JP2012236867A - Method for producing crystal nucleating agent for resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for readily producing a crystal nucleating agent for a resin, with which crystallization rate and crystallization temperature of the resin are heightened to obtain a highly transparent resin.SOLUTION: Mixed slurry including an aqueous solution of at least one metal salt of phenylphosphonic acid selected from magnesium phenylphosphonate, lithium phenylphosphonate, sodium phenylphosphonate and potassium phenylphosphonate, at least one selected from zinc oxide and zinc bicarbonate, cyanuric acid and water, is dispersed and reacted, thereby the crystal nucleating agent for a resin containing zinc basic cyanurate, zinc phenylphosphonate and a hydroxide of a metal constituting the metal salt of the phenylphosphonic acid is obtained.

Description

  The present invention relates to a method for producing a crystal nucleating agent for resin such as polylactic acid resin and polyolefin resin.

  From the standpoint of protecting the natural environment, research on aliphatic polyester that is biodegradable in the natural environment has been energetically conducted. Among them, polylactic acid resin has a high melting point of 160 to 180 ° C. and is excellent in transparency. Therefore, polylactic acid resin is expected as a molding material for packaging materials such as containers and films, clothing, fiber materials, electrical and electronic products.

  However, the polylactic acid resin has a problem that the crystallization rate is slow. When the crystallization speed is slow, the crystallinity is lowered, and the heat resistance is deteriorated. For example, when a polylactic acid resin is molded by injection molding or the like in which stretching is not performed, the molded product has a disadvantage that the degree of crystallinity is low and the glass transition temperature of about 60 ° C. is easily deformed. Therefore, in order to increase the crystallinity, an attempt has been made to increase the mold temperature at the time of injection molding and extend the cooling time in the mold. Has a problem with sex.

  In addition, as a method for increasing the crystallization speed of polylactic acid resin or polypropylene resin, for example, a method of adding a crystal nucleating agent that becomes a primary crystal nucleus of a resin that is a crystalline polymer and promotes crystal growth to increase the crystallization speed. It has been known.

  As a crystal nucleating agent for polylactic acid resin, inorganic particles composed of talc and / or boron nitride having a specific particle size or less (see Patent Document 1), amide compounds represented by a specific formula (see Patent Document 2), A sorbitol derivative represented by a specific formula (see Patent Document 3), a phosphate metal salt and a basic inorganic aluminum compound (see Patent Document 4), a metal salt of phenylphosphonic acid (see Patent Document 5), and the like. Although disclosed, development of a more effective crystal nucleating agent for resin is desired. It is also desired to increase the crystallization temperature in order to shorten the molding time. And it is desired that it is more excellent in transparency and can be easily manufactured.

JP-A-8-3432 (Claims) JP-A-10-87975 (Claims) JP-A-10-158369 (Claims) JP 2003-192883 A (Claims) International Publication No. 2005-97894 Pamphlet (Claims)

  An object of the present invention is to solve the above-mentioned problems of the prior art, and it is possible to increase the crystallization speed and crystallization temperature of a resin, and to easily produce a crystal nucleating agent for resin with high transparency. Another object of the present invention is to provide a method for producing a resin crystal nucleating agent.

  The method for producing a crystal nucleating agent for a resin according to the present invention for solving the above-mentioned problems is provided by at least one metal salt of phenylphosphonic acid selected from magnesium phenylphosphonate, lithium phenylphosphonate, sodium phenylphosphonate and potassium phenylphosphonate. By mixing and reacting a mixed slurry containing at least one selected from zinc oxide and basic zinc carbonate, cyanuric acid, and water, basic zinc cyanate and zinc phenylphosphonate A crystal nucleating agent for resin containing is obtained.

In addition, the crystal nucleating agent for resin preferably has a specific surface area of 20 to 100 m ² / g.

  The dispersion is preferably wet dispersion using a disperser type stirring blade or a dispersion medium.

  According to the present invention, an aqueous solution of at least one metal salt of phenylphosphonic acid selected from magnesium phenylphosphonate, lithium phenylphosphonate, sodium phenylphosphonate and potassium phenylphosphonate, and zinc oxide and basic zinc carbonate. By dispersing and reacting a mixed slurry containing at least one selected, cyanuric acid, and water, the crystallization speed and crystallization temperature of the resin can be increased, and the resin has high transparency. Crystal nucleating agents can be easily produced.

3 is an XRD diffraction pattern of Synthesis Example 1. 4 is a TEM photograph of Synthesis Example 2. 10 is a TEM photograph of Synthesis Example 8. 4 is a TEM photograph of zinc phenylphosphonate used in Comparative Example 2.

  The method for producing a crystal nucleating agent for resin according to the present invention comprises an aqueous solution of at least one metal salt of phenylphosphonic acid selected from magnesium phenylphosphonate, lithium phenylphosphonate, sodium phenylphosphonate and potassium phenylphosphonate, and oxidation. A mixed slurry containing at least one selected from zinc and basic zinc carbonate, cyanuric acid, and water is dispersed and reacted. Thereby, the crystal nucleating agent for resin containing basic zinc cyanurate and zinc phenylphosphonate can be obtained.

  More specifically, first, magnesium phenylphosphonate, which is a raw material, is prepared by dissolving a carbonate or metal hydroxide of at least one metal selected from, for example, magnesium, lithium, sodium and potassium, and phenylphosphonic acid in water. Preparing an aqueous solution of at least one metal salt of phenylphosphonic acid selected from lithium phenylphosphonate, sodium phenylphosphonate and potassium phenylphosphonate. For example, magnesium carbonate or magnesium hydroxide and phenylphosphonic acid are mixed so that magnesium / phenylphosphonic acid, which is a ratio of magnesium to phenylphosphonic acid, has a molar ratio of, for example, 0.3 to 0.6. It can be prepared by dissolving in Here, if the magnesium / phenylphosphonic acid (molar ratio) is less than 0.3, the pH of the produced mixed slurry is 7 or less. The resin crystal nucleating agent obtained by drying the slurry having a pH of 7 or less increases the crystallization speed and the crystallization temperature because the polylactic acid partially dissolves when kneaded into the polylactic acid resin. The crystal nucleating agent performance of the polylactic acid resin becomes smaller, and the generated zinc phenylphosphonate is coarser than magnesium / phenylphosphonic acid (molar ratio) of 0.3 or more. Performance decreases. And since the melt | dissolution part of polylactic acid resin solidifies with an amorphous state, the part becomes weak and a mechanical characteristic falls. Further, when the magnesium / phenylphosphonic acid (molar ratio) is larger than 0.6, magnesium phenylphosphonate particles are precipitated. Therefore, the magnesium / phenylphosphonic acid (molar ratio) is preferably in the range of 0.3 to 0.6.

  Next, at least one selected from zinc oxide and basic zinc carbonate, cyanuric acid, and water are used, for example, the cyanuric acid concentration is 0.1 to 10.0% by mass, preferably 1. It is added so that it may become 0-5.0 mass%, and the aqueous solution of the metal salt of the said phenylphosphonic acid is mixed continuously. For example, when an aqueous solution of phenylphosphonic acid magnesium is used as the aqueous solution of phenylphosphonic acid metal salt, the mixed slurry is prepared by blending so that the concentration of the aqueous solution of phenylphosphonic acid magnesium is 1.0 to 3.0% by mass. It is preferable to do. If the concentration of cyanuric acid with respect to water is higher than 10% by mass, the viscosity of the slurry becomes high and a paste is formed, so that it becomes difficult to disperse by a disperse type stirring blade in the latter stage or wet dispersion using a dispersion medium. On the other hand, when the cyanuric acid concentration with respect to water is lower than 0.1% by mass, the productivity is unfavorable.

  The ratio of at least one selected from zinc oxide and basic zinc carbonate and cyanuric acid is not particularly limited, but the molar ratio is the sum of zinc oxide and basic zinc carbonate in terms of zinc oxide / cyanuric acid is 1 It is preferable that it is 0.0-5.0, More preferably, it is 2.5-3.0. When the total amount of zinc oxide equivalent / cyanuric acid is higher than 5.0 or lower than 1.0, a large amount of zinc oxide, basic zinc carbonate and cyanuric acid which did not contribute to the reaction tends to remain. It is.

  Further, the blending ratio of phenylphosphonic acid contained in the metal salt of phenylphosphonic acid to water is not particularly limited, but the concentration of phenylphosphonic acid contained in the metal salt of phenylphosphonic acid is 1.5 to 3.0% by mass. Preferably there is. Even if it is higher than 3.0% by mass, the crystal nucleating agent performance of the polylactic acid resin is not greatly improved, and when it is lower than 1.5% by mass, the crystal nucleating agent performance of the polylactic acid resin is lowered.

  Next, the obtained mixed slurry is dispersed in a temperature range of, for example, 5 to 60 ° C., preferably 5 to 55 ° C., by disperse type stirring blades, wet dispersion using a dispersion medium, or the like. As a result, at least one selected from zinc oxide and basic zinc carbonate is reacted with cyanuric acid to produce basic zinc cyanurate, and zinc oxide or basic zinc carbonate is reacted with a metal salt of phenylphosphonic acid. To produce zinc phenylphosphonate. In addition, this reaction also produces a metal hydroxide or oxide constituting the metal salt of phenylphosphonic acid as a raw material. In addition, since the reaction time can be shortened by dispersing the mixed slurry by wet dispersion using a dispersion type stirring blade or a dispersion medium, the dispersion is performed by a dispersion using a dispersion type stirring blade or a dispersion medium. It is preferable to do so.

When the wet dispersion is performed at a temperature higher than 55 ° C., the generated basic zinc cyanurate and zinc phenylphosphonate become coarse particles as compared with the case where the wet dispersion is performed at 55 ° C. or less, and the polylactic acid resin Since the performance of the crystal nucleating agent is reduced, it is preferably carried out at less than 55 ° C. Thus, since it can manufacture at low temperature, it can manufacture using an apparatus weak to heat, such as resin. In addition, when dispersion is performed by a dispersion type stirring blade or wet dispersion using a dispersion medium, primary particles obtained by observation with a transmission electron microscope have a major axis of 100 to 1200 nm, a minor axis of 10 to 100 nm, and a laser diffraction method. average particle diameter D ₅₀ measured can be basic cyanuric zinc particles is 80～900Nm, long axis and short axis for producing a resin for crystal nucleating agent containing phenylphosphonic acid zinc particles of 50~800nm by .

  Here, the wet dispersion using a dispersion medium means at least one selected from zinc oxide and basic zinc carbonate, metal cyanuric acid, and metal of phenylphosphonic acid, depending on mechanical energy generated by collision of the dispersion medium. It is a mechanochemical reaction with salt. The mechanochemical reaction means that a mechanical reaction is applied to zinc oxide, basic zinc carbonate, cyanuric acid, or a metal salt of phenylphosphonic acid by applying mechanical energy from various directions by collision of dispersion media. Examples of the dispersion medium include stabilized zirconia beads, quartz glass beads, soda lime glass beads, alumina beads, and mixtures thereof. In consideration of the contamination caused by the dispersion media colliding with each other and the dispersion media being crushed, it is preferable to use stabilized zirconia beads as the dispersion media. And the magnitude | size of a dispersion medium is 0.1-10 mm in diameter, for example, Preferably it is 0.5-2.0 mm in diameter. When the diameter of the dispersion medium is less than 0.1 mm, the collision energy between the pulverization media is small, and the mechanochemical reactivity tends to be weak. Further, if the diameter of the dispersion medium is larger than 10 mm, the collision energy between the dispersion media is too large, and the dispersion medium is crushed to increase contamination, which is not preferable. Examples of apparatuses that perform wet dispersion using a dispersion medium include a sand grinder, a horizontal bead mill, an attritor, and a pearl mill (manufactured by Ashizawa Finetech Co., Ltd.). In addition, what is necessary is just to adjust suitably the rotation speed of the apparatus for stirring a dispersion medium, reaction time, etc. according to a desired particle diameter.

  Crystal nucleating agent composition containing basic cyanuric acid zinc, zinc phenylphosphonic acid thus obtained, and metal hydroxide (for example, magnesium hydroxide) constituting metal salt of phenylphosphonic acid as a raw material May be used as a crystal nucleating agent for resin in the form of a slurry containing these, or as a crystal nucleating agent for resin obtained by drying this slurry and making it into a fine powder with a pin disk or jet mill. Also good.

  Thus, according to the production method of the present invention, an aqueous solution of at least one metal salt of phenylphosphonic acid selected from magnesium phenylphosphonate, lithium phenylphosphonate, sodium phenylphosphonate and potassium phenylphosphonate, and oxidation The crystal nucleating agent for resin can be produced by a simple operation of dispersing and reacting a mixed slurry containing at least one selected from zinc and basic zinc carbonate, cyanuric acid, and water. In addition, since this reaction can be manufactured in one pot, it can manufacture with a sufficient yield.

  Further, by using the resin crystal nucleating agent obtained by the production method of the present invention, the resin crystallization speed is increased, so that the resin crystallinity is increased and the heat resistance of the resin molding is improved. be able to. In addition, since the time required for crystallization is shortened by increasing the crystallization speed, a resin molded product can be obtained in a short time, and productivity is improved. Then, by crystallization in a short time, a spherulite size is reduced, and a molded product having high density, high rigidity, and excellent transparency can be obtained. In addition, since the crystallization temperature of the resin also increases, when the resin is molded by a mold such as injection molding, the mold cooling temperature can be increased, so that a resin molded product can be obtained in a short time, and production Improves. Then, the crystallization temperature is higher and the crystallization speed is higher than that obtained by simply mixing basic zinc cyanurate, zinc phenylphosphonate, and metal hydroxide constituting the metal salt of phenylphosphonic acid.

Moreover, since the specific surface area of the crystal nucleating agent for resin obtained by the production method of the present invention is relatively large and fine, for example, 20 to 100 m ² / g, the transparency of the molded product can be further improved.

  Here, the resin crystal nucleating agent obtained by the production method of the present invention contains basic zinc cyanurate particles as described above. And this basic zinc cyanurate is a substance known as a corrosion inhibitor for iron-based metal surfaces and has not been conventionally used as a crystal nucleating agent for resins. It has been found that it can be used as a crystal nucleating agent because it has the function of becoming the primary crystal nucleus of a resin that is a crystalline polymer, promoting crystal growth, increasing the crystallization speed, and increasing the crystallization temperature. Is. The resin crystal nucleating agent obtained by the production method of the present invention contains zinc phenylphosphonate, which is a component known as a resin crystal nucleating agent, but the cost is low. There is a problem that it is expensive. In the present invention, by using zinc oxide, basic zinc carbonate, and cyanuric acid, which are lower in cost than zinc phenylphosphonate, as raw materials, the effect of increasing the crystallization speed and crystallization temperature of the resin, and low cost. It is possible to achieve both of the effects of conversion.

The content ratio of basic cyanuric acid zinc particles and phenylphosphonic acid zinc contained in the produced crystal nucleating agent for resin is not particularly limited. For example, 20-40 mass% as cyanuric acid, 10-30 mass as phenylphosphonic acid. %And it is sufficient. When the cyanuric acid component of the crystal nucleating agent composition is less than 20% by mass, the content of basic zinc cyanurate is decreased and the content of zinc phenylphosphonate is increased. At least one metal salt of phenylphosphonic acid selected from magnesium oxide, lithium phenylphosphonate, sodium phenylphosphonate and potassium phenylphosphonate is expensive, and even if the phenylphosphonic acid concentration is further increased, the crystal nucleating agent Performance does not improve. Conversely, when the cyanuric acid component concentration of the crystal nucleating agent composition is more than 40% by mass, the content of basic zinc cyanurate increases and the content of zinc phenylphosphonate decreases too much. Is not preferable. Cyanuric acid is represented by the molecular formula C ₃ N ₃ O ₃ H ₃ and can be quantified from the amount of nitrogen measured by CHN elemental analysis. 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.

  Moreover, it is preferable that the mass ratio of zinc / zinc phenylphosphonate, which is the ratio of zinc and zinc phenylphosphonate contained in the resin crystal nucleating agent, is greater than 1 and less than 4. This is because even if the mass ratio is 1 or less and the concentration of the expensive phenylphosphonic acid is increased, the performance of the crystal nucleating agent is not improved, and when it is 4 or more, the performance of the crystal nucleating agent tends to be lowered.

  And the crystal nucleating agent for resin obtained by the manufacturing method of this invention can be used with resin, and can be set as a resin composition.

  Examples of the resin include polylactic acid and polyolefin resin. Two or more kinds of resins may be used. Examples of the polylactic acid resin include homopolymers and copolymers of lactic acid, or blend polymers in which these homopolymers and copolymers of lactic acid are mainly mixed with other resins. Examples of other resins to be mixed include biodegradable resins other than polylactic acid, general-purpose synthetic resins, and general-purpose synthetic engineering plastics. When the polylactic acid resin is a copolymer, the arrangement pattern may be any of random copolymer, alternating copolymer, block copolymer, and graft copolymer. In addition, a polylactic acid resin obtained by crosslinking the polylactic acid resin with a crosslinking agent using heat, light, radiation or the like may be used. Of course, two or more of these polylactic acid resins may be used. The molecular weight of polylactic acid is not particularly limited, but for example, the number average molecular weight is about 10,000 to 500,000. Further, the production method of the polylactic acid resin is not particularly limited. For example, it can be produced by ring-opening polymerization of lactide or by directly polycondensing D-form, L-form, racemate, etc. of lactic acid. .

  Examples of the polyolefin resin include polyethylene resin, polypropylene resin, and polyamide resin. Examples of the polypropylene resin include polypropylene, ethylene-propylene copolymer, and the like, and polypropylene modified with an unsaturated carboxylic acid or acid anhydride thereof. Examples of polypropylene modified with unsaturated carboxylic acid or acid anhydride thereof include polypropylene such as propylene homopolymer and ethylene-propylene copolymer, acrylic acid, methacrylic acid, maleic acid, itaconic acid, and fumaric acid. And a copolymer or graft copolymer with an unsaturated carboxylic acid having an acid or acid anhydride unit, such as maleic anhydride or itaconic anhydride, or an acid anhydride thereof. Particularly preferred are copolymers or graft copolymers of propylene and acrylic acid or maleic anhydride. Of course, two or more of these polyolefin resins may be used. The molecular weight of the polyolefin resin is not particularly limited. For example, the number average molecular weight is about 10,000 to 500,000.

  There is no particular limitation on the blending ratio of the resin crystal nucleating agent obtained by the production method of the present invention and containing basic cyanuric acid zinc particles and zinc phenylphosphonate and the resin, but when using a polylactic acid resin as the resin It is preferable that the resin crystal nucleating agent containing basic cyanuric acid zinc particles and zinc phenylphosphonate is 0.01 to 10.0 parts by mass with respect to 100 parts by mass of the polylactic acid resin. Moreover, also when using polyolefin-type resin as resin, 0.01-10.0 mass of crystal nucleating agents for resin containing basic cyanuric-acid zinc particle and zinc phenylphosphonate zinc with respect to 100 mass parts of polyolefin-type resin. Part.

  The resin composition may contain an inorganic filler. Examples of the inorganic filler include glass fiber, carbon fiber, talc, mica, silica, kaolin, clay, wollastonite, glass beads, crow flake, potassium titanate, calcium carbonate, magnesium sulfate, titanium oxide and the like. . The shape of these inorganic fillers may be any of fibrous, granular, plate-like, needle-like, spherical, and powder. The compounding quantity of these inorganic fillers can be 300 mass parts or less with respect to 100 mass parts of resin, for example.

  Moreover, the said resin composition may contain the flame retardant. Examples of the flame retardant include halogen flame retardants such as bromine and chlorine, antimony flame retardants such as antimony trioxide and antimony pentoxide, and inorganic flame retardants such as aluminum hydroxide, magnesium hydroxide and silicone compounds. Phosphorus flame retardants such as red phosphorus, phosphate esters, ammonium polyphosphate, phosphazene, melamine, melam, melem, melon, melamine cyanurate, melamine phosphate, melamine pyrophosphate, melamine polyphosphate, melamine / melam polyphosphate -Melem double salt, melamine alkylphosphonate, melamine phenylphosphonate, melamine sulfate, melamine methanesulfonate such as melam sulfonate, and fluororesin such as PTFE. The compounding quantity of these flame retardants can be 200 mass parts or less with respect to 100 mass parts of resin, for example.

  In addition to the above components, the resin composition may include a heat stabilizer, a light stabilizer, an ultraviolet absorber, an antioxidant, an impact modifier, an antistatic agent, a pigment, a colorant, a release agent, a lubricant, and a plasticizer. , Compatibility agents, foaming agents, fragrances, antibacterial and antifungal agents, various coupling agents such as silane, titanium and aluminum, other various fillers, crystal nucleating agents other than zinc cyanurate particles, etc. In the production of such synthetic resins, various commonly used additives may be contained.

  A resin composition is produced using a resin crystal nucleating agent containing basic zinc cyanate and zinc phenylphosphonate obtained by the production method of the present invention, a resin, and various additives that are added as necessary. The method to do is not specifically limited, It can manufacture by the method similar to the resin composition containing a well-known crystal nucleating agent. For example, a crystal nucleating agent containing basic zinc cyanurate and zinc phenylphosphonate obtained by the production method of the present invention, a resin, and additives to be added as necessary are mixed with various mixers, and are uniaxial or biaxial. A resin composition can be manufactured by kneading at a temperature of about 150 to 220 ° C. using an extruder or the like. In addition, a master batch containing a high concentration of crystal nucleating agent for resins containing the basic zinc cyanurate and zinc phenylphosphonate obtained by the production method of the present invention and additives to be added as necessary is produced, A method of adding this to the resin is also possible. And the method of adding the crystal nucleating agent for resin in the superposition | polymerization stage of resin may be sufficient.

  With such a resin composition, various molded products can be easily produced by general molding methods such as injection molding, blow molding, vacuum molding, and compression molding. The molded product can be used as, for example, a packaging material such as a container or a film, clothing, a fiber material, an electric product, an electronic product, or the like.

  And since the said resin composition contains the basic cyanuric-acid zinc particle and phenylphosphonic acid zinc sub, which are crystal nucleating agents, the resin crystallization rate is high. Accordingly, the degree of crystallinity of the resin is increased, and a molded product having good heat resistance can be obtained. Further, since the time required for crystallization is shortened by increasing the crystallization speed, a resin molded product can be produced in a short time. Then, by crystallization in a short time, a spherulite size is reduced, and a molded product having high density, high rigidity, and excellent transparency can be obtained. Also, since the resin crystallization temperature is increased by containing basic zinc cyanurate particles and phenylphosphonic acid metal salt, the cooling temperature of the mold is set when molding the resin with a mold such as injection molding. Since it can be made high, a resin molded product can be produced in a short time.

  Hereinafter, although it further explains in full detail based on an Example and a comparative example, the present invention is not limited at all by this example.

(measuring device)
Analysis in Examples and Comparative Examples was performed with the following apparatus and conditions.
Transmission electron microscope observation: JEM-1010 type (manufactured by JEOL Ltd.) Applied voltage 100 KV
Laser diffraction particle size measurement: SALD-7000 type (manufactured by Shimadzu Corporation), 1 g of sample diluted 200 times with pure water and measurement Specific surface area measurement: Nitrogen adsorption method surface area measuring device monosorb machine (Yuasa Ionics Co., Ltd.) Made)
Gravimetric analysis: About 2 g of sample is put in a porcelain crucible and weighed accurately, then the solid content is calculated from the mass after drying at 110 ° C. X-ray powder diffraction identification: Powder X-ray diffraction apparatus RINT Ultimate type (manufactured by Rigaku Corporation)
Elemental analysis: fully automatic elemental analyzer CHNS / O analyzer 2400 (manufactured by Perkin Elmer)

(Synthesis Example 1)
1501 g of pure water and 79.7 g of phenylphosphonic acid (hereinafter also referred to as “PPA”) (which is also referred to as “PPA”) are put into a 2 liter plastic container, and magnesium carbonate (reagent MgO manufactured by Kanto Chemical Co., Ltd.) is stirred. 42 wt%) After adding 19.3 g, the mixture was stirred for 1 hour 50 minutes to dissolve the magnesium carbonate, and the molar ratio of Mg / PPA = 0.40, pH = 2.4, and conductivity = 11.78 mS / cm. A magnesium phenylphosphonate aqueous solution was prepared. After adding 1077 g of pure water and 313 g of the obtained magnesium phenylphosphonate aqueous solution to a new 2 liter plastic container, it was immersed in a hot tub and heated until the mixed aqueous solution reached 30 ° C. When the mixed aqueous solution reached 30 ° C., 36.4 g of cyanuric acid powder (manufactured by Nissan Chemical Industries, Ltd.) was added while vigorously stirring at 3300 rpm with a disper blade (NZEL1000 manufactured by EYELA), and further heated for 40 minutes. Stir vigorously. Subsequently, 57.4 g of zinc oxide powder (2 types of zinc oxide manufactured by Sakai Chemical Industry Co., Ltd.) was added while vigorously stirring with a disper blade, and 1483 g of white slurry was prepared. The slurry temperature at this time was 38 degreeC, and it stirred strongly with the disper blade | wing for 8 hours, heating with a warm bath so that slurry temperature might maintain 38 degreeC. As a result, 1483 g of white slurry having a pH of 7.2, an electric conductivity of 608 μS / cm, a viscosity of 400 mPa · s, and a solid content of 7.2% by mass when dried at 110 ° C. was obtained. A wet cake obtained by subjecting this slurry to Nutsche filtration using a filter paper (5C Toyo Filter Paper Co., Ltd.) was dried at 110 ° C., and then the dried cake was pulverized with a home mixer to have a specific surface area of 28 m ² / g. 103 g of powder (dried powder at 110 ° C.) was obtained. When X-ray powder diffraction analysis was performed on this powder, as shown in FIG. 1, diffraction peaks of basic zinc cyanurate, zinc phenylphosphonate and magnesium hydroxide were observed, and the powder was composed of a mixture of three compounds. there were. From this, magnesium phenylphosphonate reacts with strongly acidic phenylphosphonic acid to form zinc phenylphosphonate, magnesium becomes magnesium hydroxide, and the remaining zinc oxide reacts with cyanuric acid to form a base. It was found that the characteristic zinc cyanurate was produced. This powder contained 29% by mass as cyanuric acid, 43% by mass as zinc, 16% by mass as phenylphosphonic acid, and 1.3% by mass as magnesium. Cyanuric acid C ₃ N ₃ O ₃ H ₃ is calculated from the amount of nitrogen in the crystal nucleating agent for resin measured by CHN elemental analysis, and phenylphosphonic acid C ₆ H ₇ O ₃ P is measured by fluorescent X-ray analysis. The amount of phosphorus in the resin crystal nucleating agent was calculated. And after disperse | distributing this powder with a pure water and observing with the transmission electron microscope, the long axis is 200-800 nm, the short axis is 20-60 nm, the needle-like particles of basic cyanuric acid zinc, the long axis and the short axis Were uniformly dispersed in 100-500 nm zinc phenylphosphonate and magnesium hydroxide particles. The results are shown in Table 1.

(Synthesis Example 2)
The same operation as in Synthesis Example 1 was conducted except that 33.1 g of cyanuric acid powder (manufactured by Nissan Chemical Industries, Ltd.) was used, pH 7.2, conductivity 196 μS / cm, viscosity 500 mPa · s, when dried at 110 ° C. 1483 g of a white slurry having a solid content of 7.2% by mass was obtained. A wet cake obtained by subjecting this slurry to Nutsche filtration using a filter paper (5C Toyo Filter Paper Co., Ltd.) was dried at 110 ° C., and then the dried cake was pulverized with a home mixer to have a specific surface area of 49 m ² / g. 102 g of powder was obtained. When this powder was subjected to X-ray powder diffraction analysis, diffraction peaks of basic zinc cyanurate, zinc phenylphosphonate and magnesium hydroxide were observed. This powder contained 32% by mass as cyanuric acid, 42% by mass as zinc, 16% by mass as phenylphosphonic acid, and 1.3% by mass as magnesium. And after disperse | distributing this powder with a pure water and observing with the transmission electron microscope, the long axis is 200-800 nm, the short axis is 20-60 nm, the needle-like particles of basic cyanuric acid zinc, the long axis and the short axis Were uniformly dispersed in 100-500 nm zinc phenylphosphonate and magnesium hydroxide particles. The results are shown in Table 1. Moreover, the photograph observed with the transmission electron microscope is shown in FIG.

(Synthesis Example 3)
In a 2 liter plastic container, 313 g of the phenylphosphonate magnesium aqueous solution prepared in Synthesis Example 1 and 1160 g of pure water were mixed and then immersed in a hot tub and heated until the mixed aqueous solution reached 30 ° C. When the mixed aqueous solution reached 30 ° C., 30.3 g of cyanuric acid powder (manufactured by Nissan Chemical Industries, Ltd.) was added while vigorously stirring at 3300 rpm with a disper blade, and further stirred vigorously for 40 minutes while heating. Subsequently, 57.4 g of zinc oxide powder (2 types of zinc oxide manufactured by Sakai Chemical Co., Ltd.) was added while vigorously stirring with a disper blade, and 1560 g of white slurry was prepared. The slurry temperature at this time is 38 ° C., and the mixture is vigorously stirred with a disperse blade for 8 hours while being heated in a hot tub so as to maintain the slurry temperature at 38 ° C., pH 8.6, conductivity 133 μS / cm, viscosity 700 mPa -1560g of white slurry whose solid content at s and 110 degreeC drying is 6.6 mass% was obtained. The wet cake obtained by Nutsche filtration of the slurry using filter paper (5C Toyo Filter Paper Co., Ltd.) was dried at 110 ° C., and then the dried cake was pulverized with a home mixer to have a specific surface area of 56 m ² / g. 100 g of powder was obtained. When this powder was subjected to X-ray powder diffraction analysis, diffraction peaks of basic zinc cyanurate, zinc phenylphosphonate and magnesium hydroxide were observed. This powder contained 35% by mass as cyanuric acid, 40% by mass as zinc, 15% by mass as phenylphosphonic acid, and 1.2% by mass as magnesium. And after disperse | distributing this powder with a pure water and observing with the transmission electron microscope, the long axis is 200-800 nm, the short axis is 20-60 nm, the needle-like particles of basic cyanuric acid zinc, the long axis and the short axis Particles of zinc phenylphosphonate and magnesium hydroxide having a particle size of 100 to 500 nm were observed. The results are shown in Table 1.

(Synthesis Example 4)
To a 2-liter plastic container, 997 g of pure water and 313 g of magnesium phenylphosphonate aqueous solution obtained in Synthesis Example 1 were added. 33.1 g of cyanuric acid powder (manufactured by Nissan Chemical Industries, Ltd.) was added to this mixed aqueous solution with strong stirring at 3300 rpm with a disperse blade, and then zinc oxide powder (Sakai Chemical Co., Ltd.) with strong stirring with a disper blade. (2 types zinc oxide manufactured) 57.4g was thrown in and 1400g of white slurry was created. The slurry temperature at this time was 26 degreeC, and the slurry temperature after stirring vigorously for 8 hours with the disper blade | wing was 28 degreeC. As a result, 1400 g of a white slurry having a pH of 8.0, an electric conductivity of 275 μS / cm, a viscosity of 1040 mPa · s, and a solid content of 7.6% by mass when dried at 110 ° C. was obtained. A wet cake obtained by subjecting this slurry to Nutsche filtration using a filter paper (5C Toyo Filter Paper Co., Ltd.) was dried at 110 ° C., and then the dried cake was pulverized with a home mixer to have a specific surface area of 62 m ² / g. 105 g of powder was obtained. When X-ray powder diffraction analysis was performed on this powder, diffraction peaks of basic zinc cyanurate, zinc phenylphosphonate and magnesium hydroxide were observed. This powder contained 32% by mass as cyanuric acid, 42% by mass as zinc, 16% by mass as phenylphosphonic acid, and 1.3% by mass as magnesium. And after disperse | distributing this powder with a pure water and observing with the transmission electron microscope, the long axis is 100-300 nm, the short axis is 10-30 nm, the needle-like particles of basic cyanuric acid zinc, the long axis and the short axis Particles of zinc phenylphosphonate and magnesium hydroxide having a particle size of 50 to 200 nm were observed. The results are shown in Table 1.

(Synthesis Example 5)
A white slurry having the same operation as in Synthesis Example 2 except that the slurry temperature was 50 ° C., pH 7.7, conductivity 213 μS / cm, viscosity 720 mPa · s, and solid content 7.6% by mass when dried at 110 ° C. 1480 g was obtained. The slurry obtained by subjecting this slurry to Nutsche filtration using a filter paper (5C Toyo Filter Paper Co., Ltd.) was dried at 110 ° C., and then the dried cake was pulverized with a home mixer to have a specific surface area of 35 m ² / g. 102 g of powder was obtained. When this powder was subjected to X-ray powder diffraction analysis, diffraction peaks of basic zinc cyanurate, zinc phenylphosphonate and magnesium hydroxide were observed. This powder contained 32% by mass as cyanuric acid, 42% by mass as zinc, 16% by mass as phenylphosphonic acid, and 1.3% by mass as magnesium. And after disperse | distributing this powder with a pure water, when observing with the transmission electron microscope, the long axis is 200-1000 nm, the short axis is 40-80 nm, the needle-shaped particle | grains of a basic zinc cyanurate, a long axis, and a short axis Granular particles of zinc phenylphosphonate and magnesium hydroxide having a particle diameter of 200 to 600 nm were observed. The results are shown in Table 1.

(Synthesis Example 6)
A white slurry having the same operation as in Synthesis Example 2 except that the slurry temperature was 60 ° C., pH 7.6, conductivity 183 μS / cm, viscosity 640 mPa · s, and solid content at 110 ° C. when dried at 7.6% by mass. 1480 g was obtained. A wet cake obtained by subjecting this slurry to Nutsche filtration using a filter paper (5C Toyo Filter Paper Co., Ltd.) was dried at 110 ° C., and then the dried cake was pulverized with a home mixer to have a specific surface area of 26 m ² / g. 102 g of powder was obtained. When this powder was subjected to X-ray powder diffraction analysis, diffraction peaks of basic zinc cyanurate, zinc phenylphosphonate and magnesium hydroxide were observed. This powder contained 32% by mass as cyanuric acid, 42% by mass as zinc, 16% by mass as phenylphosphonic acid, and 1.3% by mass as magnesium. And after disperse | distributing this powder with a pure water and observing with the transmission electron microscope, the long axis is 300-1000 nm, the short axis is 40-100 nm, basic zinc cyanurate acicular particles, the long axis and the short axis Were uniformly dispersed with zinc phenylphosphonate and magnesium hydroxide particles having a particle diameter of 300 to 800 nm. The results are shown in Table 1.

(Synthesis Example 7)
After mixing 195 g of the phenylphosphonate magnesium aqueous solution prepared in Synthesis Example 1 and 1194 g of pure water in a 2 liter plastic container, it was immersed in a hot tub and heated until the mixed aqueous solution reached 30 ° C. When the mixed aqueous solution reached 30 ° C., 36.4 g of cyanuric acid powder (manufactured by Nissan Chemical Industries, Ltd.) was added while vigorously stirring at 3300 rpm with a disper blade, and further vigorously stirred for 40 minutes while heating. Subsequently, 57.4 g of zinc oxide powder (2 types of zinc oxide manufactured by Sakai Chemical Industry Co., Ltd.) was added while vigorously stirring with a disper blade, and 1483 g of white slurry was prepared. The slurry temperature at this time is 38 ° C., and it is vigorously stirred with a disperse blade for 8 hours while being heated in a hot tub so as to maintain the slurry temperature at 38 ° C., pH 8.1, conductivity 142 μS / cm, viscosity 540 mPa -1483g of white slurry whose solid content at the time of s and 110 degreeC drying is 7.2 mass% was obtained. A wet cake obtained by subjecting this slurry to Nutsche filtration using a filter paper (5C Toyo Filter Paper Co., Ltd.) was dried at 110 ° C., and then the dried cake was pulverized with a home mixer to have a specific surface area of 52 m ² / g. 104 g of powder was obtained. When this powder was subjected to X-ray powder diffraction analysis, diffraction peaks of basic zinc cyanurate, zinc phenylphosphonate and magnesium hydroxide were observed. This powder contained 33% by mass as cyanuric acid, 46% by mass as zinc, 10% by mass as phenylphosphonic acid, and 0.8% by mass as magnesium. And after disperse | distributing this powder with a pure water and observing with the transmission electron microscope, the long axis is 200-800 nm, the short axis is 20-60 nm, the needle-like particles of basic cyanuric acid zinc, the long axis and the short axis Particles of zinc phenylphosphonate and magnesium hydroxide having a particle size of 100 to 500 nm were observed. The results are shown in Table 1.

(Synthesis Example 8)
24 kg of pure water and 2 kg of zinc oxide powder (2 types of zinc oxide manufactured by Sakai Chemical Co., Ltd.) are put into a mixing tank with a capacity of 200 liters, stirred and mixed with a disper blade, and the zinc oxide equivalent concentration is 7.62% by mass. 26 kg of slurry was prepared. Next, 66 kg of crushed beads made of stabilized zirconia having a diameter of 1 mm was charged into a horizontal bead mill (System Zeta LMZ25, manufactured by Ashizawa Finetech Co., Ltd.) having an effective volume of 10.66 liters and an inner wall of urethane resin. After adding 144 kg of pure water to a circulating tank with well water at 13 ° C as jacket water, the horizontal bead mill supplies pure water at a feed rate of 22.1 kg / min while rotating the disk of the horizontal bead mill at a peripheral speed of 9.5 m / sec. And purified water was circulated. After the start of circulation, 1.19 kg of cyanuric acid powder (manufactured by Nissan Chemical Industries, Ltd.) was added. After charging the cyanuric acid powder, the temperature of the circulating slurry was adjusted to 42 ° C., and 24.6 kg of zinc oxide slurry having a zinc oxide equivalent concentration of 7.69% by mass was divided into 5 portions and added over 10 minutes. . After the addition, the slurry was circulated and dispersed for 7 hours at a feed rate of 22.1 kg / min while rotating the disk of a horizontal bead mill at a peripheral speed of 9.5 m / sec. During this time, the circulating slurry temperature was adjusted to 42 ° C. As a result, 167 kg of white slurry having a pH of 7.9, an electrical conductivity of 206 μS / cm, a viscosity of 86 mPa · s, and a basic cyanuric acid zinc equivalent concentration of 1.8% by mass was obtained. When the X-ray powder diffraction analysis was performed on the 110 ° C. dry powder of the obtained white slurry, the diffraction peak attributed to the raw material cyanuric acid and zinc oxide was not observed, but the diffraction peak of basic cyanuric acid zinc was observed. It was. This powder contained 39% by mass as cyanuric acid and 49% by mass as zinc. Then, fine particles contained in the white slurry obtained is the major axis in the transmission electron microscopic observation 400 to 1200 nm, a short axis 20 to 40 nm, average particle size _{D 50} by laser diffractometry particle size measurement is by 397nm The basic cyanuric acid zinc having a specific surface area Sw after drying at 70 ° C. of 54 m ² / g was obtained. The results are shown in Table 1. Moreover, the photograph observed with the transmission electron microscope is shown in FIG.

(Synthesis Example 9)
After mixing 156 g of the magnesium phenylphosphonate aqueous solution prepared in Synthesis Example 1 and 1233 g of pure water in a 2 liter plastic container, it was immersed in a hot tub and heated until the mixed aqueous solution reached 30 ° C. When the mixed aqueous solution reached 30 ° C., 36.4 g of cyanuric acid powder (manufactured by Nissan Chemical Industries, Ltd.) was added while vigorously stirring at 3300 rpm with a disper blade, and further vigorously stirred for 40 minutes while heating. Subsequently, 57.4 g of zinc oxide powder (2 types zinc oxide manufactured by Sakai Chemical Industry Co., Ltd.) was added while vigorously stirring with a disper blade, and 1483 g of white slurry was prepared. The slurry temperature at this time is 38 ° C., and the mixture is vigorously stirred with a disperse blade for 8 hours while being heated in a hot tub so as to maintain the slurry temperature at 38 ° C., pH 8.4, conductivity 130 μS / cm, viscosity 550 mPa -1483g of white slurry whose solid content at the time of s and 110 degreeC drying is 7.2 mass% was obtained. A wet cake obtained by subjecting this slurry to Nutsche filtration using a filter paper (5C Toyo Filter Paper Co., Ltd.) was dried at 110 ° C., and then the dried cake was pulverized with a home mixer to have a specific surface area of 60 m ² / g. 103 g of powder was obtained. When this powder was subjected to X-ray powder diffraction analysis, diffraction peaks of basic zinc cyanurate, zinc phenylphosphonate and magnesium hydroxide were observed. This powder contained 34% by mass as cyanuric acid, 46% by mass as zinc, 8% by mass as phenylphosphonic acid, and 0.6% by mass as magnesium. And after disperse | distributing this powder with a pure water and observing with the transmission electron microscope, the long axis is 200-800 nm, the short axis is 20-60 nm, the needle-like particles of basic cyanuric acid zinc, the long axis and the short axis Particles of zinc phenylphosphonate and magnesium hydroxide having a particle size of 100 to 500 nm were observed. The results are shown in Table 1.

(Synthesis Example 10)
After adding 1384 g of pure water and 4.7 g of phenylphosphonic acid (manufactured by Nissan Chemical Industries, Ltd.) to a 2 liter plastic container, it was immersed in a hot tub and heated until the mixed aqueous solution reached 30 ° C. When the mixed aqueous solution reached 30 ° C., 36.4 g of cyanuric acid powder (manufactured by Nissan Chemical Industries, Ltd.) was added while vigorously stirring at 3300 rpm with a disper blade, and further vigorously stirred for 40 minutes while heating. Subsequently, 57.4 g of zinc oxide powder (2 types of zinc oxide manufactured by Sakai Chemical Industry Co., Ltd.) was added while vigorously stirring with a disper blade, and 1483 g of white slurry was prepared. The slurry temperature at this time was 38 degreeC, and it stirred strongly with the disper blade | wing for 8 hours, heating with a hot bath so that slurry temperature might maintain 38 degreeC. As a result, 1483 g of white slurry having a pH of 6.3, an electric conductivity of 151 μS / cm, a viscosity of 640 mPa · s, and a solid content of 7.2% by mass when dried at 110 ° C. was obtained. A wet cake obtained by subjecting this slurry to Nutsche filtration using a filter paper (5C Toyo Filter Paper Co., Ltd.) was dried at 110 ° C., and then the dried cake was pulverized with a home mixer to have a specific surface area of 15 m ² / g. 98 g of powder was obtained. When this powder was subjected to X-ray powder diffraction analysis, diffraction peaks of basic zinc cyanurate and zinc phenylphosphonate were observed. This powder contained 34% by weight as cyanuric acid, 46% by weight as zinc and 10% by weight as phenylphosphonic acid. And after disperse | distributing this powder with a pure water, when observing with the transmission electron microscope, the long axis is 200-600 nm, the short axis is 20-40 nm, the basic zinc cyanurate needle-like particles, the long axis and the short axis Coarse particles of zinc phenylphosphonate having a diameter of 2000 to 3000 nm were observed. The results are shown in Table 1.

[Crystal Nucleating Agent Evaluation-1]
Example 1
The dried powder (crystal nucleating agent for resin) at 110 ° C. obtained in Synthesis Example 1 and 0.55 g of polylactic acid resin (NW3001D, number average molecular weight 72,000, melting point 164 ° C., manufactured by Nature Works) were mixed. Then, it put into the small biaxial kneading extruder (made by a brander company) heated at 170 degreeC, and knead | mixed for 15 minutes at 50 rpm, and created the resin composition. After cooling, the resin composition is taken out, sandwiched between a Teflon sheet and a brass plate, placed in a hot press machine heated to an upper part of 185 ° C. and a lower part of 185 ° C., and added at 0.5 kgf so that the thickness of the film becomes 0.4 mm. Pressed to create a film. The film sample was cut into small pieces, heated to 200 ° C. at 200 ° C./min, held for 5 minutes, and then cooled at 5 ° C./min (DSC-200 manufactured by Seiko Electronics Co., Ltd.). went. The crystallization temperature Tc was measured from the apex of the exothermic peak derived from the crystallization of polylactic acid observed during cooling.

  Also, this film sample is cut into small pieces, heated to 100 ° C./min to 200 ° C. and held for 5 minutes, then cooled to 110 ° C. at 100 ° C./min and then held at 110 ° C. for 10 minutes. The measurement (DSC-200 manufactured by Seiko Electronics Co., Ltd.) was performed. The crystallization rate was measured from the time at the top of the exothermic peak derived from the crystallization of polylactic acid observed at 110 ° C. The results are shown in Table 2. In Table 2, the concentration of the resin crystal nucleating agent is described as a part by mass of the resin crystal nucleating agent with respect to 100 parts by mass of the resin.

(Example 2)
Instead of the 110 ° C. dry powder obtained in Synthesis Example 1, the same operation as in Example 1 was carried out except that 0.55 g of the 110 ° C. dry powder obtained in Synthesis Example 2 was used. Tc and crystallization rate were measured. The results are shown in Table 2.

  Further, when the visible light transmittance of the obtained film was determined with a color difference meter (Tokyo Denshoku TC-1800MK type) and the haze was determined with SPECTRAL HAZE METER (Tokyo Denshoku TC-H3DPK-MK type), the visible light with a wavelength of 550 nm was obtained. The light transmittance was 44% and the haze was 56.

(Example 3)
Instead of the 110 ° C. dry powder obtained in Synthesis Example 1, the same operation as in Example 1 was carried out except that 0.55 g of the 110 ° C. dry powder obtained in Synthesis Example 3 was used. Tc and crystallization rate were measured. The results are shown in Table 2.

Example 4
The crystallization temperature of polylactic acid is the same as in Example 1 except that 0.55 g of the 110 ° C. dry powder obtained in Synthesis Example 4 is used instead of the 110 ° C. dry powder obtained in Synthesis Example 1. Tc and crystallization rate were measured. The results are shown in Table 2.

(Example 5)
The crystallization temperature of polylactic acid is the same as in Example 1 except that 0.55 g of the 110 ° C. dry powder obtained in Synthesis Example 5 is used instead of the 110 ° C. dry powder obtained in Synthesis Example 1. Tc and crystallization rate were measured. The results are shown in Table 2.

(Example 6)
Instead of the 110 ° C. dry powder obtained in Synthesis Example 1, the same operation as in Example 1 was carried out except that 0.11 g of the 110 ° C. dry powder obtained in Synthesis Example 2 was used. Tc and crystallization rate were measured. The results are shown in Table 2.

  Further, when the visible light transmittance of the obtained film was determined with a color difference meter (Tokyo Denshoku TC-1800MK type) and the haze was determined with SPECTRAL HAZE METER (Tokyo Denshoku TC-H3DPK-MK type), the visible light with a wavelength of 550 nm was obtained. The light transmittance was 75% and haze was 24.

(Example 7)
The crystallization temperature of polylactic acid is the same as in Example 1 except that 0.55 g of the 110 ° C. dry powder obtained in Synthesis Example 6 is used instead of the 110 ° C. dry powder obtained in Synthesis Example 1. Tc and crystallization rate were measured. The results are shown in Table 2.

(Example 8)
Instead of the 110 ° C. dry powder obtained in Synthesis Example 1, the same operation as in Example 1 was carried out except that 0.55 g of the 110 ° C. dry powder obtained in Synthesis Example 7 was used. Tc and crystallization rate were measured. The results are shown in Table 2.

Example 9
The crystallization temperature of polylactic acid is the same as in Example 1 except that 0.55 g of the 110 ° C. dry powder obtained in Synthesis Example 9 is used instead of the 110 ° C. dry powder obtained in Synthesis Example 1. Tc and crystallization rate were measured. The results are shown in Table 2.

(Comparative Example 1)
The same operation as in Example 1 was performed except that the resin nucleating agent was not added, and the crystallization temperature Tc and the crystallization rate of polylactic acid were measured. The results are shown in Table 2.

  Further, when the visible light transmittance of the obtained film was determined with a color difference meter (Tokyo Denshoku TC-1800MK type) and the haze was determined with SPECTRAL HAZE METER (Tokyo Denshoku TC-H3DPK-MK type), the visible light with a wavelength of 550 nm was obtained. The light transmittance was 87% and the haze was 14.

(Comparative Example 2)
In place of the 110 ° C. dry powder obtained in Synthesis Example 1, 0.55 g of zinc phenylphosphonate (trademark Eco Promote, manufactured by Nissan Chemical Industries, Ltd.) was used. Lactic acid crystallization temperature Tc and crystallization rate were measured. The results are shown in Table 2. Moreover, the result of having observed the said phenyl phosphonate zinc by the transmission electron microscope is shown in FIG. The zinc phenylphosphonate had a specific surface area of 12 m ² / g.

  Further, when the visible light transmittance of the obtained film was determined with a color difference meter (Tokyo Denshoku TC-1800MK type) and the haze was determined with SPECTRAL HAZE METER (Tokyo Denshoku TC-H3DPK-MK type), the visible light with a wavelength of 550 nm was obtained. The light transmittance was 30%, and the haze was 70.

(Comparative Example 3)
In place of the 110 ° C. dry powder obtained in Synthesis Example 1, 0.11 g of zinc phenylphosphonate (trademark Eco Promote manufactured by Nissan Chemical Industries, Ltd.) was used, and the same procedure as in Example 1 was performed to obtain poly Lactic acid crystallization temperature Tc and crystallization rate were measured. The results are shown in Table 2. The zinc phenylphosphonate had a specific surface area of 12 m ² / g.

  Further, when the visible light transmittance of the obtained film was determined with a color difference meter (Tokyo Denshoku TC-1800MK type) and the haze was determined with SPECTRAL HAZE METER (Tokyo Denshoku TC-H3DPK-MK type), the visible light with a wavelength of 550 nm was obtained. The light transmittance was 60% and the haze was 41.

(Comparative Example 4)
Instead of the 110 ° C. dry powder obtained in Synthesis Example 1, the same operation as in Example 1 was performed except that 0.55 g of the basic zinc cyanurate zinc powder obtained in Synthesis Example 8 was used. The crystallization temperature Tc and crystallization rate of polylactic acid were measured. The results are shown in Table 2.

  Further, when the visible light transmittance of the obtained film was determined with a color difference meter (Tokyo Denshoku TC-1800MK type) and the haze was determined with SPECTRAL HAZE METER (Tokyo Denshoku TC-H3DPK-MK type), the visible light with a wavelength of 550 nm was obtained. The light transmittance was 39% and the haze was 64.

(Comparative Example 5)
Instead of the 110 ° C. dry powder obtained in Synthesis Example 1, the same procedure as in Example 1 was performed, except that 0.11 g of the basic zinc cyanurate 110 ° C. powder obtained in Synthesis Example 8 was used. The crystallization temperature Tc and crystallization rate of polylactic acid were measured. The results are shown in Table 2.

  Further, when the visible light transmittance of the obtained film was determined with a color difference meter (Tokyo Denshoku TC-1800MK type) and the haze was determined with SPECTRAL HAZE METER (Tokyo Denshoku TC-H3DPK-MK type), it was visible at a wavelength of 550 nm. The light transmittance was 67% and haze was 29.

(Comparative Example 6)
Instead of 110 ° C. dry powder obtained in Synthesis Example 1, 110 g of basic cyanuric acid zinc powder obtained in Synthesis Example 8 and 29% by mass of zinc and 71% by mass of phenylphosphonic acid are contained. The mixed powder for evaluation was prepared by mixing 3.0 g of zinc phenylphosphonate (trademark Eco Promote, manufactured by Nissan Chemical Industries, Ltd.) with a household powder mixer. The same operation as in Example 1 was performed except that 0.55 g of this mixed powder was used instead of the 110 ° C. dry powder obtained in Synthesis Example 1, and the crystallization temperature Tc and the crystallization rate of polylactic acid were measured. . The results are shown in Table 2. The zinc phenylphosphonate had a specific surface area of 12 m ² / g.

  Further, when the visible light transmittance of the obtained film was determined with a color difference meter (Tokyo Denshoku TC-1800MK type) and the haze was determined with SPECTRAL HAZE METER (Tokyo Denshoku TC-H3DPK-MK type), the visible light with a wavelength of 550 nm was obtained. The light transmittance was 40% and the haze was 61.

(Comparative Example 7)
5.0 g of zinc phenylphosphonate (trade name Eco Promote manufactured by Nissan Chemical Industries, Ltd.), 16.9 g of 110 ° C. dry powder of basic zinc cyanurate obtained in Synthesis Example 8 and magnesium hydroxide (Kanto Chemical Co., Ltd.) Reagent) 0.4g was mixed with a household powder mixer to make 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. did. The same operation as in Example 1 was performed except that 0.55 g of this mixed powder was used instead of the 110 ° C. dry powder obtained in Synthesis Example 1, and the crystallization temperature Tc and the crystallization rate of polylactic acid were measured. . The results are shown in Table 2. The zinc phenylphosphonate had a specific surface area of 12 m ² / g.

(Comparative Example 8)
In place of the 110 ° C. dry powder obtained in Synthesis Example 1, the same operation as in Example 1 was carried out except that the 110 ° C. dry powder obtained in Synthesis Example 10 was used. When the conversion rate was measured, the slurry became pH 7 or less, and a part of polylactic acid was dissolved in the crystal nucleating agent for resin.

  As a result, as shown in Table 2, Examples 1 to 9 using the resin crystal nucleating agent produced by the production method of the present invention were comparative example 1 in which the resin crystal nucleating agent was not added, or basic. It was confirmed that the crystallization temperature was remarkably higher than those of Comparative Examples 4 and 5 containing only cyanuric acid zinc, the crystallization rate was remarkably high, and the crystal nucleating agent performance was very excellent.

  And when Example 1 and the comparative example 7 with the same containing component are compared, the direction of crystallization and the crystallization temperature of Example 1 were higher. Therefore, it is found that the crystal nucleating agent performance is superior when the raw materials are reacted as in Example 1 rather than simply mixing basic zinc cyanurate, zinc phenylphosphonate and magnesium hydroxide. It was.

  In addition, Synthesis Examples 1 to 7 and 9 which are crystal nucleating agents for resins produced by the production method of the present invention are Synthesis Example 10 and Comparative Example 6 in which phenylphosphonic acid is used as a raw material instead of a metal salt of phenylphosphonic acid. Compared with the zinc phenylphosphonate used in 1 and 7, the specific surface area is large and fine, so it can be said that the transparency is high.

  Moreover, Examples 1-9 are the crystallization temperature and crystallization speed | velocity | rate of about the same grade or more compared with the comparative examples 2 and 3 which contain only expensive zinc zinc phosphonate, compared with zinc phosphonate zinc. It is also confirmed that low-cost zinc oxide, basic zinc carbonate, and cyanuric acid can be used as raw materials to achieve both the effect of increasing the crystallization speed and crystallization temperature of the resin and the cost reduction. It was done.

[Crystal Nucleating Agent Evaluation-2]
(Example 10)
36 mg of basic zinc cyanurate obtained in Synthesis Example 1 (36 ° C. dry powder (crystal nucleating agent for resin)) and polypropylene resin (Novatech PP MA3, number average molecular weight 111,000, melting point 165 ° C., manufactured by Nippon Polychem Co., Ltd.) ) 3.6 g was put into a kneading machine (LABO PLASTOMILL, manufactured by Toyo Seiki Co., Ltd.) heated to 185 ° C. and kneaded at 50 rpm for 5 minutes to produce a resin composition. After cooling, the resin composition is taken out, sandwiched between a Teflon sheet and a brass plate, placed in a hot press machine heated to an upper part of 185 ° C. and a lower part of 185 ° C., and added at 0.5 kgf so that the thickness of the film becomes 0.4 mm. Pressed to create a film. The film sample was cut into small pieces, heated to 100 ° C./200° C., held for 5 minutes, and then cooled at 5 ° C./min (DSC-200 manufactured by Seiko Electronics Co., Ltd.). The crystallization temperature Tc was measured from the apex of the exothermic peak derived from polypropylene crystallization observed during cooling. Then, the temperature was raised to 200 ° C. at 100 ° C./min and held for 5 minutes, and then cooled to 130 ° C. at 100 ° C./min and then held at 130 ° C. for 5 minutes (DSC manufactured by Seiko Electronics Co., Ltd.) -200). The crystallization rate was measured from the time of the peak of the exothermic peak derived from crystallization of polypropylene observed at 130 ° C. The results are shown in Table 3.

(Comparative Example 9)
The same operation as in Example 10 was performed except that the resin nucleating agent was not added, and the crystallization temperature Tc and the crystallization rate of polylactic acid were measured. The results are shown in Table 3.

(Comparative Example 10)
Crystals of polylactic acid were obtained in the same manner as in Example 10 except that zinc phenylphosphonate (trademark Eco Promote, manufactured by Nissan Chemical Industries, Ltd.) was used instead of the 110 ° C. dry powder obtained in Synthesis Example 1. The crystallization temperature Tc and the crystallization rate were measured. The results are shown in Table 3. The zinc phenylphosphonate had a specific surface area of 12 m ² / g.

(Comparative Example 11)
In place of the 110 ° C. dry powder obtained in Synthesis Example 1, the same procedure as in Example 10 was performed except that 36 mg of the basic zinc cyanurate zinc powder obtained in Synthesis Example 8 was used. The crystallization temperature Tc and the crystallization rate were measured. The results are shown in Table 3.

  As shown in Table 3, Example 10 using the resin crystal nucleating agent produced by the production method of the present invention contains only Comparative Example 9 and basic zinc cyanurate that did not add the resin crystal nucleating agent. Thus, it was confirmed that the crystallization temperature was remarkably higher than that of Comparative Example 11, and the crystallization rate was remarkably high, so that the performance of the crystal nucleating agent was extremely excellent.

  Further, in Example 10, zinc oxide having a crystallization temperature and a crystallization rate equal to or higher than those of Comparative Example 10 containing only expensive zinc phenylphosphonate and lower in cost than zinc phenylphosphonate. It is also confirmed that by using basic zinc carbonate and cyanuric acid as raw materials, both the effect of increasing the crystallization speed and the crystallization temperature of the resin and the effect of reducing the cost can be achieved in polypropylene resin. It was done.

Claims (3)

  An aqueous solution of at least one metal salt of phenylphosphonic acid selected from magnesium phenylphosphonate, lithium phenylphosphonate, sodium phenylphosphonate and potassium phenylphosphonate; and at least one selected from zinc oxide and basic zinc carbonate A resin crystal characterized by obtaining a crystal nucleating agent for resin containing basic zinc cyanurate and zinc phenylphosphonate by dispersing and reacting a mixed slurry containing cyanuric acid and water. A method for producing a nucleating agent. The method for producing a resin crystal nucleating agent according to claim 1, wherein the crystal nucleating agent for resin has a specific surface area of 20 to 100 m ² / g.   The method for producing a crystal nucleating agent for a resin according to claim 1 or 2, wherein the dispersion is a wet dispersion using a dispersion type stirring blade or a dispersion medium.