exemplified, and these can be used alone or in combination of two or more kinds.

The flame retardant is not particularly limited, and for example, a halogen-based flame retardant or a non-phosphorus-based halogen-based flame retardant such as a phosphorus-based flame retardant or a metal hydrate can be used. Specific examples of the halogen-based flame retardant include halogenated bisphenol compounds such as halogenated bisphenyl alkane, halogenated bisphenyl ether, halogenated bisphenyl thioether, and halogenated bisphenyl sulfone, brominated bisphenol A, and bromine. Bisphenol-bis (alkyl ether) -based compounds such as bisphenol S, chlorinated bisphenol A, and chlorinated bisphenol S, and as phosphorus-based flame retardants, tris (diethylphosphinic acid) aluminum, bisphenol A bis (diphenyl phosphate) , Triaryl isopropyl phosphate, cresildi 2,6-xylenyl phosphate, aromatic condensed phosphate, etc., as metal hydrates, for example, aluminum trihydrate, magnesium hydroxide, or a combination thereof, etc. Can be exemplified individually, or these can be used alone or in combination of two or more. It works as a flame-retardant aid and can improve the flame-retardant effect more effectively. Further, for example, antimony oxide such as antimony trioxide and antimony pentoxide, zinc oxide, iron oxide, aluminum oxide, molybdenum oxide, titanium oxide, calcium oxide, magnesium oxide and the like can be used in combination as a flame retardant aid. ..

The foaming agent is a resin composition that is mixed or press-fitted into a resin composition that has been melted in a melt-kneader and undergoes a phase change from a solid to a gas, a liquid to a gas, or the gas itself. It is used to control the foaming ratio). As for the foaming agent, the one that is liquid at room temperature changes its phase to a gas depending on the resin temperature and dissolves in the molten resin, and the one that is gas at room temperature does not change its phase and dissolves in the molten resin as it is. When the molten resin is extruded into a sheet from an extrusion die, the foaming agent dispersed and dissolved in the molten resin expands inside the sheet because the pressure is released, and foams by forming a large number of fine closed cells in the sheet. A sheet is obtained. The foaming agent secondarily acts as a plasticizer for lowering the melt viscosity of the raw material resin composition, and lowers the temperature for bringing the raw material resin composition into a plasticized state.

Examples of the effervescent agent include aliphatic hydrocarbons such as propane, butane, pentane, hexane and heptane; alicyclic hydrocarbons such as cyclobutane, cyclopentane and cyclohexane; chlorodifluoromethane, difluoromethane, trifluoromethane and trichlorofluoro. Methane, dichloromethane, dichlorofluoromethane, dichlorodifluoromethane, chloromethane, chloroethane, dichlorotrifluoroethane, dichloropentafluoroethane, tetrafluoroethane, difluoroethane, pentafluoroethane, trifluoroethane, dichlorotetrafluoroethane, trichlorotrifluoroethane , Tetrachlorodifluoroethane, perfluorocyclobutane and other halogenated hydrocarbons; carbon dioxide, nitrogen, air and other inorganic gases; water and the like.

Further, as the foaming agent, for example, a carrier resin containing an active ingredient of the foaming agent can be preferably used. Examples of the carrier resin include crystalline olefin resins. Of these, crystalline polypropylene resin is preferable. In addition, examples of the active ingredient include hydrogen carbonate and the like. Of these, bicarbonate is preferred. A foaming agent concentrate containing a crystalline polypropylene resin as a carrier resin and a bicarbonate as a pyrolysis foaming agent is preferable.

The content of the foaming agent contained in the foaming agent in the molding step can be appropriately set according to the amount of the thermoplastic resin and the inorganic substance powder, etc., and is 0.04 to 5. It is preferably in the range of 00% by mass.

As the fluidity adjusting agent, various conventional ones can be used. Examples include, but are not limited to, peroxides such as dialkyl peroxide, such as 1,4-bis [(t-butylperoxy) isopropyl] benzene. Depending on the type of thermoplastic resin used, these peroxides also act as cross-linking agents. In particular, when the thermoplastic resin component has a constituent unit derived from diene, a part of the copolymer is crosslinked by the action of the peroxide, which helps to control the physical properties and processability of the thermoplastic resin composition. Can be. The amount of peroxide added is not particularly limited, but is in the range of 0.04 to 2.00% by mass, particularly about 0.05 to 0.50% by mass, based on the total mass of the thermoplastic resin composition. Is preferable.

<< Preparation method of resin composition >>
As a method for preparing the resin composition of the present invention, a usual method can be used, and it can be appropriately set according to the molding method (extrusion molding, injection molding, vacuum forming, etc.). For example, it can be prepared by kneading and melting a thermoplastic resin and an inorganic substance powder. In melt kneading, it is preferable to knead by applying a high shear stress while uniformly dispersing each component. As the mixing device, various devices such as a general extruder, a kneader, and a Banbury mixer can be used, but it is preferable to knead with a twin-screw kneader, for example. The prepared resin composition can be made into pellets of a desired shape and size, for example, and can be used in the production of various molded products. Further, depending on the shape of the target molded product, it is possible to knead each raw material to prepare a thermoplastic resin composition and mold it at the same time. For example, a sheet-shaped molded product can be manufactured by kneading various raw materials with a twin-screw extruder and extrusion-molding the sheet-shaped product.

≪Molded product≫
The present invention also includes a molded product made of the above-mentioned resin composition. The resin composition of the present invention has good moldability and excellent physical properties such as mechanical strength, despite the fact that the thermoplastic resin is highly filled with calcium carbonate. Therefore, it can be molded into a molded product having various shapes useful for various uses. Since the resin composition of the present invention has a small amount of elution under acidic conditions, it can also be used for molded products that come into direct contact with food, unlike conventional inorganic substance powder-filled resin compositions. Moreover, at that time, it is not necessary to form a two-layer to three-layer structure in which resin layers such as polyolefin are laminated. Therefore, the molded product of the present invention is particularly suitable for food packaging containers and tableware. The present invention further includes a food packaging container made of the above resin composition.

≪Food packaging container≫
The shape of the food packaging container according to the present invention is not particularly limited, and may be of various forms and sizes such as a lunch container, a cup, a plate, a bowl, a bowl, a spoon, a fork, and chopsticks. .. For example, a container having a wall thickness of 40 μm to 10 mm, more preferably a wall thickness of 100 μm to 5 mm may be used. If the wall thickness is within this range, calcium carbonate is uniformly dispersed in the thermoplastic resin, so that good moldability and workability can be obtained, and a uniform and defect-free container body without uneven thickness can be obtained. Can be formed.

<Manufacturing method of molded product>
The method for producing the molded product of the present invention is not particularly limited as long as it can be molded into a desired shape, and any conventionally known method such as extrusion molding, injection molding, vacuum molding, blow molding, or calendar molding can be used. Molding is possible. As described above, the resin composition of the present invention does not need to have a two-layer to three-layer structure with another resin layer when molded into a food packaging container or the like, and thus is molded by a conventional method for molded bodies having various shapes. can do. Furthermore, even when the resin composition according to the present invention contains a foaming agent to obtain a molded product in the form of a foam, if it can be molded into a desired shape, it is conventionally known as a method for molding a foam. , For example, a liquid phase foaming method such as injection foaming, extrusion foaming, foam blow, or a solid phase foaming method such as bead foaming, batch foaming, press foaming, or atmospheric secondary foaming can be used. be. In one aspect of the above-mentioned thermoplastic composition containing crystalline polypropylene as a carrier resin and hydrogen carbonate as a pyrolytic foaming agent, an injection foaming method and an extrusion foaming method can be preferably used.

The molding temperature in injection molding, extrusion molding, etc. varies to some extent depending on the molding method, the type of thermoplastic resin used, etc., and therefore cannot be unconditionally specified, but is preferably the melting point of the thermoplastic resin component. The temperature can be about +5 to 100 ° C., particularly about +10 to 50 ° C., for example, 180 to 260 ° C., more preferably 190 to 230 ° C. At such a temperature, the resin composition according to the present invention can be molded into a predetermined shape without having good draw-down characteristics and ductility, and without causing local modification of the composition.

Hereinafter, the present invention will be described in more detail based on examples. It should be noted that these examples are specific embodiments and practices in order to facilitate understanding of the concept and scope of the present invention disclosed in the present specification and described in the appended claims. The present invention is described only for the purpose of exemplifying the embodiments, and the present invention is not limited to these examples.

[Example 1]
100 parts by mass of heavy calcium carbonate (Softon (trade name) 1000 manufactured by Bikita Flour Chemical Co., Ltd.) with an average particle size of 2.2 μm (by air permeation method) and a specific surface area of 10,000 cm ^{2 / g is polyoxyethylene.} Lauryl ether phosphoric acid (Phosphanol (registered trademark) manufactured by Toho Chemical Industry Co., Ltd. ML-220: C ₁₂ H ₂₅ O (C ₂ H ₄ O) _2- P (= O) (OH) ₂ and [C ₁₂ H ₂₅ O (C ₂ H ₄ O) ₂ ] _{Mixture with 2} P (= O) OH, 1st acid value 140-160) with 3 parts by mass in a Henschel mixer at a temperature of 120 ° C. and a rotation speed of 1200 rpm for 30 minutes. Stirred and surface treated.

60 parts by mass of the surface-treated calcium carbonate obtained above and 40 parts by mass of a polypropylene homopolymer (Prime Polypro® E111G manufactured by Prime Polymer Co., Ltd., melting point 160 ° C.) were added to 0.5 parts by mass of magnesium stearate lubricant. Along with the mass part, it is put into a co-rotating twin-screw kneading extruder HK-25D (φ25 mm, L / D = 41) manufactured by Parker Corporation, and the strands are extruded at a cylinder temperature of 190 to 200 ° C., then cooled and cut. It was pelletized.

Each of the pellets produced as described above is extruded at 220 ° C. by a lab plast mill uniaxial T-die extrusion molding device (φ20 mm, L / D = 25) manufactured by Toyo Seiki Seisakusho Co., Ltd., and a sheet having a thickness of 0.3 mm. Molded into. The obtained sheet was evaluated for physical properties such as strength and elongation by the following test method. The test results are shown in Table 1.
(Acetic acid elution test)
Cut out strip specimen of 30 mm × 30 mm from the sheet, to which 4% acetic acid 45 ml (amount of acetic contact area 1 cm ² per: about 2 ml), was immersed for 30 minutes at 60 ° C.. The sample after immersion was dried and the mass was measured, and the acetic acid elution amount (mass%) was calculated from the mass change before and after immersion. The test was performed at n = 3, and the average value was adopted.
(Tensile strength, elongation)
For tensile strength and elongation, a dumbbell-shaped sample cut out from the above sheet was used, and according to JIS K 7161-2: 2014, under the conditions of 23 ° C. and 50% RH, Autograph AG-100kNXplus (Shimadzu Co., Ltd.) It was measured using Mfg. Co., Ltd.). The tensile direction was the extrusion direction, and the tensile speed was 50 mm / min.
(Stretching characteristics)
The sheet was stretched up to 4 times in the extrusion direction at 100 ° C., and it was observed how many times the sheet was stretched to break.

[Comparative Example 1]
Untreated Softon 1000 was used as the inorganic substance powder, and the same operation as in Example 1 was carried out. The test results are shown in Table 1.

[Example 2]
Polyoxyethylene laurylphenol phosphoric acid instead of polyoxyethylene lauryl ether phosphoric acid (aromatic EO phosphoric acid ester, Phosphanol (registered trademark) manufactured by Toho Kagaku Kogyo Co., Ltd.) LF-200: C ₁₂ H ₂₅ C ₄ H ₄ O (C ₂ H ₄ O) _2- P (= O) (OH) ₂ and [C ₁₂ H ₂₅ OC ₄ H ₄ (C ₂ H ₄ O) ₂ ] ₂ P (= O) OH mixture, No. The same operation as in Example 1 was carried out using 1 acid value 95 to 115). The test results are shown in Table 1.

[Example 3]
Lauryl phosphoric acid instead of polyoxyethylene lauryl ether phosphoric acid (Phosphanol (registered trademark) ML-200: C ₁₂ H ₂₅ OP (= O) (OH) ₂ and (C _{12) manufactured by Toho Chemical Industry Co., Ltd.} Using _{a mixture of H 25} O) ₂ P (= O) OH and a first acid value of 190 to 210), the same operation as in Example 1 was carried out. The test results are shown in Table 1.

[Example 4]
Softon 1000 was dispersed in purified water (concentration 100 g / L) to prepare a slurry. In this slurry, a sodium salt of a phosphate ester having a long-chain unsaturated aliphatic hydrocarbon chain and an ethylene oxide unit (unsaturated EO phosphate ester salt, Phosphanol® RD-720 manufactured by Toho Kagaku Kogyo Co., Ltd.) , The number of carbon atoms of the hydrocarbon chain is 18, and the number of ethylene oxide units is 7) is added to 1 L of the slurry (3% by mass based on calcium carbonate), stirred at 50 ° C. for 30 minutes, filtered, dried and surface-treated. Obtained calcium carbonate.
Using this surface-treated calcium carbonate, a sheet was prepared in the same manner as in Example 1, and the physical properties were evaluated. The test results are shown in Table 1.

[Comparative Example 2]
As the surface-treated calcium carbonate, commercially available fatty acid surface-treated heavy calcium carbonate (average particle size 2.2 μm; Ryton (registered trademark) S-4 manufactured by Bihoku Powder Industry Co., Ltd.) was used, and the same operation as in Example 1 was performed. went. The test results are shown in Table 1.

[Comparative Example 3]
Maleic anhydride-modified polypropylene (maleic anhydride-modified resin; Umex® 1010 manufactured by Sanyo Kasei Kogyo Co., Ltd.) was used as the surface treatment agent instead of polyoxyethylene lauryl ether phosphoric acid, and the temperature during surface treatment was 180 ° C. The same operation as in Example 1 was performed except that. The test results are shown in Table 1.

[Comparative Example 4]
A styrene-maleic acid ester (maleic acid-modified resin; Regit (registered trademark) SM-101 manufactured by Sanyo Chemical Industries, Ltd.) was used as a surface treatment agent, and the same operation as in Comparative Example 3 was carried out. The test results are shown in Table 1.

According to the present invention, it was found that the samples of Examples 1 to 4 containing calcium carbonate surface-treated with a phosphoric acid ester all had a small amount of acetic acid eluted and were suitable for food use. In particular, in the sample of Example 1 which was surface-treated with a phosphoric acid ester having an ethylene oxide unit, particularly polyoxyethylene lauryl ether phosphoric acid, the amount of acetic acid eluted was significantly reduced. As shown in Comparative Example 1, in a resin composition filled with a large amount of calcium carbonate, the amount of acetic acid eluted tends to be large, and the tensile strength and the like tend to be small. On the other hand, in the samples of Examples 1 to 4, although the sample was filled with a large amount of inorganic substance powder, not only the amount of acetic acid eluted but also the tensile property was good, and the effect of surface treatment with a phosphoric acid ester was shown. rice field. Since the raw material calcium carbonate is different, a simple comparison cannot be made, but the amount of acetic acid eluted in the examples is reduced and the tensile strength is also higher than that of the sample of Comparative Example 2 using calcium carbonate surface-treated with fatty acid. Especially, the sample of Example 1 was large. In addition, it did not break even when stretched up to 4 times, and was excellent in moldability. Compared with the results of Comparative Examples 3 and 4 in which the surface was treated with the modified resin, the surface treatment effect of the phosphoric acid ester, particularly polyoxyethylene lauryl ether phosphoric acid, is more remarkable.

[Example 5, Comparative Example 5]
The same operations as in Example 1 and Comparative Example 2 were carried out except that 70 parts by mass of the surface-treated calcium carbonate and 30 parts by mass of the polypropylene homopolymer were used. The test results are shown in Table 2.

[Example 6]
The same operation as in Example 5 was carried out except that the amount of phosphoric acid ester at the time of surface treatment was 1 part by mass. The test results are shown in Table 2.

[Comparative Example 6]
A surface-treated calcium carbonate was prepared in the same manner as in Comparative Example 3 by using maleic anhydride-modified polypropylene (maleic anhydride-modified resin; Umex® 5200 manufactured by Sanyo Kasei Kogyo Co., Ltd.) instead of maleic anhydride-modified polypropylene. .. Using 70 parts by mass of the obtained surface-treated calcium carbonate and 30 parts by mass of the polypropylene homopolymer, the same operations as in Examples 5 to 6 were carried out. The test results are shown in Table 2.

[Comparative Examples 7 to 8]
The same operations as in Comparative Examples 3 and 4 were carried out except that 70 parts by mass of the surface-treated calcium carbonate and 30 parts by mass of the polypropylene homopolymer were used. The test results are shown in Table 2.

According to the present invention, the samples of Examples 5 and 6 containing calcium carbonate surface-treated with a phosphate ester all had a smaller amount of acetic acid eluted than the sample of Comparative Example 5 containing general-purpose fatty acid-treated calcium carbonate. It turned out to be suitable for food applications. The tensile properties were also good. On the other hand, in Comparative Examples 6 to 8, the amount of acetic acid eluted was low because the calcium carbonate particles were covered with the modified resin, but the tensile properties were significantly deteriorated. It has been shown that the present invention has a remarkable effect.

Based on the above, the thermoplastic resin composition containing calcium carbonate, which has been surface-treated with a surface treatment agent containing a phosphoric acid ester according to the present invention, is under acidic conditions despite being highly filled with an inorganic substance powder. It has been clarified that the elution amount is small, the moldability is good, and the physical properties such as mechanical strength are excellent, and it is particularly suitable for food packaging containers and tableware.

Claims (7)

In a resin composition containing a thermoplastic resin and an inorganic substance powder in a mass ratio of 50:50 to 10:90.
The inorganic substance powder, Ri surface treated calcium carbonate der with a surface treating agent containing a phosphoric acid ester,
A resin composition , wherein the phosphoric acid ester is polyoxyethylene lauryl ether phosphoric acid. The resin composition according to claim 1 , wherein the calcium carbonate is calcium carbonate particles having an average particle diameter of 0.7 μm or more and 6.0 μm or less by an air permeation method according to JIS M-8511. The resin composition according to claim 1 or 2 , wherein the calcium carbonate is heavy calcium carbonate. The resin composition according to any one of claims 1 to 3 , wherein the thermoplastic resin is a polyolefin resin. The resin composition according to claim 4 , wherein the polyolefin-based resin comprises a polyethylene-based resin and / or a polypropylene-based resin. A molded product comprising the resin composition according to any one of claims 1 to 5. A food packaging container comprising the resin composition according to any one of claims 1 to 5.