TWI529175B - Resin nucleating agent and resin composition - Google Patents

Description

Crystal nucleating agent and resin composition for resin

The present invention relates to a nucleating agent for a resin such as a polylactic acid resin or a polyolefin resin, and a resin composition.

In terms of protecting the natural environment, research on aliphatic polyesters which are biodegradable in the natural environment is being carried out in large quantities. Among them, polylactic acid resin is widely used as a packaging material for packaging materials, clothing materials, fiber materials, and electrical and electronic products because it has a melting point of 160 to 180 ° C and excellent transparency.

However, polylactic acid resins have a problem that the so-called crystallization rate is slow. When the crystallization rate is slow, the degree of crystallization becomes low, and heat resistance is deteriorated. For example, when the polylactic acid resin is molded by injection molding or the like which cannot be stretched, the degree of crystallization of the molded article is lowered, and when it exceeds the glass transition temperature before and after 60 ° C, it is disadvantageous in that it is easily deformed. Therefore, in order to increase the degree of crystallization, an attempt has been made to increase the temperature of the mold at the time of injection molding and to lengthen the cooling time in the mold. However, in this method, since the molding time is prolonged, productivity is a problem.

Further, as a method of increasing the crystallization rate of the polylactic acid resin or the polypropylene resin, for example, a method of adding a crystal nucleating agent which is a primary crystal nucleus of a resin of a crystalline polymer is known. And promote crystal growth and increase the speed of crystallization.

In the case of the nucleating agent of the polylactic acid resin, the inorganic particles are formed of talc and/or boron nitride having a specific particle diameter or less (refer to Patent Document 1), and the guanamine compound is represented by a specific formula (refer to Patent Document 2). a sorbitol derivative (refer to Patent Document 3), a phosphate metal salt, a basic inorganic aluminum compound (refer to Patent Document 4), a metal salt of phenylphosphonic acid (refer to Patent Document 5), etc. It is revealed that a more effective development of a nucleating agent for a resin is desired. Further, in order to shorten the molding time, it is also desirable to increase the crystallization temperature.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Publication No. Hei 8-3432 (Application No.)

[Patent Document 2] Japanese Patent Publication No. Hei 10-87975 (Application No.)

[Patent Document 3] Japanese Patent Publication No. Hei 10-158369 (Application No.)

[Patent Document 4] Japanese Laid-Open Patent Publication No. 2003-192883 (Application No.)

[Patent Document 5] International Publication No. 2005-97894 (Application Patent Range)

An object of the present invention is to provide a novel resin nucleating agent and a resin composition which can improve the crystallization rate and the crystallization temperature of a resin, in order to solve the above problems of the prior art.

The crystal nucleating agent for a resin of the present invention which solves the above problems is characterized in that it contains basic zinc cyanurate particles.

Further, it may be a nucleating agent for a polylactic acid resin or a nucleating agent for a polyolefin resin.

The alkaline cyanuric acid cyanide particles may have an average particle diameter D ₅₀ of 80 to 900 nm and a specific surface area of 20 to 100 m ² /g as measured by a laser diffraction method.

Further, the alkaline cyanuric acid cyanide particles may be at least one selected from zinc oxide and basic zinc carbonate, cyanuric acid and water, and the cyanuric acid concentration is 0.1 to 10.0% by mass based on water. Generally, the blended slurry is produced by wet dispersion using a dispersion medium having a temperature range of 5 to 55 °C.

Further, it may contain a metal salt of phenylphosphonic acid, and the metal salt of the above phenylphosphonic acid may be zinc phenylphosphonate, lithium phenylphosphonate, sodium phenylphosphonate, potassium phenylphosphonate, calcium phenylphosphonate, magnesium phenylphosphonate and benzene. At least one selected from the group consisting of manganese phosphonates.

The resin composition of the present invention is characterized by comprising a resin and basic zinc cyanuric acid particles.

In particular, the resin-based polylactic acid resin preferably contains 0.01 to 10.0 parts by mass of the basic zinc cyanuric acid particles per 100 parts by mass of the polylactic acid resin.

In addition, the resin-based polyolefin resin preferably contains 0.01 to 10.0 parts by mass of the basic zinc cyanurate particles per 100 parts by mass of the polyolefin resin.

Further, the polyolefin-based resin may be at least one selected from the group consisting of a polypropylene resin, a polyethylene resin, and a polyamide resin.

Among them, a metal salt of phenylphosphonic acid may be contained.

According to the present invention, a novel resin nucleating agent can be provided by using basic zinc cyanurate particles. Among them, the resin composition containing the crystal nucleating agent and the resin has a high crystallization rate and a high crystallization temperature. Therefore, a molded article having high crystallinity and compactness and high rigidity can be obtained in a short time. Then, by using a zinc citrate particle having an average particle diameter D ₅₀ of 80 to 900 nm and a specific surface area of 20 to 100 m ² /g as measured by a laser diffraction method, a molded article can be obtained. The transparency is enhanced. Further, by further containing a metal salt of basic zinc cyanurate particles and phenylphosphonic acid, it is more excellent as a nucleating agent for a resin.

[Best form of implementing the invention]

The crystal nucleating agent for a resin of the present invention is one containing basic zinc cyanuric acid particles. Basic zinc cyanurate, which is known as a corrosion inhibitor for iron-based metal surfaces, has not been used as a nucleating agent for resins, and has been discovered as a crystalline polymer by the team of the present invention. The primary nucleus of the resin promotes crystal growth and increases the crystallization rate. Moreover, since it has a function of increasing the crystallization temperature, it can be used as a crystal nucleating agent.

By using the basic zinc cyanurate particles as a crystal nucleating agent, the crystallization rate of the resin is increased, so that the degree of crystallization of the resin is increased, and the heat resistance of the molded product of the resin can be improved. In addition, when the crystallization rate is increased, the time required for crystallization is shortened, and a molded product of a resin can be obtained in a short time, thereby improving productivity. Among them, by performing crystallization in a short time, the spherulite size is reduced, and a molded article having excellent transparency and high rigidity can be obtained. In addition, since the crystallization temperature of the resin is also increased, when the resin is molded by using a mold such as injection molding, the cooling temperature of the mold can be increased, so that a molded product of the resin can be obtained in a short time, and productivity can be improved. .

The size of the basic zinc cyanuric acid particles is not particularly limited, for example, by using a laser having a mean particle diameter D ₅₀ of 80 to 900 nm and a specific surface area of 20 to 100 m ² /g as measured by a laser diffraction method. The zinc cyanurate particles can be used as a crystal nucleating agent for resins having high transparency.

The basic zinc cyanurate particles can be produced, for example, by reacting at least one selected from zinc oxide and basic zinc carbonate with cyanuric acid, if necessary, by heating or the like. Since zinc oxide, basic zinc carbonate, and cyanuric acid are inexpensive, an inexpensive nucleating agent for a resin can be provided. The method for producing basic zinc cyanurate by reacting at least one selected from zinc oxide and basic zinc carbonate with cyanuric acid is not particularly limited, and for example, zinc oxide and cyanuric acid are used, for example. A method for producing a reaction in boiling water or a paste in which zinc oxide and cyanuric acid are mixed, and heated at 50 to 250 ° C, and pulverized by a pin disc mill or a wing type Machine, a method of manufacturing by adding shearing action.

Further, it is also possible to use a blended slurry obtained by using at least one selected from zinc oxide and basic zinc carbonate, cyanuric acid and water to have a concentration of cyanuric acid of 0.1 to 10.0% by mass based on water. The alkaline zinc cyanurate particles are produced by wet dispersion using a dispersion medium having a temperature range of 5 to 55 °C. By this production method, fine alkaline zinc cyanurate particles having an average particle diameter D ₅₀ of 80 to 900 nm and a specific surface area of 20 to 100 m ² /g as measured by a laser diffraction method can be produced. This manufacturing method will be described in detail below.

Specifically, first, at least one selected from zinc oxide and basic zinc carbonate, cyanuric acid and water are used to make the concentration of cyanuric acid 0.1 to 10.0% by mass, preferably 0.1 to 5.0, with respect to water. The blending was adjusted to form a mixed slurry. When the concentration of cyanuric acid in water is more than 10% by mass, the viscosity of the slurry becomes high in a paste form, and when the dispersion medium is wet-dispersed in the subsequent stage, the dispersion medium cannot move. On the other hand, when the concentration of cyanuric acid in water is lower than 0.1% by mass, the productivity is deteriorated, which is not preferable.

Further, the ratio of at least one selected from zinc oxide and basic zinc carbonate to the cyanuric acid is not particularly limited, and the total amount of zinc oxide in terms of molar ratio, zinc oxide and basic zinc carbonate/cyanide is The acid is preferably 1.0 to 5.0, more preferably 2.0 to 3.0. When the total amount of zinc oxide conversion/cyanuric acid is higher than 5.0 or lower than 1.0, zinc oxide, basic zinc carbonate or cyanuric acid which does not contribute to the reaction tends to remain in a large amount.

Next, the obtained mixed slurry is wet-dispersed by using a dispersion medium having a temperature range of 5 to 55 ° C, and at least one selected from zinc oxide and basic zinc carbonate is reacted with cyanuric acid to produce Basic zinc cyanurate particles.

The wet dispersion is carried out using a dispersion medium. By wet dispersion using a dispersion medium, at least one selected from zinc oxide and basic zinc carbonate can be subjected to mechanochemical polishing reaction with cyanuric acid by mechanical energy generated by the impact of the dispersion medium. . The so-called mechanochemical polishing reaction refers to a process in which mechanical energy is imparted to zinc oxide, alkaline zinc carbonate or cyanuric acid in a plurality of ways by the impact of a dispersion medium to cause a chemical reaction.

Examples of the dispersion medium include, for example, stabilized zirconium beads, quartz glass beads, soda lime glass beads, alumina beads, or a mixture thereof. When it is considered that the dispersion medium collides with each other to cause the dispersion of the dispersion medium, it is preferable to use the stabilized zirconium beads as the dispersion medium. Then, the size of the dispersion medium, for example, 0.1 to 10 mm in diameter, preferably 0.5 to 2.0 mm in diameter. When the diameter of the dispersion medium is less than 0.1 mm, the impact energy of the pulverization medium is small, and the mechanochemical polishing reactivity tends to be weak. Further, when the diameter of the dispersion medium is larger than 10 mm, the impact energy of the dispersion medium is too large, and the dispersion of the dispersion medium causes a large amount of contamination, which is not preferable.

A device for wet dispersion using a dispersion medium, as long as the mixed slurry can be added to a container into which a dispersion medium has been introduced, and stirred, by dispersing the medium with zinc oxide, basic zinc carbonate or cyanuric acid. The impact is generated, and the zinc oxide or the basic zinc carbonate and the cyanuric acid are subjected to a mechanochemical polishing reaction, and are not particularly limited. For example, for example, a sand grinder, a horizontal bead mill, A grinder, a bead mill (made by Ashizawa Finetech Co., Ltd.), and the like. In addition, the number of revolutions of the apparatus for stirring the dispersion medium, the reaction time, and the like may be appropriately adjusted in accordance with a desired particle diameter or the like.

Further, it is necessary to carry out wet dispersion at 5 to 55 ° C, preferably 5 to 45 ° C. When wet dispersion is carried out at a temperature higher than 55 ° C, cyanuric acid is dissolved in water, and the dissolved cyanuric acid reacts rapidly with zinc oxide or basic zinc carbonate, thereby promoting grain growth. Or, as shown in the synthesis example described later, the produced basic zinc cyanurate has a large particle size. In particular, when the wet dispersion is carried out at a low temperature of 45 ° C or lower, the particles are particularly small, and fine particles having an average particle diameter D ₅₀ of 500 nm or less can be produced, for example, by a laser diffraction method. Further, since it can be produced at such a low temperature, it can be produced by using a device such as a resin having a weak heat.

Here, the wet dispersion of the dispersion medium is not used as described above, and the shearing action is applied by a bar mill or a wing mill, or because it is relative to zinc oxide, alkaline zinc carbonate or melamine. The acid-cut member can generate an impact in only one direction, and cannot produce a mechanochemical polishing reaction, and it is impossible to obtain an alkali zinc cyanurate particle having a small particle diameter.

In this manner, at least one selected from the group consisting of zinc oxide and basic zinc carbonate, cyanuric acid, and water are mixed with a concentration of cyanuric acid of 0.1 to 10.0% by mass relative to water. The average particle diameter D ₅₀ of the zinc cyanurate microparticles obtained by the wet dispersion method using a dispersion medium having a temperature range of 5 to 55 ° C is 80 to 900 nm by a laser diffraction method. It is preferably 100 to 500 nm and has a specific surface area of 20 to 100 m ² /g, preferably 30 to 80 m ² /g. That is, it is a particle diameter small and a large specific surface area. In addition, even if the zinc cyanurate granules having such a large amount of zinc cyanuric acid microparticles and the particle diameter are relatively large, and pulverized by a pulverizer such as a back spray mill, it is impossible to The average particle diameter D ₅₀ measured by the diffraction method is as small as 80 to 900 nm.

In addition, the basic zinc cyanuric acid microparticles obtained by the above-described production method are non-spherical, and are acicular or plate-shaped as shown in the synthesis example described later, that is, they can be elongated microparticles. Such basic zinc cyanuric acid microparticles have, for example, a primary particle diameter observed by a transmission electron microscope, and have a major axis of 100 to 800 nm and a minor axis of 10 to 60 nm.

Further, the alkaline zinc cyanuric acid slurry containing the obtained basic zinc cyanuric acid microparticles can be used as a resin nucleating agent as it is, and the slurry can be dried to form a powder. As a crystal nucleating agent for resins.

Further, the crystal nucleating agent for a resin of the present invention may contain both a basic zinc cyanurate particle and a metal salt of phenylphosphonic acid. By containing a metal salt of phenylphosphonic acid, the crystallization rate of the resin and the crystallization temperature can be further increased as compared with the nucleating agent for the resin formed only from the basic zinc cyanurate particles.

Here, the metal salt of phenylphosphonic acid is a crystal nucleating agent for a resin, but has a problem of so-called high cost. In the present invention, by simultaneously using a metal salt of phenylphosphonic acid as a low-cost metal salt of basic zinc cyanurate particles and phenylphosphonic acid, it is possible to simultaneously increase the crystallization rate and crystallization temperature of the resin. The effect is the result of the so-called cost reduction.

Examples of the metal salt of phenylphosphonic acid include zinc phenylphosphonate, lithium phenylphosphonate, sodium phenylphosphonate, potassium phenylphosphonate, calcium phenylphosphonate, magnesium phenylphosphonate, manganese phenylphosphonate and the like.

The crystal nucleating agent for a resin containing a basic metal cyanurate particle and a metal salt of phenylphosphonic acid, and the content ratio of each component is not particularly limited. For example, if the cyanuric acid is 20 to 40% by mass, the phenylphosphine is used. The acid is 10 to 30% by mass. When the cyanuric acid component of the crystal nucleating agent composition is less than 20% by mass, the content of the basic zinc cyanurate is small, and the content of zinc phenylphosphonate is high, and the phenylphosphonic acid is high in price, even if it is high. By increasing the concentration of these above phenylphosphonic acids, the performance of the nucleating agent cannot be improved. On the other hand, when the concentration of the cyanuric acid component of the crystal nucleating agent composition is more than 40% by mass, the content of the basic zinc cyanurate increases, and the content of the zinc phenylphosphonate becomes too small, and the crystal nucleating agent Performance will be reduced, so it is not appropriate. Further, the cyanuric acid is represented by the molecular formula C ₃ N ₃ O ₃ H ₃ and can be quantified by the amount of nitrogen measured by CHN elemental analysis. The phenylphosphonic acid is represented by the molecular formula C ₆ H ₇ O ₃ P and can be quantified by the amount of phosphorus measured by fluorescent X-ray analysis.

Further, the ratio of zinc to zinc phenylphosphonate in the ratio of zinc to zinc phenylphosphonate contained in the nucleating agent for the resin containing the basic zinc cyanurate particles and the metal salt of phenylphosphonic acid is preferably 1 in quality. Big but less than 4. Even if the concentration of phenylphosphonic acid is 1 or less and the price is increased, the performance of the crystal nucleating agent cannot be improved, and when it is 4 or more, the performance of the crystal nucleating agent tends to decrease.

Further, the crystal nucleating agent for the resin may contain magnesium hydroxide, magnesium oxide or the like.

The method for producing a nucleating agent for a resin containing the basic zinc cyanuric acid particles of the present invention and the metal salt of phenylphosphonic acid is not particularly limited. For example, the basic zinc cyanurate particles can be used. It is produced by mixing a metal salt of phenylphosphonic acid with a mixer or the like.

Further, the crystal nucleating agent for a resin containing basic zinc cyanurate particles and a metal salt of phenylphosphonic acid may also be used as a raw material of magnesium phenylphosphonate, lithium phenylphosphonate, sodium phenylphosphonate or phenylphosphine. An aqueous solution of a metal salt of phenylphosphonic acid such as potassium acid, at least one selected from zinc oxide and basic zinc carbonate, and cyanuric acid are produced by heating or the like as needed to cause a reaction.

Further, the crystal nucleating agent for a resin containing basic zinc cyanurate particles and a metal salt of phenylphosphonic acid may also be used as a raw material of magnesium phenylphosphonate, lithium phenylphosphonate, sodium phenylphosphonate or phenylphosphine. An aqueous solution of a metal salt of phenylphosphonic acid such as potassium acid, at least one selected from zinc oxide and basic zinc carbonate, cyanuric acid and water, and a concentration of cyanuric acid of 0.1 to 10.0% by mass relative to water. The blended slurry is produced in a temperature range of 5 to 55 ° C by using a dispersion type stirring blade or a wet dispersion of a dispersion medium to strongly stir and disperse, and reacting the respective raw materials. The slurry obtained by the production method is dried at 110 ° C to produce a metal hydrogen containing fine basic zinc cyanurate, zinc phenylphosphonate, and a metal salt of the above phenylphosphonic acid constituting the raw material. A nucleating agent for a resin of an oxide (for example, magnesium hydroxide or the like). The resin nucleating agent has a specific surface area of 15 to 100 m ² /g, preferably 20 to 100 m ² /g. This manufacturing method will be described in detail below.

First, an aqueous solution of a metal salt of phenylphosphonic acid as a raw material is adjusted by dissolving a carbonate or a metal hydroxide with phenylphosphonic acid in water. For example, magnesium carbonate or magnesium hydroxide and phenylphosphonic acid can be prepared by dissolving magnesium/phenylphosphonic acid in a ratio of magnesium to phenylphosphonic acid in a molar ratio of, for example, 0.3 to 0.6. . Here, when the magnesium/phenylphosphonic acid (mole ratio) is less than 0.3, the pH of the mixed slurry is 7 or less. Then, when the slurry for drying the slurry having a pH of 7 or less is kneaded in the polylactic acid resin, a part of the polylactic acid is dissolved, so that the crystallization rate is high and the crystallization temperature is high. Therefore, the performance of the so-called crystal nucleating agent is small, and the resulting zinc phenylphosphonate becomes coarse particles, and the performance of the nucleating agent of the polylactic acid resin is lowered. Among them, the dissolved portion of the polylactic acid resin is solidified as it is, and the portion becomes brittle and the mechanical properties are lowered. Further, when magnesium/phenylphosphonic acid (mole ratio) is larger than 0.6, magnesium benzene phosphonate particles are precipitated. Therefore, magnesium/phenylphosphonic acid (mole ratio) is preferably in the range of 0.3 to 0.6.

Next, at least one selected from the group consisting of zinc oxide and basic zinc carbonate, cyanuric acid and water are used to make the concentration of cyanuric acid 0.1 to 10.0% by mass, preferably 1.0 to 5.0% by mass, based on the water. The addition is carried out, and then an aqueous solution of the above metal salt of phenylphosphonic acid is mixed. For example, when an aqueous solution of a metal salt of phenylphosphonic acid is used as an aqueous solution of magnesium phenylphosphonate, the concentration of the aqueous solution of magnesium phenylphosphonate is preferably adjusted to be 1.0 to 3.0% by mass to adjust the mixed slurry. When the concentration of cyanuric acid in water is higher than 10% by mass, the viscosity of the slurry becomes high and becomes a paste, and when the dispersion type stirring blade in the subsequent stage or the wet dispersion using a dispersion medium is used, It will become difficult to stir and disperse strongly. On the other hand, when the concentration of cyanuric acid in water is lower than 0.1% by mass, the productivity is poor, which is not preferable.

Further, the ratio of at least one selected from zinc oxide and basic zinc carbonate to the cyanuric acid is not particularly limited, and the total amount of zinc oxide in terms of molar ratio, zinc oxide and basic zinc carbonate/cyanide is The acid is preferably from 1.0 to 5.0, more preferably from 2.5 to 3.0. When the total amount of zinc oxide conversion/cyanuric acid is higher than 5.0 or lower than 1.0, zinc oxide, basic zinc carbonate or cyanuric acid which does not contribute to the reaction tends to remain in a large amount.

Further, the blending ratio of phenylphosphonic acid contained in the metal salt of phenylphosphonic acid is not particularly limited, and the concentration of phenylphosphonic acid contained in the metal salt of phenylphosphonic acid is preferably 1.5 to 3.0% by mass. . This is because even when it is more than 3.0% by mass, the performance of the nucleating agent of the polylactic acid resin cannot be greatly improved, and if it is lower than 1.5% by mass, the performance of the nucleating agent of the polylactic acid resin is lowered.

Next, the obtained mixed slurry is strongly stirred and dispersed in a temperature range of, for example, 5 to 55 ° C by a dispersion type stirring blade or a wet dispersion using a dispersion medium. Therefore, a metal salt of zinc oxide or basic zinc carbonate and phenylphosphonic acid is obtained while reacting at least one selected from zinc oxide and basic zinc carbonate with cyanuric acid to form basic zinc cyanurate. A reaction is produced to form zinc phenylphosphonate.

Still, it is strongly stirred and dispersed. If it is wet-dispersed at a temperature higher than 55 ° C, the resulting basic zinc cyanurate and zinc phenylphosphonate will become coarse particles, due to the nucleating agent of polylactic acid resin. The performance is lowered, so it is preferably carried out at less than 55 °C. Further, when it is produced by wet dispersion using a dispersion medium, it is possible to produce a primary particle having a long axis of 100 to 1200 nm and a short axis of 10 to 100 nm, which are observed by a transmission electron microscope, by laser diffraction. The crystal nucleating agent for resin having an average particle diameter D ₅₀ of 80 to 900 nm and a zinc phenylphosphonate having a major axis and a short axis of 50 to 800 nm was measured by the method.

a crystal nucleating agent composition containing a metal hydroxide (for example, magnesium hydroxide) of a basic zinc cyanide, zinc phenylphosphonate or a metal salt of a phenylphosphonic acid constituting a raw material thus obtained The slurry containing the same is used as a nucleating agent for a resin as it is, and the slurry can be dried, and it can be used as a resin crystal by using a rod or a jet mill or the like. Nuclear agent.

The size of the nucleating agent for a resin is not particularly limited, and a fine nucleating agent for a resin having high transparency can be obtained by using fine particles having a specific surface area of 20 to 100 m ² /g.

Then, the resin composition of the present invention is a basic zinc cyanurate particle and a resin containing the above-mentioned resin nucleating agent, or a basic zinc cyanurate particle or a phenylphosphine containing the above-mentioned resin nucleating agent. Acid metal salts and resins.

As the resin, for example, polylactic acid or a polyolefin resin is exemplified. Further, two or more kinds of resins can be used. The polylactic acid resin is, for example, a homopolymer or a copolymer of lactic acid, or a blend polymer in which a homopolymer or a copolymer of such lactic acid is used as a main component and a mixture of other resins is mixed. Examples of the other resin to be mixed include a biodegradable resin other than polylactic acid, a general-purpose synthetic resin, and a general-purpose synthetic industrial plastic. When the polylactic acid resin is a copolymer, the arrangement pattern may be any random copolymer, alternating copolymer, block copolymer, or graft copolymer. Moreover, the polylactic acid resin can be used as a polylactic acid resin by crosslinking the above polylactic acid resin with a crosslinking agent by heat, light, radiation, or the like. Of course, two or more kinds of these polylactic acid resins can be used. The molecular weight of the polylactic acid is not particularly limited, and for example, the number average molecular weight is about 10,000 to 500,000. Further, the method for producing the polylactic acid resin is not particularly limited. For example, it is possible to produce a lactide lactide by ring-opening polymerization, or to directly condense a D-form, a L-form, a racemic or the like of lactic acid.

Further, examples of the polyolefin resin include a polyethylene resin, a polypropylene resin, and a polyamide resin. Among them, examples of the polypropylene resin include polypropylene, an ethylene-propylene copolymer, and the like, or a polypropylene which is denatured with an unsaturated carboxylic acid or the acid anhydride. The polypropylene which is denatured with an unsaturated carboxylic acid or the acid anhydride, for example, a polypropylene such as a propylene single polymer or an ethylene-propylene copolymer, or acrylic acid, methacrylic acid, maleic acid, and itaconic acid, An unsaturated carboxylic acid such as fumaric acid, maleic anhydride or itaconic acid anhydride or a copolymer of the acid anhydride or a graft copolymer or the like. Particularly preferred are copolymers of propylene with acrylic acid or maleic anhydride, or graft copolymers. Of course, two or more kinds of these polyolefin resins can be used. The molecular weight of the polyolefin resin is not particularly limited, and for example, the number average molecular weight is about 10,000 to 500,000.

The ratio of the mixing ratio of the basic zinc cyanurate particles to the resin is not particularly limited. When the polylactic acid resin is used as the resin, it is preferred to make the basic zinc cyanurate particles 0.01 based on 100 parts by mass of the polylactic acid resin. ~10.0 parts by mass. In addition, when a polyolefin resin is used as the resin, it is preferable to make the basic zinc cyanurate particles 0.01 to 10.0 parts by mass based on 100 parts by mass of the polyolefin resin. When the amount of the basic zinc cyanurate particles is less than 0.01 parts by mass based on 100 parts by mass of the resin, the effect of increasing the crystallization rate or the crystallization temperature of the resin may be inconspicuous. In addition, when the amount of the basic zinc cyanuric acid particles is more than 10.0 parts by mass based on 100 parts by mass of the resin, the specific gravity of the resin composition becomes too heavy.

Further, in the same manner, when a nucleating agent for a resin containing a basic metal salt of zinc cyanurate particles and phenylphosphonic acid is used, the blending ratio is not particularly limited, and when a polylactic acid resin is used as the resin, the polymer is used. 100 parts by mass of the lactic acid resin is preferably 0.01 to 10.0 parts by mass of the resin nucleating agent containing the metal salt of the basic zinc cyanurate particles and the phenylphosphonic acid. In addition, when a polyolefin resin is used as the resin, it is preferably a resin nucleating agent for a resin containing a basic metal salt of zinc cyanurate particles and phenylphosphonic acid, based on 100 parts by mass of the polyolefin resin. It is 0.01 to 10.0 parts by mass.

The resin composition of the present invention may contain an inorganic filler. Examples of the inorganic filler include glass fiber, carbon fiber, talc, mica, vermiculite, kaolin, clay, apatite, glass beads, glass flakes, potassium titanate, calcium carbonate, magnesium sulfate, and titanium oxide. The shape of the inorganic filler may be any fibrous, granular, plate-like, needle-like, spherical, or powder. The blending amount of the inorganic filler can be, for example, 300 parts by mass or less based on 100 parts by mass of the resin.

Further, the resin composition of the present invention may contain a flame retardant. Examples of the flame retardant include a halogen-based flame retardant such as bromine or chlorine, a lanthanum-based flame retardant such as antimony trioxide or antimony pentoxide, aluminum hydroxide or magnesium hydroxide, and a polyfluorene-based compound. Inorganic flame retardants, red phosphorus, phosphates, ammonium polyphosphate, phosphazene and other phosphorus-based flame retardants, melamine, melam, melem, melamine, trimer Cyanuric acid melamine salt, melamine phosphate, melamine pyrophosphate, melamine polyphosphate, melamine polyphosphate, melamamine ‧ melemamine double salt, melamine alkylphosphonic acid, melamine phenylphosphonate, melamine sulfate, melam mesylate A melamine-based flame retardant, a fluororesin such as PTFE, or the like. The blending amount of the flame retardant can be, for example, 200 parts by mass or less based on 100 parts by mass of the resin.

Further, the resin composition may contain, in addition to the above components, a heat stabilizer, a light stabilizer, an ultraviolet absorber, an antioxidant, a rinse improver, an antistatic agent, a pigment, a colorant, a release agent, a lubricant, and a plasticizer. Various kinds of coupling agents such as a compatibilizing agent, a foaming agent, a fragrance, an antibacterial antifungal agent, a decane system, a titanium system, an aluminum system, and the like, other various fillers, or a nucleating agent other than the zinc cyanurate particles, Various additives commonly used in the manufacture of general synthetic resins.

The method for producing a resin composition using a resin and a basic metal salt of zinc cyanurate or basic zinc cyanurate and phenylphosphonic acid, and various additives to be added as needed, is not particularly limited and can be used. It is produced in the same manner as the resin composition containing a conventional crystal nucleating agent. For example, the resin and the basic zinc cyanurate, or the metal salt of basic zinc cyanurate and phenylphosphonic acid, and the additives added as needed are mixed in various mixers, using uniaxial or two A resin composition can be produced by kneading at a temperature of, for example, about 150 to 220 ° C in a shaft extruder or the like. Further, a precursor mixture containing a high concentration of basic zinc cyanurate or a metal salt of basic zinc cyanurate and phenylphosphonic acid, and an additive added as needed, is added to the resin. The method is also possible. Further, it may be a method of adding a basic zinc cyanurate or a basic metal salt of zinc cyanurate and phenylphosphonic acid in the polymerization stage of the resin.

In the resin composition of the present invention, various molded articles can be easily produced by a general molding method such as injection molding, air blowing molding, vacuum molding, or compression molding. The molded article can be used, for example, as a packaging material for a container, a film, or the like, a clothing material, a fiber material, an electric or electronic product, or the like.

Next, the resin composition of the present invention has a high crystallization rate of the resin because of the basic zinc cyanurate particles containing the crystal nucleating agent or the basic zinc cyanurate particles and the metal salt of phenylphosphonic acid. Therefore, the degree of crystallization of the resin becomes high, and a molded article having good heat resistance can be obtained. Moreover, by increasing the crystallization rate, the time required for crystallization is shortened, and the molded product of the resin can be produced in a short time. Then, by crystallization in a short time, the spherulite size is reduced, and a molded article having excellent transparency and high rigidity can be obtained ^. In addition, by containing basic zinc cyanurate particles, or basic zinc cyanurate particles and a metal salt of phenylphosphonic acid, the crystallization temperature of the resin is also increased, and the resin is used for injection molding or the like. When the mold is molded, since the cooling temperature of the mold can be increased, the molded product of the resin can be produced in a short time.

[Examples]

Hereinafter, the present invention and the comparative examples will be further described in detail, but the present invention is not limited to the embodiments.

(measuring device)

The analysis of the examples and comparative examples was carried out using the following apparatus and conditions.

Penetrating electron microscope observation: JEM-1010 (manufactured by JEOL Ltd.) was applied with a voltage of 100 kV.

Laser diffraction method particle diameter measurement: SALD-7000 type (manufactured by Shimadzu Corporation), and 1 g of the sample was diluted 200 times with pure water to measure.

Specific surface area measurement: a nitrogen sorption method surface area measuring device Monosorb machine (manufactured by yuasa-ionics Co., Ltd.).

Gravimetric analysis: After about 2 g of the sample was placed in a precision scale of a magnetic system, the solid content was calculated by mass after drying at 110 °C.

X-ray powder diffraction analysis: powder X-ray diffraction device RINT Ultima type (manufactured by Rigaku).

Elemental analysis: Fully automatic elemental analysis device CHNS/OAnalyzer 2400 (manufactured by PerkinElmer Co., Ltd.).

(Synthesis Example 1)

In a batch sander container with a volume of 1 liter of the inner wall of the urethane resin, 1140 g of pulverized beads of zirconia Φ 1 mm and 300 g of pure water were placed, and the sand mill container was placed. After cooling with a condenser of -5 ° C, the mixture was rotated at 500 rpm using a stir plate, and 5.9 g of cyanuric acid powder (manufactured by Nissan Chemical Industries Co., Ltd.) was charged. The sander container was continuously cooled at a condenser of -5 ° C, and rotated at 500 rpm using a stir plate, and 9.3 g of zinc oxide powder (two types of zinc oxide manufactured by Seiko Chemical Co., Ltd.) was charged. The molar ratio of zinc oxide/cyanuric acid was 2.5, and the concentration of cyanuric acid relative to water was 2.0% by mass. After the zinc oxide powder was charged, the sand mill container was cooled at -5 ° C for 12 hours, and the mixture was rotated at 500 rpm using a stirring disk to disperse. The slurry temperature at this time was 9 °C. Therefore, a solid slurry having a pH of 7.1, a conductivity of 84 μS/cm, and a dry state at 110 ° C was obtained, and was obtained in an amount of 4.8 mass% of a white slurry of 310 g. The 110 ° C dry powder of the obtained white slurry was subjected to elemental analysis, and found to be 10.37 mass% of carbon, 1.35 mass% of hydrogen, 12.05 mass% of nitrogen, and 28.20 mass% of oxygen. Further, this 110 ° C dry powder was thermally decomposed into zinc oxide at 1000 ° C, and then mass measurement was performed to obtain an effective component amount of Zn of the dried powder at 110 ° C. As a result, it was 48.03 mass %. Further, X-ray powder diffraction analysis was performed on the dried powder at 110 ° C. As a result, as shown in Fig. 1, no diffraction peak of cyanuric acid and zinc oxide belonging to the raw material was observed, and alkaline melamine was observed. The diffraction peak of zinc acid. From these results, the dry powder at 110 ° C can be determined to be zinc cyanurate of Zn ₅ (C ₃ N ₃ O ₃ ) ₂ (OH) ₃ ‧3H ₂ O. The fine particles contained in the obtained white slurry were observed by a transmission electron microscope, and the long axis was 100 to 200 nm, and the short axis was 10 to 15 nm. The average particle diameter D measured by the laser diffraction method was used. ₅₀ is 103 nm, and the specific surface area Sw after drying at 70 ° C is 59 m ² /g of basic zinc cyanurate. The results are shown in Table 1. Further, a photograph observed by a transmission electron microscope is shown in Fig. 2.

(Synthesis Example 2)

In a 1-liter inner wall of an amine urethane resin batch sand mill vessel, Φ 1mm into the grinding beads made of zirconia stabilization and 1140g water 300g, a sand mill vessel -5 ℃ While cooling, the condenser was rotated at 1,500 rpm using a stir plate, and 5.9 g of cyanuric acid powder (manufactured by Nissan Chemical Industries Co., Ltd.) was charged. The sander container was continuously cooled while being cooled at -5 ° C, and was rotated at 1,500 rpm using a stir plate, and 9.3 g of zinc oxide powder (two types of zinc oxide manufactured by Nippon Chemical Co., Ltd.) was charged. The molar ratio of zinc oxide/cyanuric acid was 2.5, and the concentration of cyanuric acid relative to water was 2.0% by mass. After the zinc oxide powder was charged, the sand mill container was cooled at 0 ° C for 8 hours, and the mixture was rotated at 1,500 rpm using a stirring disk to disperse. The slurry temperature at this time was 16 °C. Therefore, 311 g of a white slurry having a solid content of pH 7.1, a conductivity of 109 μS/cm, and a dry state at 110 ° C was obtained in an amount of 4.8% by mass. Further, X-ray powder diffraction analysis was performed on the dried powder of 110 ° C of the obtained white slurry, and as a result, the same diffraction pattern as in Synthesis Example 1 was obtained. When the fine particles contained in the obtained white slurry were observed by a transmission electron microscope, the long axis was 100 to 300 nm, and the short axis was 10 to 20 nm. The average particle diameter D measured by the laser diffraction method was used. ₅₀ is 155 nm, and the specific surface area Sw after drying at 70 ° C is 49 m ² /g of basic zinc cyanurate. The results are shown in Table 1.

(Synthesis Example 3)

In a 1-liter inner wall of an amine urethane resin batch sand mill vessel, Φ 1mm into the grinding beads made of zirconia stabilization and 1140g water 300g, a sand mill vessel -5 ℃ While cooling, the condenser was rotated at 2000 rpm using a stir plate, and 5.9 g of cyanuric acid powder (manufactured by Nissan Chemical Industries Co., Ltd.) was charged. The sander container was continuously cooled while being cooled at -5 ° C, and was rotated at 2000 rpm using a stir plate, and 9.3 g of zinc oxide powder (two types of zinc oxide manufactured by Seiko Chemical Co., Ltd.) was charged. The molar ratio of zinc oxide/cyanuric acid was 2.5, and the concentration of cyanuric acid relative to water was 2.0% by mass. After the zinc oxide powder was charged, the sand mill container was cooled at -5 ° C for 8 hours, and the mixture was rotated at 2000 rpm using a stirring disk to disperse. The slurry temperature at this time was 23 °C. Therefore, 305 g of a white slurry having a solid content of 4.8% by mass at pH 7.0, a conductivity of 120 μS/cm, and a drying temperature of 110 ° C was obtained. Further, X-ray powder diffraction analysis was performed on the dried powder of 110 ° C of the obtained white slurry, and as a result, the same diffraction pattern as in Synthesis Example 1 was obtained. The fine particles contained in the obtained white slurry were observed by a transmission electron microscope, and the long axis was 100 to 400 nm, and the short axis was 20 to 30 nm. The average particle diameter D measured by the laser diffraction method was used. ₅₀ is 175 nm, and the specific surface area Sw after drying at 70 ° C is 32 m ² /g of basic zinc cyanurate. The results are shown in Table 1. Further, a photograph observed by a transmission electron microscope is shown in Fig. 3.

(Synthesis Example 4)

In a batch-type sand mill container with a volume of 1 liter of inner wall of urethane resin, 1140 g of pulverized beads of Φ 1 mm and 290 g of pure water were placed, and the container of the sand mill was placed at 20 ° C. While the tap water was cooled, the mixture was rotated at 1,500 rpm using a stir plate, and 9.2 g of cyanuric acid powder (manufactured by Nissan Chemical Industries Co., Ltd.) was charged. The sander container was continuously cooled with tap water of 20 ° C, and the mixture was rotated at 1,500 rpm using a stir plate, and 14.5 g of zinc oxide powder (two types of zinc oxide manufactured by Seiko Chemical Co., Ltd.) was charged. The molar ratio of zinc oxide/cyanuric acid was 2.5, and the concentration of cyanuric acid relative to water was 3.2% by mass. After the zinc oxide powder was charged, the sand mill container was cooled with tap water of 20 ° C for 10 hours, and the mixture was rotated at 1,500 rpm using a stirring disk to disperse. The slurry temperature at this time was 40 °C. Therefore, 300 g of a white slurry having a solid content of 6.8 mass% at pH 6.8, a conductivity of 148 μS/cm, and a drying temperature of 110 ° C was obtained. Further, X-ray powder diffraction analysis was performed on the dried powder of 110 ° C of the obtained white slurry, and as a result, the same diffraction pattern as in Synthesis Example 1 was obtained. The fine particles contained in the obtained white slurry were observed by a transmission electron microscope, and the long axis was 100 to 300 nm, and the short axis was 20 to 30 nm. The average particle diameter D measured by the laser diffraction method was used. ₅₀ is 188 nm, and the specific surface area Sw after drying at 70 ° C is 26 m ² /g of basic zinc cyanurate.

(Synthesis Example 5)

In a batch-type sand mill container in which the inner wall of the volume of 1 liter is a urethane resin, 1140 g of pulverized beads of zirconia Φ 1 mm and 290 g of pure water were placed, and the stirring tray was rotated at 1500 rpm, and 3.9 g of cyanuric acid powder (manufactured by Nissan Chemical Industries Co., Ltd.) was charged. The stirring tray was continuously rotated at 1,500 rpm, and 9.3 g of zinc oxide powder (two types of zinc oxide manufactured by Seiko Chemical Co., Ltd.) was charged. The molar ratio of zinc oxide/cyanuric acid was 2.5, and the concentration of cyanuric acid relative to water was 2.0% by mass. After the zinc oxide powder was charged, the stirring disk was rotated at 1,500 rpm for 5 hours to be dispersed. The slurry temperature at this time was 50 °C. Therefore, 300 g of a white slurry having a pH of 8.2, a conductivity of 176 μS/cm, and a dry state at 110 ° C was obtained in an amount of 4.8% by mass. Further, X-ray powder diffraction analysis was performed on the dried powder of 110 ° C of the obtained white slurry, and as a result, the same diffraction pattern as in Synthesis Example 1 was obtained. The fine particles contained in the obtained white slurry were observed by a transmission electron microscope, and the long axis was 100 to 200 nm, and the short axis was 20 to 40 nm. The average particle diameter D measured by the laser diffraction method was used. ₅₀ is 623 nm, and the specific surface area Sw after drying at 70 ° C is 25 m ² /g of basic zinc cyanurate. The results are shown in Table 1.

(Synthesis Example 6)

In a batch-type sand mill container with a volume of 1 liter of inner wall of urethane resin, 1140 g of pulverized beads of Φ 1 mm and 298 g of pure water were placed, and the container of the sand mill was set at 10 ° C. While cooling, the condenser was rotated at 2000 rpm using a stir plate, and 4.3 g of cyanuric acid powder (manufactured by Nissan Chemical Industries Co., Ltd.) was charged. The sander container was continuously cooled at a condenser of 10 ° C, and the mixture was rotated at 1,500 rpm using a stir plate, and 9.0 g of an alkali zinc carbonate powder (zinc oxide component: 74.8 mass%, manufactured by Seiko Chemical Co., Ltd.) was charged. The amount of zinc oxide converted / the molar ratio of cyanuric acid was 2.5, and the concentration of cyanuric acid with respect to water was 1.4% by mass. After the zinc oxide powder was charged, the sand mill container was cooled at 10 ° C for 8 hours, and the mixture was rotated at 1,500 rpm using a stirring disk to disperse. The slurry temperature at this time was 30 °C. Therefore, a solid slurry having a pH of 6.3, a conductivity of 556 μS/cm, a viscosity of 198 mPa·s, and a dry state at 110 ° C was obtained, and was 3.0 g of a white slurry of 3.5% by mass. Further, X-ray powder diffraction analysis was performed on the dried powder of 110 ° C of the obtained white slurry, and as a result, the same diffraction pattern as in Synthesis Example 1 was obtained. The fine particles contained in the obtained white slurry were observed by a transmission electron microscope, and the long axis was 100 to 300 nm, and the short axis was 20 to 40 nm. The average particle diameter D measured by the laser diffraction method was used. ₅₀ is 303 nm, and the specific surface area Sw after drying at 70 ° C is 30 m ² /g of basic zinc cyanurate. The results are shown in Table 1.

(Synthesis Example 7)

Into a mixing tank of a volume of 200 liters, 24 kg of pure water and 1.80 kg of zinc oxide powder (two kinds of zinc oxides manufactured by Seiko Chemical Co., Ltd.) were mixed and dispersed, and the concentration of zinc oxide was 7.69 mass%. The slurry is 26kg. Next, 66 kg of Φ 1 mm stabilized zirconium pulverized beads were placed in a horizontal bead mill with an effective volume of 10.66 liters of urethane resin (Ashizawa Finetech bead mill PM25TEX- H). 144 kg of pure water was placed in a circulation tank equipped with a condenser, and the disk of the bead mill was rotated at a peripheral speed of 10 m/sec, and pure water was supplied to the bead mill at a supply rate of 5 kg/min. Circulate pure water. After the start of the cycle, 1.39 kg of cyanuric acid powder (manufactured by Nissan Chemical Industries Co., Ltd.) was charged. After the cyanuric acid powder was charged, the temperature of the circulating slurry was adjusted to 32° C. by a condenser, and then 24.5 kg of a zinc oxide slurry having a zinc oxide equivalent concentration of 7.69 mass% was divided into 5 times and taken for 10 minutes. Add it. The molar ratio of zinc oxide/cyanuric acid was 2.5, and the concentration of cyanuric acid relative to water was 0.7% by mass. After the addition of the zinc oxide slurry, the disk of the bead mill was also rotated at a peripheral speed of 10 m/sec, and the slurry was circulated at a supply rate of 5 kg/min for 15 hours to be dispersed. Further, the temperature of the circulating slurry was adjusted to 32 ° C by a condenser. Therefore, a solid slurry having a pH of 6.8, a conductivity of 67 μS/cm, a viscosity of 51 mPa·s, and a solid content of 110% by weight of 166 kg of a 1.8% by mass white slurry was obtained. The X-ray powder diffraction analysis of the dried powder of 110 ° C of the obtained white slurry was carried out, and the same diffraction pattern as in Synthesis Example 1 was obtained. The fine particles contained in the obtained white slurry were observed by a transmission electron microscope with a long axis of 100 to 600 nm and a minor axis of 25 to 50 nm, and the average particle diameter D measured by the laser diffraction method. ₅₀ is 310 nm, and the specific surface area Sw after drying at 70 ° C is ₅₁ m ² /g of basic zinc cyanurate. The results are shown in Table 1. Further, a photograph observed by a transmission electron microscope is shown in Fig. 4.

(Synthesis Example 8)

In a batch-type sand mill container in which the inner wall of the volume of 1 liter is a urethane resin, 1140 g of pulverized beads of zirconia Φ 1 mm and 290 g of pure water were placed, and the stirring tray was rotated at 1500 rpm, and 3.9 g of cyanuric acid powder (manufactured by Nissan Chemical Industries Co., Ltd.) was charged. The stirring tray was continuously rotated at 1,500 rpm, and 11.2 g of zinc oxide powder (two types of zinc oxide manufactured by Seiko Chemical Co., Ltd.) was charged. The molar ratio of zinc oxide/cyanuric acid was 3.0, and the concentration of cyanuric acid relative to water was 2.0% by mass. After the zinc oxide powder was charged, the stirring disk was rotated at 1,500 rpm for 5 hours to be dispersed. The slurry temperature at this time was 23 °C. Therefore, 300 g of a white slurry having a solid content of 7.8 mass% at pH 7.8, a conductivity of 98 μS/cm, and a drying temperature of 110 ° C was obtained. The X-ray powder diffraction analysis of the dried powder of 110 ° C of the obtained white slurry was carried out, and the same diffraction pattern as in Synthesis Example 1 was obtained. When the fine particles contained in the obtained white slurry were observed by a transmission electron microscope, the long axis was 100 to 300 nm, the short axis was 15 to 20 nm, and the average particle diameter D measured by the laser diffraction method was used. ₅₀ is 152 nm, and the specific surface area Sw after drying at 70 ° C is 40 m ² /g of basic zinc cyanurate. The results are shown in Table 1.

(Synthesis Example 9)

A 1 liter beaker in which 900 g of pure water was placed was placed on a hot plate with a magnetic stirrer, and while stirring, a cyanuric acid powder (manufactured by Nissan Chemical Industries Co., Ltd.) was added in an amount of 18.9 g. . Next, 30.0 g of zinc oxide powder (two kinds of zinc oxides manufactured by Seiko Chemical Co., Ltd.) was charged, and the mixed slurry was stirred with a stir bar and heated to a boil using a hot plate. The molar ratio of zinc oxide/cyanuric acid was 2.5, and the concentration of cyanuric acid relative to water was 2.1% by mass. After stirring at 100 ° C for 8 hours under boiling, 716 g of a white slurry having a pH of 7.1, a conductivity of 46 μS/cm, a viscosity of 500 mPa·s, and a solid content of 6.8 mass% when dried at 110 ° C was obtained. The X-ray powder diffraction analysis of the dried powder of 110 ° C of the obtained white slurry was carried out, and the same diffraction pattern as in Synthesis Example 1 was obtained. The fine particles contained in the obtained white slurry were observed by a transmission electron microscope, and the long axis was 2000 to 20000 nm, and the short axis was 200 to 500 nm. The average particle diameter D measured by the laser diffraction method was used. ₅₀ is 2620 nm, and the specific surface area Sw after drying at 70 ° C is 5 m ² /g of basic zinc cyanurate. The results are shown in Table 1. Further, a photograph observed by a transmission electron microscope is shown in Fig. 5.

(Synthesis Example 10)

A bead mill was replaced with a horizontal bead mill (system zeta LMZ25 manufactured by Ashizawa Finetech Co., Ltd.) having an inner wall of an effective volume of 10.66 liters, and the same ratio as the raw material ratio of Synthesis Example 7 was carried out. As a result, a solid slurry having a pH of 7.9, a conductivity of 206 μS/cm, a viscosity of 76 mPa·s, and a solid content of 110% by weight of 1.8 mass% of a white slurry of 168 kg was obtained. The X-ray powder diffraction analysis of the dried powder of 110 ° C of the obtained white slurry was carried out, and the same diffraction pattern as in Synthesis Example 1 was obtained. When the fine particles contained in the obtained white slurry were observed by a transmission electron microscope, the long axis was 100 to 800 nm, and the short axis was 10 to 60 nm. The average particle diameter D measured by the laser diffraction method was used. ₅₀ is 397 nm, and the specific surface area Sw after drying at 70 ° C is 54 m ² /g of basic zinc cyanurate. The results are shown in Table 1.

(Example 1)

40 mg of dry powder of 110 ° C of basic zinc cyanide obtained in Synthesis Example 9 and 4.0 g of polylactic acid resin (NW3001D, number average molecular weight 72,000, melting point 164 ° C, manufactured by Natureworks) were placed in heated to 185. The resin composition was produced by kneading at 50 rpm for 5 minutes in a °C kneading machine (LABO PLASTOMILL manufactured by Toyo Seiki Co., Ltd.). After cooling, the resin composition was taken out, and the Teflon (registered trademark) sheet was held by a brass plate, and placed in a hot press heated to 185 ° C at the upper portion and 185 ° C at the lower portion to make the thickness of the film 0.4 mm. The ground was pressed at 0.5 kgf to form a film. The film sample was cut into small pieces, and the temperature was raised to 200 ° C at 100 ° C / min and held for 5 minutes as it was, and then cooled at 5 ° C / min to carry out DSC measurement (Seiko Electronics Co., Ltd. DSC-200). The crystallization temperature Tc was measured from the apex of the exothermic peak from the crystallization of polylactic acid observed at the time of cooling.

Further, the film sample was cut into small pieces, and the temperature was raised to 200 ° C at 100 ° C / min and held for 5 minutes as it was, and then cooled to 130 ° C at 200 ° C / min, and then subjected to DSC measurement at 130 ° C for 10 minutes. (Seiko Electronics Co., Ltd. DSC-200). The crystallization rate was measured from the time when the apex of the heat generation peak derived from the crystallization of polylactic acid was observed at 130 ° C. The results are shown in Table 2. In addition, in Table 2, the nucleating agent concentration is described as a part by mass based on 100 parts by mass of the basic zinc cyanurate.

Further, the visible light transmittance of the obtained film was determined by using a color difference meter (Tokyo Electric Color TC-1800MK type), and the haze was obtained by using SPECTRAL HAZE METER (Tokyo Electric Color TC-H3DPK-MK type), and the visible light was transmitted. The rate is 24% and the haze is 70.

(Example 2)

The same operation as in Example 1 was carried out, except that the 110 ° C dry powder of the basic zinc cyanurate obtained in Synthesis Example 7 was used instead of the 110 ° C dry powder of the basic zinc cyanide obtained in Synthesis Example 9. The crystallization temperature Tc and the crystallization rate of the polylactic acid were measured. The results are shown in Table 2. Further, the visible light transmittance and haze of the obtained film were determined in the same manner as in Example 1. As a result, the visible light transmittance was 52% and the haze was 50.

(Example 3)

The same operation as in Example 1 was carried out, except that the 110 ° C dry powder of the basic zinc cyanurate obtained in Synthesis Example 10 was used instead of the 110 ° C dry powder of the basic zinc cyanide obtained in Synthesis Example 9. The crystallization temperature Tc and the crystallization rate of the polylactic acid were measured. The results are shown in Table 2. Further, the visible light transmittance and haze of the obtained film were determined in the same manner as in Example 1. As a result, the visible light transmittance was 44% and the haze was 57.

(Example 4)

The crystallization temperature Tc and the crystallization rate of the polylactic acid were measured in the same manner as in Example 3 except that the amount of the 110 ° C dry powder of the basic zinc cyanurate obtained in Synthesis Example 10 was changed to 8 mg. The results are shown in Table 2. Further, the visible light transmittance and haze of the obtained film were determined in the same manner as in Example 1. As a result, the visible light transmittance was 78% and the haze was 21.

(Example 5)

The crystallization temperature Tc and the crystallization rate of the polylactic acid were measured in the same manner as in Example 3 except that the amount of the 110 ° C dry powder of the basic zinc cyanurate obtained in Synthesis Example 10 was changed to 80 mg. The results are shown in Table 2. Further, in the same manner as in Example 1, the visible light transmittance and haze of the obtained film were determined, and as a result, the visible light transmittance was 22% and the haze was 80.

(Example 6)

36 mg of dry powder of 110 ° C of basic zinc cyanide obtained in Synthesis Example 9 and 3.6 g of polypropylene resin (novatec PP MA3, number average molecular weight 111,000, melting point 165 ° C, manufactured by Japan Polychem Co., Ltd.) The resin composition was kneaded at 50 rpm for 5 minutes in a kneading machine (LABO PLASTOMILL manufactured by Toyo Seiki Co., Ltd.) heated to 185 ° C to produce a resin composition. After cooling, the resin composition was taken out, and the Teflon sheet was held with a brass plate, and placed in a hot press heated to an upper portion of 185 ° C and a lower portion of 185 ° C so that the thickness of the film became 0.4 mm as 0.5 kgf. Pressurization is carried out to form a film. The film sample was cut into small pieces, and the temperature was raised to 200 ° C at 100 ° C / min and held for 5 minutes as it was, and then cooled at 5 ° C / min to carry out DSC measurement (Seiko Electronics Co., Ltd. DSC-200). The crystallization temperature Tc was measured from the apex of the exothermic peak from the crystallization of polypropylene observed upon cooling.

Further, the film sample was cut into small pieces, and the temperature was raised to 200 ° C at 100 ° C / min and held for 5 minutes as it was, and then cooled to 130 ° C at 200 ° C / min, and then subjected to DSC measurement at 130 ° C for 10 minutes. (Seiko Electronics Co., Ltd. DSC-200). The crystallization rate was measured from the time when the apex of the heat generation peak derived from the crystallization of polypropylene was observed at 130 ° C. The results are shown in Table 2. Further, the visible light transmittance and haze of the obtained film were determined in the same manner as in Example 1. As a result, the visible light transmittance was 30% and the haze was 85.

(Example 7)

The same operation as in Example 6 was carried out, except that the 110 ° C dry powder of the basic zinc cyanurate obtained in Synthesis Example 7 was used instead of the 110 ° C dry powder of the basic zinc cyanide obtained in Synthesis Example 9. The crystallization temperature Tc of the polypropylene and the crystallization rate were measured. The results are shown in Table 2. Further, the visible light transmittance and haze of the obtained film were determined in the same manner as in Example 1. As a result, the visible light transmittance was 40% and the haze was 71.

(Example 8)

The same operation as in Example 6 was carried out, except that the 110 ° C dry powder of the basic zinc cyanurate obtained in Synthesis Example 10 was used instead of the 110 ° C dry powder of the basic zinc cyanide obtained in Synthesis Example 9. The crystallization temperature Tc of the polypropylene and the crystallization rate were measured. The results are shown in Table 2. Further, the visible light transmittance and haze of the obtained film were determined in the same manner as in Example 1. As a result, the visible light transmittance was 38% and the haze was 78.

(Comparative Example 1)

The same operation as in Example 1 was carried out except that basic zinc cyanuric acid was not added to the polylactic acid resin. Further, the visible light transmittance and the haze of the obtained film were determined in the same manner as in Example 1. As a result, the visible light transmittance was 74% and the haze was 22.

(Comparative Example 2)

The same operation as in Example 6 was carried out except that basic zinc cyanuric acid was not added to the polypropylene resin. Further, the visible light transmittance and haze of the obtained film were determined in the same manner as in Example 1. As a result, the visible light transmittance was 57% and the haze was 31.

As a result, as shown in Table 2, by adding basic zinc cyanurate, the crystallization temperature and the crystallization rate of the resin became high, and it was found that the basic zinc cyanurate can be used as a crystal nucleating agent for the resin. In this way, since the crystallization rate of the resin is high, the degree of crystallization of the resin is increased, and a molded article having good heat resistance can be obtained. Moreover, by increasing the crystallization rate, the time required for crystallization is shortened, and the molded product of the resin can be produced in a short time. In addition, by crystallization in a short time, the spherulite size is reduced, and a molded article which is dense and has high rigidity and excellent transparency even without adding glass fibers can be obtained. Further, since the crystallization temperature of the resin is also high, since the cooling temperature of the mold can be increased, the molded product of the resin can be produced in a short time.

Further, in the basic zinc cyanurate particles of Synthesis Example 7 or Synthesis Example 10, since the basic zinc cyanuric acid particles of Synthesis Example 9 are remarkably small particles, the basic melamine of Synthesis Example 7 was used. Example 2 and Example 7 of the zinc silicate particle, or Example 3 and Example 8 using the basic zinc cyanurate of Synthesis Example 10, compared to the basic zinc cyanurate particle of Synthesis Example 9. In Example 1 and Example 6, the visible light transmittance was high, the haze was low, and the transparency was excellent.

(Synthesis Example 11)

Into a polymer container of 2 liters, 1501 g of pure water and 79.7 g of phenylphosphonic acid (hereinafter referred to as "PPA"), and magnesium carbonate (manufactured by Kanto Chemical Co., Ltd.) were added while stirring. After MgO was 42 wt% of 19.3 g, magnesium carbonate was dissolved by stirring for 1 hour and 50 minutes to prepare an aqueous magnesium phenylphosphonate solution having a molar ratio of Mg/PPA = 0.40, pH = 2.4, and conductivity = 11.78 mS/cm. Into another two-liter polymer container, 1077 g of pure water and 313 g of the obtained aqueous magnesium phenylphosphonate solution were added, and the mixture was immersed in a warm bath and heated to bring the mixed aqueous solution to 30 °C. After the mixed aqueous solution reached 30 ° C, 36.4 g of cyanuric acid powder (manufactured by Nissan Chemical Industries Co., Ltd.) was added to the mixture while stirring at 3,300 rpm, and the mixture was heated while being heated at 3,300 rpm. Stir vigorously for 40 minutes. Then, 57.4 g of zinc oxide powder (two kinds of zinc oxides manufactured by Seiko Chemical Co., Ltd.) was charged while stirring vigorously, and a white slurry of 1,48 g was obtained. The slurry temperature at this time was 38 ° C, and the slurry temperature was maintained at 38 ° C, and the mixture was vigorously stirred with a dispersion wing for 8 hours while being heated in a warm bath. Therefore, a solid slurry having a pH of 7.2, a conductivity of 608 μS/cm, a viscosity of 400 mPa·s, and a solid content of 7.2% by mass at a temperature of 110 ° C was obtained, which was 1,48 g. The slurry was subjected to Nutsche filtration using a filter paper (5C, manufactured by Toyo Filter Co., Ltd.), and the obtained wet cake was dried at 110 ° C, and then the dried cake was pulverized using a household mixer to obtain a specific surface area of 28 m ^{2 .} / g of powder (dried powder at 110 ° C) 103g. The powder was subjected to X-ray powder diffraction analysis. As a result, as shown in Fig. 6, a diffraction peak of basic zinc cyanurate, zinc phenylphosphonate and magnesium hydroxide was observed, which was a mixture of three compounds. Into the powder. It can be seen that magnesium phenylphosphonate is a zinc phenylphosphonate due to the reaction of strongly acidic phenylphosphonic acid with zinc oxide, magnesium is magnesium hydroxide, and residual zinc oxide reacts with cyanuric acid to form alkaline trimerization. Zinc cyanate. The powder was 29% by mass in terms of cyanuric acid, 43% by mass in terms of zinc, 16% by mass in terms of phenylphosphonic acid, and 1.3% by mass in terms of magnesium. Further, C ₃ N ₃ O ₃ H _{3 of} cyanuric acid is calculated from the elemental analysis of CHN by the amount of nitrogen in the nucleating agent for the resin to be measured, and the phenylphosphonic acid C ₆ H ₇ O ₃ P is Fluorescence X-ray analysis was calculated from the amount of phosphorus in the nucleating agent for the resin used. Then, after dispersing the powder in pure water, the acicular particles of the basic zinc cyanurate having a long axis of 200 to 800 nm and a short axis of 20 to 60 nm and a long axis are observed by a transmission electron microscope. The granular particles of zinc phenylphosphonate having a short axis of 100 to 500 nm and magnesium hydroxide are uniformly dispersed. The results are shown in Table 3.

(Synthesis Example 12)

The same operation as in Synthesis Example 11 was carried out except that the cyanuric acid powder (manufactured by Nissan Chemical Industries Co., Ltd.) was set to 33.1 g, and pH 7.2, conductivity 196 μS/cm, viscosity 500 mPa ‧ s, and 110 ° C were dried. The solid form at that time was divided into 7.2% by mass of a white slurry of 1483 g. The slurry was subjected to Nutsche filtration using a filter paper (5C, manufactured by Toyo Filter Co., Ltd.), and the obtained wet cake was dried at 110 ° C, and then the dried cake was pulverized using a household mixer to obtain a specific surface area of 49 m ^{2 .} /g of powder 102g. As a result of X-ray powder diffraction analysis of this powder, diffraction peaks of basic zinc cyanurate, zinc phenylphosphonate and magnesium hydroxide were observed. The powder was 32% by mass in terms of cyanuric acid, 42% by mass in terms of zinc, 16% by mass in terms of phenylphosphonic acid, and 1.3% by mass in terms of magnesium. Then, after dispersing the powder in pure water, the acicular particles of the basic zinc cyanurate having a long axis of 200 to 800 nm and a short axis of 20 to 60 nm and a long axis are observed by a transmission electron microscope. The granular particles of zinc phenylphosphonate having a short axis of 100 to 500 nm and magnesium hydroxide are uniformly dispersed. The results are shown in Table 3. Further, a photograph observed by a transmission electron microscope is shown in Fig. 7.

(Synthesis Example 13)

313 g of an aqueous solution of magnesium phenylphosphonate prepared in Synthesis Example 11 and 1160 g of pure water were mixed in a polymer container of 2 liters, and then immersed in a bath, and the mixture was heated to a temperature of 30 ° C. After the mixture was stirred at a temperature of 3,300 rpm, 30.3 g of cyanuric acid powder (manufactured by Nissan Chemical Industries Co., Ltd.) was added, and the mixture was vigorously stirred for 40 minutes while heating. Then, 57.4 g of zinc oxide powder (two kinds of zinc oxides manufactured by Seiko Chemical Co., Ltd.) was placed while stirring vigorously, and a white slurry of 1,560 g was obtained. The slurry temperature at this time was 38 ° C, and the slurry temperature was maintained at 38 ° C, and the mixture was vigorously stirred with a dispersion wing for 8 hours while being heated in a warm bath. Therefore, a solid slurry having a pH of 8.6, a conductivity of 133 μS/cm, a viscosity of 700 mPa·s, and a dry state at 110 ° C was obtained, and was divided into a white slurry of 6.6 mass%, which was 1,560 g. The slurry was subjected to Nutsche filtration using a filter paper (5C, manufactured by Toyo Filter Co., Ltd.), and the obtained wet cake was dried at 110 ° C, and then the dried cake was pulverized using a household mixer to obtain a specific surface area of 56 m ^{2 .} /g of powder 100g. As a result of X-ray powder diffraction analysis of this powder, diffraction peaks of basic zinc cyanurate, zinc phenylphosphonate and magnesium hydroxide were observed. The powder was 35 mass% in terms of cyanuric acid, 40% by mass in terms of zinc, 15% by mass in terms of phenylphosphonic acid, and 1.2% by mass in terms of magnesium. Then, after the powder was dispersed in pure water, the needle-like particles of alkaline zinc cyanurate having a long axis of 200 to 800 nm and a short axis of 20 to 60 nm were observed by a transmission electron microscope. The axial and minor axes are 100 to 500 nm of zinc phenylphosphonate and granular particles of magnesium hydroxide. The results are shown in Table 3.

(Synthesis Example 14)

997 g of pure water and 313 g of an aqueous magnesium phenylphosphonate solution obtained in Synthesis Example 11 were placed in a 2-liter polymer container. In the mixed aqueous solution, 33.1 g of cyanuric acid powder (manufactured by Nissan Chemical Industries Co., Ltd.) was charged with a dispersing blade at a concentration of 3,300 rpm, and zinc oxide powder was added thereto while vigorously stirring the dispersion wings. 57.4 g of two types of zinc oxide produced by the company) was prepared into a white slurry of 1400 g. The slurry temperature at this time was 26 ° C, and then the slurry temperature was vigorously stirred for 8 hours with the dispersion wings to 28 ° C. Therefore, 1400 g of a white slurry having a solid content of 7.6 mass% at pH 8.0, a conductivity of 275 μS/cm, a viscosity of 1040 mPa·s, and a dry state at 110 ° C was obtained. This slurry was subjected to Nutsche filtration using a filter paper (5C, manufactured by Toyo Filter Co., Ltd.), and the obtained wet cake was dried at 110 ° C, and then the dried cake was pulverized using a household mixer to obtain a specific surface area of 62 m ^{2 .} /g of powder 105g. As a result of X-ray powder diffraction analysis of this powder, diffraction peaks of basic zinc cyanurate, zinc phenylphosphonate and magnesium hydroxide were observed. The powder was 32% by mass in terms of cyanuric acid, 42% by mass in terms of zinc, 16% by mass in terms of phenylphosphonic acid, and 1.3% by mass in terms of magnesium. Then, after the powder was dispersed in pure water, the needle-like particles of the basic zinc cyanurate having a long axis of 100 to 300 nm and a short axis of 10 to 30 nm were observed by a transmission electron microscope. The axial and minor axes are 50 to 200 nm of zinc phenylphosphonate and granular particles of magnesium hydroxide. The results are shown in Table 3.

(Synthesis Example 15)

The same procedure as in Synthesis Example 12 was carried out except that the slurry temperature was changed to 50 ° C to obtain a white pulp having a solid content of 7.7% by mass at pH 7.7, a conductivity of 213 μS/cm, a viscosity of 720 mPa·s, and a drying at 110 °C. Material 1480g. The slurry was subjected to Nutsche filtration using a filter paper (5C, manufactured by Toyo Filter Co., Ltd.), and the obtained wet cake was dried at 110 ° C, and then the dried cake was pulverized using a household mixer to obtain a specific surface area of 35 m ^{2 .} /g of powder 102g. As a result of X-ray powder diffraction analysis of this powder, diffraction peaks of basic zinc cyanurate, zinc phenylphosphonate and magnesium hydroxide were observed. The powder was 32% by mass in terms of cyanuric acid, 42% by mass in terms of zinc, 16% by mass in terms of phenylphosphonic acid, and 1.3% by mass in terms of magnesium. Then, after the powder was dispersed in pure water, the needle-like particles of alkaline zinc cyanurate having a long axis of 200 to 1000 nm and a short axis of 40 to 80 nm were observed by a transmission electron microscope. The axial and minor axes are 200 to 600 nm of zinc phenylphosphonate and granular particles of magnesium hydroxide. The results are shown in Table 3.

(Synthesis Example 16)

The same procedure as in Synthesis Example 12 was carried out except that the slurry temperature was changed to 60 ° C to obtain a white pulp having a solid content of 7.6 mass% at pH 7.6, a conductivity of 183 μS/cm, a viscosity of 640 mPa·s, and a drying at 110 °C. Material 1480g. The slurry was subjected to Nutsche filtration using a filter paper (5C, manufactured by Toyo Filter Co., Ltd.), and the obtained wet cake was dried at 110 ° C, and then the dried cake was pulverized using a household mixer to obtain a specific surface area of 26 m ^{2 .} /g of powder 102g. As a result of X-ray powder diffraction analysis of this powder, diffraction peaks of basic zinc cyanurate, zinc phenylphosphonate and magnesium hydroxide were observed. The powder was 32% by mass in terms of cyanuric acid, 42% by mass in terms of zinc, 16% by mass in terms of phenylphosphonic acid, and 1.3% by mass in terms of magnesium. Then, after dispersing the powder in pure water, the acicular particles of the basic zinc cyanurate having a major axis of 300 to 1000 nm and a short axis of 40 to 100 nm and a long axis are observed by a transmission electron microscope. The granular particles of zinc phenylphosphonate and magnesium hydroxide having a short axis of 300 to 800 nm are uniformly dispersed. The results are shown in Table 3.

(Synthesis Example 17)

195 g of an aqueous solution of magnesium phenylphosphonate prepared in Synthesis Example 11 and 1194 g of pure water were mixed in a polymer container of 2 liters, and then immersed in a warm bath and heated to a temperature of 30 ° C. After the mixture was stirred at a temperature of 3,300 rpm, 33.1 g of cyanuric acid powder (manufactured by Nissan Chemical Industries Co., Ltd.) was added, and the mixture was vigorously stirred for 40 minutes while heating. Then, 57.4 g of zinc oxide powder (two kinds of zinc oxides manufactured by Seiko Chemical Co., Ltd.) was charged while stirring vigorously, and a white slurry of 1,48 g was obtained. The slurry temperature at this time was 38° C., and the slurry temperature was maintained at 38° C., and the mixture was stirred while stirring in a warm bath for 8 hours to obtain a pH of 8.1, a conductivity of 142 μS/cm, and a viscosity of 540 mPa. ‧ s, solid state at 110 ° C when dry is divided into 7.2% by mass of white pulp 1483g. The slurry was subjected to Nutsche filtration using a filter paper (5C, manufactured by Toyo Filter Co., Ltd.), and the obtained wet cake was dried at 110 ° C, and then the dried cake was pulverized using a household mixer to obtain a specific surface area of 52 m ^{2 .} /g of powder 104g. As a result of X-ray powder diffraction analysis of this powder, diffraction peaks of basic zinc cyanurate, zinc phenylphosphonate and magnesium hydroxide were observed. The powder was 33% by mass in terms of cyanuric acid, 46% by mass in terms of zinc, 10% by mass in terms of phenylphosphonic acid, and 0.8% by mass in terms of magnesium. Then, after the powder was dispersed in pure water, the needle-like particles of alkaline zinc cyanurate having a long axis of 200 to 800 nm and a short axis of 20 to 60 nm were observed by a transmission electron microscope. The axial and minor axes are 100 to 500 nm of zinc phenylphosphonate and granular particles of magnesium hydroxide. The results are shown in Table 3.

(Synthesis Example 18)

368 kg of pure water was placed in a SUS container with a jacket of 700 liters in volume, and a mixer (Hyper made by Ashizawa Finetech Co., Ltd.) equipped with a dispersion wing having a diameter of 300 mm was used to disperse the wings at 500 rpm. 20.3 kg of zinc oxide powder (two kinds of zinc oxides manufactured by Seiki Chemical Co., Ltd.) was charged while dispersing. In order to raise the temperature of the zinc oxide slurry to 49 ° C, the jacket water was warmed. When the zinc oxide slurry reached 40 ° C in the middle, the amount of the dispersing wing was increased to 800 rpm, and 11.7 kg of cyanuric acid powder (manufactured by Nissan Chemical Industries Co., Ltd.) was dispensed three times at intervals of 30 minutes. Invest. After the cyanuric acid powder was charged, the temperature of the slurry was changed to 49 ° C, and the temperature of the jacket water was adjusted to maintain the temperature. The molar ratio of zinc oxide/cyanuric acid was 2.75, and the concentration of cyanuric acid relative to water was 2.9% by mass. This slurry was strongly dispersed for 9 hours as it was at a number of revolutions of the dispersed wings of 800 rpm. Therefore, 395 kg of a white slurry having a pH of 7.5, a conductivity of 29 μS/cm, a viscosity of 866 mPa·s, and a dry state at 110 ° C was obtained in an amount of 8.3% by mass. As a result of X-ray powder diffraction analysis of the dried powder of 110 ° C of the obtained white slurry, a diffraction peak of basic zinc cyanurate was observed. The fine particles contained in the obtained white slurry were observed by a transmission electron microscope, and the long axis was 200 to 800 nm, the short axis was 20 to 50 nm, and the specific surface area Sw after drying at 110 ° C was 35 m ² /g. Zinc cyanurate.

589 g of a white slurry of the obtained basic zinc cyanuric acid in an amount of 8.3% by mass was placed in a 1 liter polymer bottle, and the dispersion was spread at 3,200 rpm using a dispersion blade having a diameter of 30 mm, and the synthesis example 11 was put in. After 168 g of the prepared aqueous magnesium phenylphosphonate solution, it was more strongly dispersed for 6 hours. Therefore, a slurry having a pH of 8.5, a conductivity of 188 μS/cm, and a viscosity of 840 mPa·s was obtained, and Nutsche filtration was carried out using a filter paper (5C, manufactured by Toyo Filter Co., Ltd.), and the obtained wet cake was dried at 110 ° C. The dried filter cake was pulverized using a household mixer to obtain 56 g of a powder having a specific surface area of 35 m ² /g. As a result of X-ray powder diffraction analysis of this powder, diffraction peaks of basic zinc cyanurate, zinc phenylphosphonate and magnesium hydroxide were observed. The powder was 32% by mass in terms of cyanuric acid, 42% by mass in terms of zinc, 16% by mass in terms of phenylphosphonic acid, and 1.3% by mass in terms of magnesium. Then, after the powder was dispersed in pure water, the needle-like particles of alkaline zinc cyanurate having a long axis of 200 to 800 nm and a short axis of 20 to 60 nm were observed by a transmission electron microscope. The axial and minor axes are 100 to 500 nm of zinc phenylphosphonate and granular particles of magnesium hydroxide. The results are shown in Table 3.

(Synthesis Example 19)

Into a mixing tank of a volume of 200 liters, 24 kg of pure water and 1.80 kg of zinc oxide powder (two kinds of zinc oxides manufactured by Seiko Chemical Co., Ltd.) were mixed and stirred, and the concentration of zinc oxide was 7.62% by mass. The slurry is 26kg. Next, 10.66 liters effective volume of the inner wall of the horizontal bead mill amine urethane resin (Ashizawa Finetech (shares) manufactured system zetaLMZ25), the Φ 1mm into the grinding beads made of zirconia stabilization 66kg. After 144 kg of pure water was placed in the circulation tank of the jacket water having a water temperature of 13 ° C, the disk of the horizontal bead mill was rotated at a peripheral speed of 9.5 m/sec. 22.1 kg/min of pure water was supplied to the horizontal bead mill to circulate pure water. After the start of the cycle, 1.39 kg of cyanuric acid powder (manufactured by Nissan Chemical Industries Co., Ltd.) was charged. After the cyanuric acid powder was charged, the temperature of the circulating slurry was adjusted to 42° C., and then 24.6 kg of the zinc oxide slurry having a zinc oxide equivalent concentration of 7.69 mass% was added in 5 minutes, and the addition was carried out for 10 minutes. After the addition, the pan of the horizontal bead mill was also rotated at a peripheral speed of 9.5 m/sec, and the slurry was circulated at a supply rate of 22.1 kg/min for 7 hours to be dispersed. Further, the temperature of the circulating slurry was adjusted to be 42 °C. Therefore, 167 kg of a white slurry having a pH of 7.9, a conductivity of 206 μS/cm, a viscosity of 86 mPa·s, and a basic zinc cyanuric acid conversion concentration of 1.8% by mass were obtained. As a result of X-ray powder diffraction analysis of the dried powder of 110 ° C of the obtained white slurry, no diffraction peak of cyanuric acid and zinc oxide belonging to the raw material was observed, but basic zinc cyanurate was observed. The diffraction peak. This powder was 39% by mass in terms of cyanuric acid and 49% by mass in terms of zinc. Then, when the fine particles contained in the obtained white slurry were observed by a transmission electron microscope, the long axis was 400 to 1200 nm, and the short axis was 20 to 40 nm, and the average particle measured by the laser diffraction method was used. The diameter D ₅₀ was 397 nm, and the specific surface area Sw after drying at 70 ° C was 54 m ² /g of basic zinc cyanurate. The results are shown in Table 3. Further, a photograph observed by a transmission electron microscope is shown in Fig. 8.

(Synthesis Example 20)

156 g of an aqueous magnesium phenylphosphonate solution prepared in Synthesis Example 11 and 1233 g of pure water were mixed in a polymer container of 2 liters, and then immersed in a warm bath and heated to a temperature of 30 ° C. After the mixture was stirred at a temperature of 3,300 rpm, 36.4 g of cyanuric acid powder (manufactured by Nissan Chemical Industries Co., Ltd.) was added, and the mixture was vigorously stirred for 40 minutes while heating. Then, 57.4 g of zinc oxide powder (two kinds of zinc oxides manufactured by Seiko Chemical Co., Ltd.) was charged while stirring vigorously, and a white slurry of 1,48 g was obtained. The slurry temperature at this time was 38 ° C, and the slurry temperature was maintained at 38 ° C. The mixture was stirred while stirring in a warm bath for 8 hours to obtain a pH of 8.4, a conductivity of 130 μS/cm, and a viscosity of 550 mPa. ‧ s, solid state at 110 ° C when dry is divided into 7.2% by mass of white pulp 1483g. The slurry was subjected to Nutsche filtration using a filter paper (5C, manufactured by Toyo Filter Co., Ltd.), and the obtained wet cake was dried at 110 ° C, and then the dried cake was pulverized using a household mixer to obtain a specific surface area of 60 m ^{2 .} /g powder 103g. As a result of X-ray powder diffraction analysis of this powder, diffraction peaks of basic zinc cyanurate, zinc phenylphosphonate and magnesium hydroxide were observed. The powder was 34% by mass in terms of cyanuric acid, 46% by mass in terms of zinc, 8% by mass in terms of phenylphosphonic acid, and 0.6% by mass in terms of magnesium. Then, after the powder was dispersed in pure water, the needle-like particles of alkaline zinc cyanurate having a long axis of 200 to 800 nm and a short axis of 20 to 60 nm were observed by a transmission electron microscope. The axial and minor axes are 100 to 500 nm of zinc phenylphosphonate and granular particles of magnesium hydroxide. The results are shown in Table 3.

(Synthesis Example 21)

After adding 1384 g of pure water and 4.7 g of phenylphosphonic acid (manufactured by Nissan Chemical Industries Co., Ltd.) to a polymer container of 2 liters, the mixture was immersed in a warm bath and heated to obtain a mixed aqueous solution of 30 °C. After the mixture was stirred at a temperature of 3,300 rpm, 36.4 g of cyanuric acid powder (manufactured by Nissan Chemical Industries Co., Ltd.) was added, and the mixture was vigorously stirred for 40 minutes while heating. Then, 57.4 g of zinc oxide powder (two kinds of zinc oxides manufactured by Seiko Chemical Co., Ltd.) was charged while stirring vigorously, and a white slurry of 1,48 g was obtained. The slurry temperature at this time was 38 ° C, and the slurry temperature was maintained at 38 ° C, and the mixture was vigorously stirred with a dispersion wing for 8 hours while being heated in a warm bath. Therefore, a solid slurry having a pH of 6.3, a conductivity of 151 μS/cm, a viscosity of 640 mPa·s, and a solid content of 7.2% by mass at a temperature of 110 ° C was obtained, which was 1,48 g. The slurry was subjected to Nutsche filtration using a filter paper (5C, manufactured by Toyo Filter Co., Ltd.), and the obtained wet cake was dried at 110 ° C, and then the dried cake was pulverized using a household mixer to obtain a specific surface area of 15 m ^{2 .} /g of powder 98g. As a result of X-ray powder diffraction analysis of this powder, diffraction peaks of basic zinc cyanurate and zinc phenylphosphonate were observed. This powder was 34% by mass in terms of cyanuric acid, 46% by mass in terms of zinc, and 10% by mass in terms of phenylphosphonic acid. Then, after the powder was dispersed in pure water, the needle-like particles of alkaline zinc cyanurate having a long axis of 200 to 600 nm and a short axis of 20 to 40 nm were observed by a transmission electron microscope. The coarse and granular particles of zinc phenylphosphonate having a shaft and a minor axis of 2000 to 3000 nm. The results are shown in Table 3.

[Crystal nucleus evaluation-1] (Example 9)

0.55 g of a dry powder (resin for resin) obtained in Synthesis Example 11 and 54.5 g of polylactic acid resin (NW3001D, number average molecular weight 72,000, melting point 164 ° C, manufactured by Natureworks) were mixed and placed in a heated state. A small two-axis kneading extruder (manufactured by Brenda Co., Ltd.) to 170 ° C was kneaded at 50 rpm for 15 minutes to prepare a resin composition. After cooling, the resin composition was taken out, and the Teflon sheet was held with a brass plate, and placed in a hot press heated to an upper portion of 185 ° C and a lower portion of 185 ° C to have a film thickness of 0.4 mm at 0.5 kgf. Pressurized to form a film. The film sample was cut into small pieces, and the temperature was raised to 200 ° C at 200 ° C / min and held for 5 minutes as it was, and then cooled at 5 ° C / min to carry out DSC measurement (DSC-200 manufactured by Seiko Electronics Co., Ltd.). The crystallization temperature Tc was measured from the apex of the exothermic peak from the crystallization of polylactic acid observed at the time of cooling.

Further, the film sample was cut into small pieces, and the temperature was raised to 200 ° C at 100 ° C / min and held for 5 minutes as it was, and then cooled to 110 ° C at 100 ° C / min, and then subjected to DSC measurement at 110 ° C for 10 minutes. (Seiko Electronics Co., Ltd. DSC-200). The crystallization rate was measured from the time when the apex of the heat generation peak derived from the crystallization of polylactic acid was observed at 110 ° C. The results are shown in Table 4. Further, in Table 4, the concentration of the nucleating agent for the resin is described in parts by mass based on 100 parts by mass of the resin nucleating agent for the resin.

(Embodiment 10)

The crystallization temperature Tc and the crystallization rate of the polylactic acid were measured in the same manner as in Example 9 except that 0.55 g of the 110 ° C dry powder obtained in Synthesis Example 12 was used instead of the 110 ° C dry powder obtained in Synthesis Example 11. The results are shown in Table 4.

Further, the visible light transmittance of the obtained film was measured by a color difference meter (Tokyo Electric Color TC-1800MK type), and the haze was obtained by using SPECTRAL HAZE METER (Tokyo Electric Color TC-H3DPK-MK type), and the result was a wavelength of 550 nm. The visible light transmittance was 44% and the haze was 56.

(Example 11)

The crystallization temperature Tc and the crystallization rate of the polylactic acid were measured in the same manner as in Example 9 except that 0.55 g of the 110 ° C dry powder obtained in Synthesis Example 13 was used instead of the 110 ° C dry powder obtained in Synthesis Example 11. The results are shown in Table 4.

(Embodiment 12)

The crystallization temperature Tc and the crystallization rate of the polylactic acid were measured in the same manner as in Example 9 except that 0.55 g of the 110 ° C dry powder obtained in Synthesis Example 14 was used instead of the 110 ° C dry powder obtained in Synthesis Example 11. The results are shown in Table 4.

(Example 13)

The crystallization temperature Tc and the crystallization rate of the polylactic acid were measured in the same manner as in Example 9 except that 0.55 g of the 110 ° C dry powder obtained in Synthesis Example 15 was used instead of the 110 ° C dry powder obtained in Synthesis Example 11. The results are shown in Table 4.

(Example 14)

The crystallization temperature Tc and the crystallization rate of the polylactic acid were measured in the same manner as in Example 9 except that 0.11 g of the 110 ° C dry powder obtained in Synthesis Example 12 was used instead of the 110 ° C dry powder obtained in Synthesis Example 11. The results are shown in Table 4.

Further, the visible light transmittance of the obtained film was measured by a color difference meter (Tokyo Electric Color TC-1800MK type), and the haze was obtained by using SPECTRAL HAZE METER (Tokyo Electric Color TC-H3DPK-MK type), and the result was a wavelength of 550 nm. The visible light transmittance is 75% and the haze is 24.

(Example 15)

The crystallization temperature Tc and the crystallization rate of the polylactic acid were measured in the same manner as in Example 9 except that 0.55 g of the 110 ° C dry powder obtained in Synthesis Example 16 was used instead of the 110 ° C dry powder obtained in Synthesis Example 11. The results are shown in Table 4.

(Embodiment 16)

The crystallization temperature Tc and the crystallization rate of the polylactic acid were measured in the same manner as in Example 9 except that 0.55 g of the 110 ° C dry powder obtained in Synthesis Example 17 was used instead of the 110 ° C dry powder obtained in Synthesis Example 11. The results are shown in Table 4.

(Example 17)

The crystallization temperature Tc and the crystallization rate of the polylactic acid were measured in the same manner as in Example 9 except that 0.55 g of the 110 ° C dry powder obtained in Synthesis Example 18 was used instead of the 110 ° C dry powder obtained in Synthesis Example 11. The results are shown in Table 4.

(Embodiment 18)

7.0 g of dry powder of 110 ° C of basic zinc cyanide obtained in Synthesis Example 19 and zinc phenylphosphonate containing 29% by mass of zinc and 71% by mass of phenylphosphonic acid (trademark ECOPROMOTE manufactured by Nissan Chemical Industries Co., Ltd.) The 110 ° C dry powder obtained in Synthesis Example 11 was replaced with 3.0 g, and mixed with a household powder mixer to prepare a mixed powder for evaluation. The crystallization temperature Tc and the crystallization rate of the polylactic acid were measured in the same manner as in Example 9 except that 0.55 g of the mixed powder was used instead of the 110 ° C dry powder obtained in Synthesis Example 11. The results are shown in Table 4.

Further, the visible light transmittance of the obtained film was measured by a color difference meter (Tokyo Electric Color TC-1800MK type), and the haze was obtained by using SPECTRAL HAZE METER (Tokyo Electric Color TC-H3DPK-MK type), and the result was a wavelength of 550 nm. The visible light transmittance was 40% and the haze was 61.

(Embodiment 19)

5.0 g of zinc phenylphosphonate (trademark ECOPROMOTE manufactured by Nissan Chemical Industries Co., Ltd.), and 16.9 g of dry powder of 110 ° C of basic zinc cyanurate obtained in Synthesis Example 19 and magnesium hydroxide (Kanto Chemical Co., Ltd.) 0.4 g of a reagent was mixed using a household powder mixer to obtain a mixed powder containing 29% by mass of cyanuric acid, 43% by mass of zinc, 16% by mass of phenylphosphonic acid, and 1.3% by mass of magnesium. The crystallization temperature Tc and the crystallization rate of the polylactic acid were measured in the same manner as in Example 9 except that 0.55 g of the mixed powder was used instead of the 110 ° C dry powder obtained in Synthesis Example 11. The results are shown in Table 4.

(Embodiment 20)

The crystallization temperature Tc and the crystallization rate of the polylactic acid were measured in the same manner as in Example 9 except that 0.55 g of the 110 ° C dry powder obtained in Synthesis Example 20 was used instead of the 110 ° C dry powder obtained in Synthesis Example 11. The results are shown in Table 4.

(Example 21)

The same procedure as in Example 9 was carried out except that 0.55 g of the dried powder of 110 ° C obtained in Synthesis Example 21 was used instead of the dried powder of 110 ° C obtained in Synthesis Example 11, and the crystallization temperature Tc and the crystallization rate of the polylactic acid were measured. At this time, the slurry becomes pH 7 or lower, and a part of the polylactic acid is dissolved in the nucleating agent for the resin.

(Comparative Example 3)

The crystallization temperature Tc and the crystallization rate of the polylactic acid were measured in the same manner as in Example 9 except that the crystal nucleating agent for the resin was not added. The results are shown in Table 4.

Further, the visible light transmittance of the obtained film was measured by a color difference meter (Tokyo Electric Color TC-1800MK type), and the haze was obtained by using SPECTRAL HAZE METER (Tokyo Electric Color TC-H3DPK-MK type), and the result was a wavelength of 550 nm. The visible light transmittance was 87% and the haze was 14.

(Comparative Example 4)

The crystallization temperature Tc of the polylactic acid was measured in the same manner as in Example 9 except that 0.55 g of zinc phenylphosphonate (trade name: ECOPROMOTE Co., Ltd.) was used instead of the dried powder of 110 ° C obtained in Synthesis Example 11. Crystallization speed. The results are shown in Table 4. Further, the results of observation of the above zinc phenylphosphonate by a transmission electron microscope are shown in Fig. 9 . Further, the above zinc phenylphosphonate has a specific surface area of 12 m ² /g.

Further, the visible light transmittance of the obtained film was measured by a color difference meter (Tokyo Electric Color TC-1800MK type), and the haze was obtained by using SPECTRAL HAZE METER (Tokyo Electric Color TC-H3DPK-MK type), and the result was a wavelength of 550 nm. The visible light transmittance is 30% and the haze is 70.

(Comparative Example 5)

The crystallization temperature Tc of the polylactic acid was measured in the same manner as in Example 9 except that 0.11 g of zinc phenylphosphonate (trade name: ECOPROMOTE Co., Ltd.) was used instead of the dried powder of 110 ° C obtained in Synthesis Example 11. Crystallization speed. The results are shown in Table 4.

Further, the visible light transmittance of the obtained film was measured by a color difference meter (Tokyo Electric Color TC-1800MK type), and the haze was obtained by using SPECTRAL HAZE METER (Tokyo Electric Color TC-H3DPK-MK type), and the result was a wavelength of 550 nm. The visible light transmittance is 60% and the haze is 41.

(Reference Example 1)

The crystallization of polylactic acid was measured in the same manner as in Example 9 except that 0.55 g of a 110 ° C dry powder of basic zinc cyanide obtained in Synthesis Example 19 was used instead of the dried powder of 110 ° C obtained in Synthesis Example 11. Temperature Tc and crystallization rate. The results are shown in Table 4.

Further, the visible light transmittance of the obtained film was measured by a color difference meter (Tokyo Electric Color TC-1800MK type), and the haze was obtained by using SPECTRAL HAZE METER (Tokyo Electric Color TC-H3DPK-MK type), and the result was a wavelength of 550 nm. The visible light transmittance was 39% and the haze was 64.

(Reference Example 2)

The same procedure as in Example 9 was carried out, except that 0.11 g of the 110 ° C dry powder of the basic zinc cyanide obtained in Synthesis Example 19 was used instead of the 110 ° C dry powder obtained in Synthesis Example 11, and the crystallization of polylactic acid was measured. Temperature Tc and crystallization rate. The results are shown in Table 4.

Further, the visible light transmittance of the obtained film was measured by a color difference meter (Tokyo Electric Color TC-1800MK type), and the haze was obtained by using SPECTRAL HAZE METER (Tokyo Electric Color TC-H3DPK-MK type), and the result was a wavelength of 550 nm. The visible light transmittance was 67% and the haze was 29.

As a result, as shown in Table 4, it was confirmed that Examples 9 to 21 were compared with Comparative Example 3 in which no nucleating agent for a resin was added or Reference Examples 1 and 2 containing only basic zinc cyanurate. The crystallization temperature is remarkably high, and the crystallization rate is remarkably high, and the nucleating agent performance is extremely excellent.

Further, Examples 9 to 21 have the same degree of crystallization temperature and crystallization rate as compared with Comparative Examples 4 and 5 containing only high-priced zinc phenylphosphonate, and are lower than the metal salt of phenylphosphonic acid. The use of a metal salt of phenylphosphonic acid in the cost of the basic zinc cyanurate microparticles has also been found to have the effect of increasing the crystallization rate and the crystallization temperature of the resin, and the effect of cost reduction.

Further, the crystallization rate and the crystallization temperature of Example 1 were higher than those of Example 9 and Example 19 in which the components were the same. Therefore, it was found that the performance of the crystal nucleating agent was excellent when the raw material was mixed with zinc phenylphosphonate and magnesium hydroxide, and the raw material was reacted as in Example 9.

[Crystal nucleus evaluation-2] (Example 22)

The dried zinc cyanurate obtained in Synthesis Example 11 was dried at 110 ° C (resin for resin) 36 mg, and polypropylene resin (novatec PP MA3, number average molecular weight 111,000, melting point 165 ° C, Japan Polychem ( 3.6 g was placed in a kneading machine (LABO PLASTOMILL manufactured by Toyo Seiki Co., Ltd.) heated to 185 ° C for 5 minutes, and kneaded at 50 rpm to produce a resin composition. After cooling, the resin composition was taken out, and the Teflon sheet was held with a brass plate, and placed in a hot press heated to an upper portion of 185 ° C and a lower portion of 185 ° C so that the thickness of the film became 0.4 mm as 0.5 kgf. Pressurization is carried out to form a film. The film sample was cut into small pieces, and the temperature was raised to 200 ° C at 100 ° C / min and held for 5 minutes as it was, and then cooled at 5 ° C / min to carry out DSC measurement (Seiko Electronics Co., Ltd. DSC-200). The crystallization temperature Tc was measured from the apex of the exothermic peak from the crystallization of polypropylene observed upon cooling. Thereafter, the temperature was raised to 200 ° C at 100 ° C /min and held for 5 minutes as it was, and then cooled to 130 ° C at 100 ° C / min, and then subjected to DSC measurement at 130 ° C for 5 minutes (Seiko Electronics Co., Ltd. DSC- 200). The crystallization rate was measured from the time when the apex of the heat generation peak derived from the crystallization of polypropylene was observed at 130 ° C. The results are shown in Table 5.

(Comparative Example 6)

The crystallization temperature Tc and the crystallization rate of the polypropylene were measured in the same manner as in Example 22 except that the crystal nucleating agent for the resin was not added. The results are shown in Table 5.

(Comparative Example 7)

The crystallization temperature Tc and crystallization of the polypropylene were measured in the same manner as in Example 22 except that the zinc phenylphosphonate (trademark ECOPROMOTE manufactured by Nissan Chemical Industries Co., Ltd.) was used instead of the dried powder of 110 ° C obtained in Synthesis Example 11. speed. The results are shown in Table 5.

(Reference Example 3)

The crystallization temperature of the polypropylene was measured in the same manner as in Example 22 except that 36 mg of the 110 ° C dry powder of the basic zinc cyanide obtained in Synthesis Example 19 was used instead of the 110 ° C dry powder obtained in Synthesis Example 11. Tc and crystallization rate. The results are shown in Table 5.

As shown in Table 5, it was confirmed that the crystallization temperature of Example 22 was significantly higher than that of Comparative Example 6 in which no nucleating agent for a resin was added or Reference Example 3 containing only basic zinc cyanurate. It is high, and the crystallization rate is remarkably high, and the performance of the nucleating agent is extremely excellent.

Further, in Comparative Example 7 containing only a high-priced zinc phenylphosphonate, Example 22 has the same degree of crystallization temperature and crystallization rate, and is low-cost alkaline with a metal salt of phenylphosphonic acid. When a metal salt of phenylphosphonic acid is used together with the zinc cyanurate fine particles, it has been confirmed that the effect of increasing the crystallization rate and the crystallization temperature of the resin can be achieved even in the case of the polypropylene resin, and the so-called cost reduction is achieved. The effect.

[Fig. 1] An XRD diffraction pattern of Synthesis Example 1.

Fig. 2 is a TEM photograph of Synthesis Example 1.

Fig. 3 is a TEM photograph of Synthesis Example 3.

Fig. 4 is a TEM photograph of Synthesis Example 7.

Fig. 5 is a TEM photograph of Synthesis Example 9.

Fig. 6 is an XRD diffraction pattern of Synthesis Example 11.

Fig. 7 is a TEM photograph of Synthesis Example 12.

Fig. 8 is a TEM photograph of Synthesis Example 19.

Fig. 9 is a TEM photograph of zinc phenylphosphonate used in Comparative Example 4.

Claims (10)

A crystal nucleating agent for a resin characterized by containing zinc cyanurate particles having an average particle diameter D ₅₀ of 80 to 900 nm and a specific surface area of 20 to 100 m ² /g as determined by a laser diffraction method. The nucleating agent for a resin according to the first aspect of the invention is a nucleating agent for a polylactic acid resin or a nucleating agent for a polyolefin resin. The nucleating agent for a resin according to the first aspect of the invention, wherein the alkaline zinc cyanurate particles are at least one selected from zinc oxide and basic zinc carbonate, cyanuric acid and water, relative to water. The concentration of the cyanuric acid is 0.1 to 10.0% by mass, and the blended slurry is produced by wet dispersion using a dispersion medium having a temperature range of 5 to 55 °C. The crystal nucleating agent for a resin according to any one of claims 1 to 3, which contains a metal salt of phenylphosphonic acid. The crystal nucleating agent for resin according to claim 4, wherein the metal salt of the phenylphosphonic acid is zinc phenylphosphonate, lithium phenylphosphonate, sodium phenylphosphonate, potassium phenylphosphonate, calcium phenylphosphonate or benzene. At least one selected from the group consisting of magnesium phosphonate and manganese phenylphosphonate. A resin composition comprising a resin and basic zinc cyanurate particles having an average particle diameter D ₅₀ of 80 to 900 nm and a specific surface area of 20 to 100 m ² /g as measured by a laser diffraction method. The resin composition of the sixth aspect of the invention, wherein the resin-based polylactic acid resin contains 0.01 to 10.0 parts by mass of the basic zinc cyanurate particles per 100 parts by mass of the polylactic acid resin. Such as the resin composition of claim 6 of the patent scope, wherein the aforementioned tree The aliphatic polyolefin resin contains 0.01 to 10.0 parts by mass of the above-mentioned basic zinc cyanurate particles per 100 parts by mass of the polyolefin resin. The resin composition of claim 8, wherein the polyolefin-based resin is at least one selected from the group consisting of a polypropylene resin, a polyethylene resin, and a polyamide resin. The resin composition according to any one of claims 6 to 9, which contains a metal salt of phenylphosphonic acid.