JP5861838B2 - Method for promoting crystallization and method for producing molded product - Google Patents

Description

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

  From the viewpoint of protecting the natural environment, research on aliphatic polyester that is biodegradable in the natural environment has been actively 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.

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 to provide a novel crystal nucleating agent for resin and a resin composition capable of increasing the crystallization speed and crystallization temperature of the resin. It is in.

The present invention which solves the above-mentioned problems is obtained by adding a resin crystal nucleating agent containing basic zinc cyanurate particles to a polylactic acid resin or polyolefin resin which is a crystalline polymer, and molding the resin. A crystallization promoting method is characterized in that crystallization is promoted by using a crystal nucleating agent as a primary crystal nucleus of the resin.
In addition, by adding a resin crystal nucleating agent containing basic zinc cyanurate particles to a polylactic acid resin or polyolefin resin , which is a crystalline polymer, to increase the crystallization speed of the resin The crystallization promoting method is characterized by the following .
Their to, said basic cyanuric zinc particles, an average particle diameter _{D 50} measured by a laser diffraction method at 80～900Nm, specific surface area may be 20 to 100 m ² / g.

  Moreover, the said basic cyanuric-acid particle has at least 1 type selected from a zinc oxide and basic zinc carbonate, cyanuric acid, and water, and cyanuric acid density | concentration is 0.1-10.0 mass% with respect to water. The mixed slurry blended as described above may be manufactured by performing wet dispersion using a dispersion medium in a temperature range of 5 to 55 ° C.

Further, the resin crystal nucleating agent may contain a metal salt of phenylphosphonic acid, and the metal salt of phenylphosphonic acid is zinc phenylphosphonate, lithium phenylphosphonate, sodium phenylphosphonate, phenylphosphonic acid. It is preferably at least one selected from potassium acid, calcium phenylphosphonate, magnesium phenylphosphonate and manganese phenylphosphonate.

And it is preferable that the said resin is a polylactic acid resin and contains the basic cyanuric-acid zinc particle 0.01-10.0 mass parts with respect to 100 mass parts of this polylactic acid resin.
Moreover, it is preferable that the said resin is polyolefin resin and contains 0.01-10.0 mass parts of said basic cyanuric-acid zinc particles with respect to 100 mass parts of this polyolefin resin.
Also, the polyolefin resin may be at least one selected polypropylene resin and polyethylene resins or al.
Furthermore, the present invention resides in a method for producing a molded product characterized in that crystallization is promoted by the crystallization promoting method to obtain a molded product.

According to the present invention, a novel crystal nucleating agent for resin can be provided by using basic zinc cyanurate particles. And the resin composition containing this crystal nucleating agent and resin has a high crystallization speed and a high crystallization temperature. Therefore, a molded product having a high degree of crystallinity, a dense and high rigidity, and excellent transparency can be obtained in a short time. Then, by using basic zinc cyanurate particles having an average particle diameter D ₅₀ measured by laser diffraction method of 80 to 900 nm and a specific surface area of 20 to 100 m ² / g as a crystal nucleating agent, the transparency of the molded product. Can be further improved. Moreover, it becomes the more excellent crystal nucleating agent for resin by containing the metal salt of phenylphosphonic acid with basic zinc cyanurate particle.

3 is an XRD diffraction pattern of Synthesis Example 1. 4 is a TEM photograph of Synthesis Example 1. 10 is a TEM photograph of Synthesis Example 3. 10 is a TEM photograph of Synthesis Example 7. 10 is a TEM photograph of Synthesis Example 9. 10 is an XRD diffraction pattern of Synthesis Example 11. 14 is a TEM photograph of Synthesis Example 12. 14 is a TEM photograph of Synthesis Example 19. 4 is a TEM photograph of zinc phenylphosphonate used in Comparative Example 4.

  The resin crystal nucleating agent of the present invention contains basic zinc cyanurate particles. Basic zinc cyanurate is a substance known as a corrosion inhibitor for iron-based metal surfaces, and is not conventionally used as a crystal nucleating agent for resins. It has been discovered that it can be used as a crystal nucleating agent because it has the function of increasing the crystallization speed by increasing the crystallization speed by increasing the crystallization temperature by becoming the primary crystal nucleus of the resin that is a functional polymer. .

  By using the basic zinc cyanurate particles as a crystal nucleating agent, the crystallization speed of the resin is increased, so that the crystallization degree of the resin is increased and the heat resistance of the molded product of the resin can be improved. 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.

Not particularly limited on the size of the basic cyanuric zinc particles. For example, the average particle diameter _{D 50} measured by a laser diffraction method 80～900Nm, fine cyanuric acid having a specific surface area of 20 to 100 m ² / g By using zinc particles, a highly transparent crystal nucleating agent for resin can be obtained.

  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. Since zinc oxide, basic zinc carbonate, and cyanuric acid are inexpensive, an inexpensive crystal nucleating agent for resin can be provided. Although there is no particular limitation on the method of producing basic zinc cyanurate by reacting at least one selected from zinc oxide and basic zinc carbonate and cyanuric acid, for example, zinc oxide and cyanuric acid in boiling water The manufacturing method to make it react and the method of manufacturing by adding a shearing effect with a pin disk mill or a blade mill, heating the paste which mixed zinc oxide and cyanuric acid at 50-250 degreeC are mentioned.

Moreover, the mixed slurry which mix | blended so that the cyanuric acid density | concentration might be 0.1-10.0 mass% with respect to water, at least 1 type chosen from a zinc oxide and basic zinc carbonate, cyanuric acid, and water, Basic zinc cyanurate particles may be produced by wet dispersion using a dispersion medium in a temperature range of 5 to 55 ° C. According to this manufacturing method, the average particle diameter _{D 50} measured by a laser diffraction method 80～900Nm, can specific surface area to produce a fine basic cyanuric acid zinc particles is 20 to 100 m ² / g. 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, the cyanuric acid concentration with respect to water is 0.1 to 10.0% by mass, preferably It mix | blends so that it may become 0.1-5.0 mass%, and adjusts a mixing slurry. When the concentration of cyanuric acid with respect to water is higher than 10% by mass, the slurry viscosity becomes high and becomes a paste, so that the dispersion medium does not move when performing wet dispersion using the subsequent 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 2.0-3.0. 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.

  Next, the obtained mixed slurry is subjected to wet dispersion using a dispersion medium in a temperature range of 5 to 55 ° C., thereby reacting at least one selected from zinc oxide and basic zinc carbonate with cyanuric acid. To produce basic zinc cyanurate particles.

  Wet dispersion is performed using a dispersion medium. By performing wet dispersion using a dispersion medium, mechanochemical reaction between cyanuric acid and at least one selected from zinc oxide and basic zinc carbonate can be performed by mechanical energy generated by collision of the dispersion medium. it can. The mechanochemical reaction is a chemical reaction in which mechanical energy is applied from various directions to zinc oxide, basic zinc carbonate, and cyanuric acid 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.

  An apparatus for performing wet dispersion using a dispersion medium is a method in which a mixed slurry is added to a container charged with a dispersion medium, and then stirred to cause the dispersion medium to collide with zinc oxide, basic zinc carbonate or cyanuric acid. And basic zinc carbonate and cyanuric acid are not particularly limited as long as they can be mechanochemically reacted. Examples include sand grinders, horizontal bead mills, attritors, and pearl mills (manufactured by Ashizawa Finetech Co., Ltd.). It is done. 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.

Moreover, it is necessary to perform wet dispersion at 5-55 degreeC, Preferably it is 5-45 degreeC. If wet dispersion is performed at a temperature higher than 55 ° C., cyanuric acid dissolves in water, and this dissolved cyanuric acid reacts quickly with zinc oxide or basic zinc carbonate to promote grain growth. As shown in the synthesis examples, the basic zinc cyanurate produced has a large particle size. Then, by performing wet dispersion at a low temperature of 45 ° C. or less, the particles become particularly small. For example, fine particles having an average particle diameter D ₅₀ measured by a laser diffraction method of 500 nm or less can be produced. In addition, since it can manufacture at such low temperature, it can manufacture using an apparatus weak to heat, such as resin.

  Here, in the method of applying a shearing action with a pin disc mill or a blade mill instead of the wet dispersion using a dispersion medium as described above, the shearing member is one of the zinc oxide, basic zinc carbonate and cyanuric acid. It is impossible to obtain basic zinc cyanurate particles having a small particle size, either because they collide only in the direction and no mechanochemical reaction occurs.

Thus, the mixed slurry which mix | blended at least 1 type selected from a zinc oxide and basic zinc carbonate, cyanuric acid, and water so that the cyanuric acid density | concentration might be 0.1-10.0 mass% with respect to water. The basic cyanuric acid zinc fine particles obtained by a production method in which wet dispersion using a dispersion medium is performed in a temperature range of 5 to 55 ° C. has an average particle diameter D ₅₀ measured by a laser diffraction method of 80 to 900 nm, preferably The specific surface area is 100 to 500 nm and the specific surface area is 20 to 100 m ² / g, preferably 30 to 80 m ² / g. That is, the particle diameter is small and the specific surface area is large. Even when basic zinc cyanurate having a particle size larger than that of such cyanuric acid zinc fine particles is pulverized by a pulverizer such as a counter jet mill, the average particle size D ₅₀ measured by the laser diffraction method is 80. It cannot be as fine as ˜900 nm.

  Further, the basic zinc cyanurate fine particles obtained by the above production method are not spherical but can be needle-shaped or plate-shaped, that is, elongated fine particles, as shown in the synthesis examples described later. For such basic zinc cyanurate fine particles, for example, the primary particle diameter by observation with a transmission electron microscope has a major axis of 100 to 800 nm and a minor axis of 10 to 60 nm.

  In addition, the basic zinc cyanurate slurry containing the basic zinc cyanurate fine particles obtained may be used as a crystal nucleating agent for resin, and the slurry is dried to form a powder. It may be a crystal nucleating agent.

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

  Here, the metal salt of phenylphosphonic acid is a crystal nucleating agent for resin, but has a problem of high cost. In the present invention, by using the metal salt of phenylphosphonic acid together with the basic cyanuric acid zinc particles having a lower cost than the metal salt of phenylphosphonic acid, the effect of increasing the crystallization speed and crystallization temperature of the resin, The effect of cost reduction can be achieved at the same time.

  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 content ratio of each component of the resin crystal nucleating agent containing the basic zinc cyanurate particles and the metal salt of phenylphosphonic acid is not particularly limited. For example, 20 to 40% by mass as cyanuric acid and 10 to 10 as phenylphosphonic acid. What is necessary is just to set it as 30 mass%. When the cyanuric acid component of the crystal nucleating agent composition is less than 20% by mass, the basic zinc cyanurate content decreases and the phenyl phenylphosphonate content increases, but the phenylphosphonic acid is expensive and more Even if the phenylphosphonic acid concentration is increased, the performance of the crystal nucleating agent is not improved. 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, the zinc / phenylphosphonate zinc, which is the ratio of zinc and zinc phenylphosphonate contained in the resin crystal nucleating agent containing the basic zinc cyanurate particles and the metal salt of phenylphosphonic acid, has a mass ratio of 1 It is preferably less than 4. This is because even if the concentration of expensive phenylphosphonic acid is increased to 1 or less, 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 decrease.

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

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

  Moreover, the crystal nucleating agent for resin containing the basic zinc cyanurate particles and the metal salt of phenylphosphonic acid is phenyl phenylphosphonate such as magnesium phenylphosphonate, lithium phenylphosphonate, sodium phenylphosphonate, potassium phenylphosphonate. It can also be produced by reacting an aqueous solution of a metal salt of phosphonic acid, at least one selected from zinc oxide and basic zinc carbonate, and cyanuric acid, if necessary, by heating.

Moreover, the crystal nucleating agent for resin containing the basic zinc cyanurate particles and the metal salt of phenylphosphonic acid is phenyl phenylphosphonate such as magnesium phenylphosphonate, lithium phenylphosphonate, sodium phenylphosphonate, potassium phenylphosphonate. An aqueous solution of a metal salt of phosphonic acid, at least one selected from zinc oxide and basic zinc carbonate, cyanuric acid, and water, the cyanuric acid concentration is 0.1 to 10.0% by mass with respect to this water It is also possible to produce a mixed slurry blended so as to be, for example, in a temperature range of 5 to 55 ° C. by vigorously stirring and dispersing with a disperser type stirring blade or a wet dispersion using a dispersion medium and reacting each raw material. it can. By drying the slurry obtained by this production method at 110 ° C., fine basic cyanuric acid zinc, zinc phenylphosphonic acid, and metal hydroxide constituting the metal salt of the above-mentioned phenylphosphonic acid as a raw material A crystal nucleating agent for resin containing (for example, magnesium hydroxide) can be produced. The crystal nucleating agent for resin 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 prepared by dissolving carbonate or metal hydroxide and phenylphosphonic acid in water. 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 is said to have a high crystallization speed and a high crystallization temperature because the polylactic acid partially dissolves when kneaded into the polylactic acid resin. The crystal nucleating agent performance becomes small, and the generated phenylphosphonate zinc becomes coarse particles, and the crystal nucleating agent performance of the polylactic acid resin is lowered. 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, the cyanuric acid concentration is 0.1 to 10.0% by mass, preferably 1.0, based on this water. It is added so that it may become -5.0 mass%, and the aqueous solution of the said metal salt of phenylphosphonic acid is mixed subsequently. 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 slurry viscosity becomes high and becomes a paste, so that it is difficult to perform strong stirring and dispersion by wet dispersion using a disperse type stirring blade in the latter stage or 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 strongly stirred and dispersed by a disperser type stirring blade, a wet dispersion using a dispersion medium, or the like in a temperature range of 5 to 55 ° C., for example. 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 the case of strong stirring dispersion, when wet dispersion is performed at a temperature higher than 55 ° C., the basic zinc cyanurate and zinc phenylphosphonate that are produced become coarse particles, and the crystal nucleating agent performance of the polylactic acid resin is reduced. It is preferable to carry out at less than 55 ° C. Moreover, when it manufactures by performing wet dispersion using a dispersion medium, the primary particle by observation with a transmission electron microscope has a major axis of 100 to 1200 nm, a minor axis of 10 to 100 nm, and an average particle diameter D ₅₀ measured by a laser diffraction method of 80. A crystal nucleating agent for resin containing basic zinc cyanurate particles having a diameter of ˜900 nm and zinc phenylphosphonate particles having a major axis and a minor axis of 50 to 800 nm can be produced.

  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.

Although there is no restriction | limiting in particular in the magnitude | size of such a crystal nucleating agent for resin, It can be set as the crystal nucleating agent for resins with high transparency by using the fine particle whose specific surface area is 20-100 m < ² > / g. it can.

  And the resin composition of the present invention contains basic zinc cyanurate particles that are the above-mentioned crystal nucleating agent for resin and resin, and basic zinc cyanurate particles that are the above-mentioned crystal nucleating agent for resin, It contains a metal salt of phenylphosphonic acid and a resin.

  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. The production method of the polylactic acid resin is not particularly limited, but can be produced, for example, by ring-opening polymerization of lactide, or by directly polycondensing D-form, L-form, racemate, etc. of lactic acid. .

As the polyolefin resins, polyethylene resins, polypropylene resins, and the like. 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.

  Although there is no limitation in particular in the compounding ratio of basic cyanuric-acid zinc particle and resin, when using polylactic acid resin as resin, basic cyanuric-acid zinc particle 0.01-100 mass parts of polylactic acid resin. It is preferable to set it as 10.0 mass parts. Moreover, when using polyolefin-type resin as resin, it is preferable to make basic cyanuric-acid zinc particle 0.01-10.0 mass parts with respect to 100 mass parts of polyolefin-type resin. This is because when the amount of basic zinc cyanurate particles is less than 0.01 parts by mass with respect to 100 parts by mass of the resin, the effect of increasing the crystallization speed and crystallization temperature of the resin may not be significant. Moreover, it is because the specific gravity of the resin composition becomes too heavy when the amount of basic cyanuric acid zinc particles is more than 10.0 parts by mass with respect to 100 parts by mass of the resin.

  Similarly, there is no particular limitation on the blending ratio when using a resin crystal nucleating agent containing basic zinc cyanurate particles and a metal salt of phenylphosphonic acid, but when using a polylactic acid resin as a resin, The resin crystal nucleating agent containing basic zinc cyanurate particles and a metal salt of phenylphosphonic acid is preferably 0.01 to 10.0 parts by mass with respect to 100 parts by mass of the lactic acid resin. Moreover, also when using polyolefin-type resin as resin, the crystal nucleating agent for resin containing the basic zinc cyanurate particle and the metal salt of phenylphosphonic acid with respect to 100 mass parts of polyolefin-type resin is 0.01-10. The content is preferably 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, 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 resin composition of the present invention may contain a 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.

  The method of producing a resin composition using a resin, basic zinc cyanurate, or a metal salt of basic cyanuric acid zinc and phenylphosphonic acid, and various additives added as necessary is not particularly limited. It can be produced by the same method as that for a resin composition containing a known crystal nucleating agent. For example, a resin, basic zinc cyanurate, or a metal salt of basic cyanuric acid zinc and phenylphosphonic acid, and additives to be added as necessary are mixed with various mixers, and a single screw or twin screw extruder is used. For example, the resin composition can be produced by kneading at a temperature of about 150 to 220 ° C. Further, a method for producing a master batch containing a basic zinc cyanurate or a metal salt of basic cyanuric acid zinc and phenylphosphonic acid or an additive to be added if necessary at a high concentration and adding this to a resin Is also possible. And the method of adding the basic cyanuric acid zinc or the metal salt of basic cyanuric acid zinc and phenylphosphonic acid in the superposition | polymerization stage of resin may be sufficient.

  With such a resin composition of the present invention, various molded products can be easily produced by a general molding method such as injection molding, blow molding, vacuum molding, compression molding or the like. 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 resin composition of this invention contains the basic cyanuric-acid zinc particle which is a crystal nucleating agent, or the basic cyanuric-acid zinc particle and the metal salt of phenylphosphonic acid, the crystallization rate of resin 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. Moreover, since the crystallization temperature of the resin is increased by containing basic zinc cyanurate particles, or the metal salt of basic cyanuric acid zinc particles and phenylphosphonic acid, the resin is molded with a mold such as injection molding. In this case, since the mold cooling temperature can be increased, a resin molding 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)
The 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)
A batch type sand grinder vessel with a volume of 1 liter and an inner wall of urethane resin was charged with 1140 g of stabilized zirconia crushed beads of φ1 mm and 300 g of pure water, and the stirring disc was rotated at 500 rpm while cooling the sand grinder vessel with a -5 ° C chiller. 5.9 g of cyanuric acid powder (manufactured by Nissan Chemical Industries, Ltd.) was added. Subsequently, the stirring disk was rotated at 500 rpm while the sand grinder container was cooled with a -5 ° C. chiller, and 9.3 g of zinc oxide powder (2 types zinc oxide manufactured by Sakai Chemical Co., Ltd.) was added. 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 charging the zinc oxide powder, the stirring disc was rotated at 500 rpm while dispersing the sand grinder container with a -5 ° C chiller for 12 hours to disperse. The slurry temperature at this time was 9 degreeC. As a result, 310 g of a white slurry having a pH of 7.1, an electrical conductivity of 84 μS / cm, and a solid content of 4.8% by mass when dried at 110 ° C. was obtained. When the elemental analysis of the 110 degreeC dry powder of the obtained white slurry was performed, they were 10.37 mass% carbon, 1.35 mass% hydrogen, 12.05 mass% nitrogen, and 28.20 mass% oxygen. Moreover, mass measurement after thermally decomposing this 110 degreeC dry powder at 1000 degreeC to zinc oxide was performed, and it was 48.03 mass% when the amount of active ingredients of Zn of 110 degreeC dry powder was calculated | required. Further, when X-ray powder diffraction analysis was performed on the dried powder at 110 ° C., as shown in FIG. 1, no diffraction peak attributed to the raw materials cyanuric acid and zinc oxide was observed, and the diffraction peak of basic cyanuric acid zinc was Observed. From these results, the 110 ° C. dry powder was determined to be basic zinc cyanurate of Zn ₅ (C ₃ N ₃ O ₃ ) ₂ (OH) ₃ .3H ₂ O. Fine particles contained in the resulting white slurry is transmissive long axis 100~200nm the electron microscopic observation, the minor axis is at 10 to 15 nm, the average particle size _{D 50} by laser diffractometry particle size measurement is 103 nm, 70 It was basic cyanuric acid zinc having a specific surface area Sw after drying at ° C. of 59 m ² / g. The results are shown in Table 1. Moreover, the photograph observed with the transmission electron microscope is shown in FIG.

(Synthesis Example 2)
A batch type sand grinder vessel with a volume of 1 liter and an inner wall of urethane resin was charged with 1140 g of stabilized zirconia crushed beads of φ1 mm and 300 g of pure water, and the stirring disc was rotated at 1500 rpm while cooling the sand grinder vessel with a -5 ° C chiller. 5.9 g of cyanuric acid powder (manufactured by Nissan Chemical Industries, Ltd.) was added. Subsequently, the stirring disk was rotated at 1500 rpm while cooling the sand grinder container with a -5 ° C. chiller, and 9.3 g of zinc oxide powder (2 types zinc oxide manufactured by Sakai Chemical Co., Ltd.) was added. 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 charging the zinc oxide powder, the stirring disc was rotated at 1500 rpm while dispersing the sand grinder container with a 0 ° C. chiller for 8 hours to disperse. The slurry temperature at this time was 16 degreeC. As a result, 311 g of a white slurry having a pH of 7.1, an electric conductivity of 109 μS / cm, and a solid content of 4.8% by mass when dried at 110 ° C. was obtained. Moreover, when the X-ray powder diffraction analysis was performed about the 110 degreeC dry powder of the obtained white slurry, it was the same diffraction pattern as the synthesis example 1. FIG. The fine particles contained in the obtained white slurry have a major axis of 100 to 300 nm and a minor axis of 10 to 20 nm in observation with a transmission electron microscope, an average particle diameter D ₅₀ by laser diffraction particle diameter measurement is 155 nm, and 70 It was a basic zinc cyanurate having a specific surface area Sw after drying at 49 ° C. of 49 m ² / g. The results are shown in Table 1.

(Synthesis Example 3)
A batch sand grinder container with a volume of 1 liter and an inner wall of urethane resin was charged with 1140 g of stabilized zirconia crushed beads of φ1 mm and 300 g of pure water, and the stirring disk was rotated at 2000 rpm while cooling the sand grinder container with a -5 ° C chiller. 5.9 g of cyanuric acid powder (manufactured by Nissan Chemical Industries, Ltd.) was added. Subsequently, the stirring disk was rotated at 2000 rpm while cooling the sand grinder container with a -5 ° C. chiller, and 9.3 g of zinc oxide powder (2 types of zinc oxide manufactured by Sakai Chemical Co., Ltd.) was added. 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 charging the zinc oxide powder, the stirring disc was rotated at 2000 rpm while dispersing the sand grinder container with a -5 ° C chiller for 8 hours to disperse. The slurry temperature at this time was 23 degreeC. As a result, 305 g of a white slurry having a pH of 7.0, an electric conductivity of 120 μS / cm, and a solid content of 4.8% by mass when dried at 110 ° C. was obtained. When the X-ray powder diffraction analysis was performed about the 110 degreeC dry powder of the obtained white slurry, it was the same diffraction pattern as the synthesis example 1. FIG. The resulting fine particles contained in the white slurry, transmission electron long axis in the microscope observation 100 to 400 nm, a short axis 20 to 30 nm, average particle size _{D 50} by laser diffractometry particle size measurement is 175 nm, 70 It was a basic zinc cyanurate with a specific surface area Sw after drying at 32 ° C. of 32 m ² / g. The results are shown in Table 1. Moreover, the photograph observed with the transmission electron microscope is shown in FIG.

(Synthesis Example 4)
A batch type sand grinder vessel with a volume of 1 liter and urethane resin inside is charged with 1140 g of stabilized zirconia crushed beads of φ1 mm and 290 g of pure water, and the stirring disc is rotated at 1500 rpm while cooling the sand grinder vessel with tap water at 20 ° C. 9.2 g of cyanuric acid powder (manufactured by Nissan Chemical Industries, Ltd.) was added. Subsequently, while the sand grinder container was cooled with 20 ° C. tap water, the stirring disk was rotated at 1500 rpm, and 14.5 g of zinc oxide powder (2 types zinc oxide manufactured by Sakai Chemical Co., Ltd.) was added. 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 charging the zinc oxide powder, the stirring disc was rotated at 1500 rpm while dispersing the sand grinder container with 20 ° C. tap water for 10 hours. The slurry temperature at this time was 40 degreeC. As a result, 300 g of a white slurry having a pH of 6.8, an electric conductivity of 148 μS / cm, and a solid content of 7.5% by mass when dried at 110 ° C. was obtained. When the X-ray powder diffraction analysis was performed about the 110 degreeC dry powder of the obtained white slurry, it was the same diffraction pattern as the synthesis example 1. FIG. The resulting fine particles contained in the white slurry, transmission electron microscopy major axis at observation 100 to 300 nm, minor axis is 20 to 30 nm, an average particle size _{D 50} by laser diffractometry particle size measurement 188 nm, 70 ° C. It was a basic zinc cyanurate having a specific surface area Sw after drying of 26 m ² / g.

(Synthesis Example 5)
A batch sand grinder container with a volume of 1 liter and an inner wall of urethane resin was charged with 1140 g of stabilized zirconia crushed beads of φ1 mm and 290 g of pure water, and the stirring disk was rotated at 1500 rpm to obtain cyanuric acid powder (manufactured by Nissan Chemical Industries, Ltd.) 5.9 g was charged. Subsequently, the stirring disk was rotated at 1500 rpm, and 9.3 g of zinc oxide powder (2 types zinc oxide manufactured by Sakai Chemical Co., Ltd.) was added. 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 adding zinc oxide powder, the stirring disk was rotated at 1500 rpm and dispersed for 5 hours. The slurry temperature at this time was 50 degreeC. As a result, 300 g of a white slurry having a pH of 8.2, an electric conductivity of 176 μS / cm, and a solid content of 4.8% by mass when dried at 110 ° C. was obtained. When the X-ray powder diffraction analysis was performed about the 110 degreeC dry powder of the obtained white slurry, it was the same diffraction pattern as the synthesis example 1. FIG. The fine particles contained in the obtained white slurry have a major axis of 100 to 200 nm and a minor axis of 20 to 40 nm in transmission electron microscope observation, an average particle diameter D ₅₀ by laser diffraction particle diameter measurement is 623 nm, and 70 This was basic zinc cyanurate having a specific surface area Sw after drying at 25 ° C. of 25 m ² / g. The results are shown in Table 1.

(Synthesis Example 6)
A batch type sand grinder container having a volume of 1 liter and an inner wall of urethane resin was charged with 1140 g of stabilized zirconia crushed beads of φ1 mm and 298 g of pure water, and the stirring disk was rotated at 2000 rpm while cooling the sand grinder container with a 10 ° C. chiller. 4.3 g of cyanuric acid powder (Nissan Chemical Industry Co., Ltd.) was added. Subsequently, while the sand grinder container was cooled with a chiller at 10 ° C., the stirring disk was rotated at 1500 rpm, and 9.0 g of basic zinc carbonate powder (74.8% by mass of zinc oxide component, manufactured by Sakai Chemical Co., Ltd.) was added. The molar ratio of zinc oxide equivalent / cyanuric acid was 2.5, and the cyanuric acid concentration relative to water was 1.4% by mass. After charging the zinc oxide powder, the stirring disc was rotated at 1500 rpm while dispersing the sand grinder container with a chiller at 10 ° C. for 8 hours to disperse. The slurry temperature at this time was 30 degreeC. As a result, 310 g of white slurry having a pH of 6.3, an electrical conductivity of 556 μS / cm, a viscosity of 198 mPa · s, and a solid content of 3.5% by mass when dried at 110 ° C. was obtained. When the X-ray powder diffraction analysis was performed about the 110 degreeC dry powder of the obtained white slurry, it was the same diffraction pattern as the synthesis example 1. FIG. The resulting fine particles contained in the white slurry, transmission electron long axis in the microscope observation 100 to 300 nm, a short axis 20 to 40 nm, average particle size _{D 50} by laser diffractometry particle size measurement is 303 nm, 70 This was basic zinc cyanurate having a specific surface area Sw after drying at 30 ° C. of 30 m ² / g. The results are shown in Table 1.

(Synthesis Example 7)
24 kg of pure water and 1.88 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, and after stirring and mixing with a disper, the zinc oxide equivalent concentration is 7.69% by mass. 26 kg of slurry was prepared. Next, 66 kg of stabilized zirconia crushed beads having a diameter of 1 mm were charged into a horizontal bead mill (pearl mill PM25TEX-H manufactured by Ashizawa Finetech Co., Ltd.) having an effective volume of 10.66 liters and an inner wall of urethane resin. After 144 kg of pure water was charged into a circulation tank equipped with a chiller, the disk of the pearl mill was rotated at a peripheral speed of 10 m / second, and pure water was circulated while supplying pure water to the pearl mill at a supply speed of 5 kg / min. After the start of circulation, 1.19 kg of cyanuric acid powder (manufactured by Nissan Chemical Industries, Ltd.) was added. After adding the cyanuric acid powder, after adjusting with a chiller so that the temperature of the circulating slurry is 32 ° C., 24.5 kg of zinc oxide slurry having a zinc oxide equivalent concentration of 7.69% by mass is divided into 5 parts over 10 minutes. Added. 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. Even after the addition of the zinc oxide slurry, the slurry was circulated and dispersed for 15 hours at a feed rate of 5 kg / min while rotating the disk of the pearl mill at a peripheral speed of 10 m / sec. Also during this time, the circulating slurry temperature was adjusted with a chiller so as to be 32 ° C. As a result, 166 kg of white slurry having a pH of 6.8, an electrical conductivity of 67 μS / cm, a viscosity of 51 mPa · s, and a solid content of 1.8% by mass when dried at 110 ° C. was obtained. When the X-ray powder diffraction analysis was performed about the 110 degreeC dry powder of the obtained white slurry, it was the same diffraction pattern as the synthesis example 1. FIG. The fine particles contained in the obtained white slurry have a major axis of 100 to 600 and a minor axis of 25 to ₅₀ nm in observation with a transmission electron microscope, and an average particle diameter D50 by laser diffraction particle diameter measurement is 310 nm. This was basic zinc cyanurate having a specific surface area Sw after drying at 50 ° C. of 51 m ² / g. The results are shown in Table 1. Moreover, the photograph observed with the transmission electron microscope is shown in FIG.

(Synthesis Example 8)
A batch sand grinder container with a volume of 1 liter and an inner wall of urethane resin was charged with 1140 g of stabilized zirconia crushed beads of φ1 mm and 290 g of pure water, and the stirring disk was rotated at 1500 rpm to obtain cyanuric acid powder (manufactured by Nissan Chemical Industries, Ltd.) 5.9 g was charged. Subsequently, the stirring disk was rotated at 1500 rpm, and 11.2 g of zinc oxide powder (2 types zinc oxide manufactured by Sakai Chemical Co., Ltd.) was charged. The molar ratio of zinc oxide / cyanuric acid was 3.0, and the cyanuric acid concentration relative to water was 2.0% by mass. After adding zinc oxide powder, the stirring disk was rotated at 1500 rpm and dispersed for 5 hours. The slurry temperature at this time was 23 degreeC. As a result, 300 g of a white slurry having a pH of 7.8, an electrical conductivity of 98 μS / cm, and a solid content of 5.6% by mass when dried at 110 ° C. was obtained. When the X-ray powder diffraction analysis was performed about the 110 degreeC dry powder of the obtained white slurry, it was the same diffraction pattern as the synthesis example 1. FIG. The resulting fine particles contained in the white slurry, transmission electron long axis in the microscope observation 100 to 300 nm, a short axis 15-20 nm, the average particle size _{D 50} by laser diffractometry particle size measurement is 152 nm, 70 This was basic zinc cyanurate with a specific surface area Sw after drying at 40 ° C. of 40 m ² / g. The results are shown in Table 1.

(Synthesis Example 9)
A 1 liter beaker charged with 900 g of pure water was placed on a hot plate equipped with a magnetic stirrer, and 18.9 g of cyanuric acid powder (manufactured by Nissan Chemical Industries, Ltd.) was added while stirring with a stirrer. Subsequently, 30.0 g of zinc oxide powder (2 types of zinc oxide manufactured by Sakai Chemical Co., Ltd.) was added, and then the mixed slurry was heated until boiling with a hot plate while stirring with a stirrer. 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 for 8 hours under boiling at 100 ° C., 716 g of a white slurry having a pH of 7.1, an electric conductivity of 46 μS / cm, a viscosity of 500 mPa · s, and a solid content of 6.8% by mass when dried at 110 ° C. was obtained. When the X-ray powder diffraction analysis was performed about the 110 degreeC dry powder of the obtained white slurry, it was the same diffraction pattern as the synthesis example 1. FIG. The resulting fine particles contained in the white slurry, transmission electron microscopy long axis is observed 2000～20000Nm, minor axis at 200 to 500 nm, the average particle size _{D 50} by laser diffraction method is 2620nm, 70 ℃ dried Was a basic zinc cyanurate having a specific surface area Sw of 5 m ² / g. The results are shown in Table 1. Moreover, the photograph observed with the transmission electron microscope is shown in FIG.

(Synthesis Example 10)
Instead of using a pearl mill, a horizontal bead mill (System Zeta LMZ25 manufactured by Ashizawa Finetech Co., Ltd.) with an effective volume of 10.66 liters and an inner wall is used, and the same operation is performed with the same ratio of raw materials in Synthesis Example 7. As a result, 168 kg of white slurry having a pH of 7.9, an electric conductivity of 206 μS / cm, a viscosity of 76 mPa · s, and a solid content of 1.8% by mass when dried at 110 ° C. was obtained. When the X-ray powder diffraction analysis was performed about the 110 degreeC dry powder of the obtained white slurry, it was the same diffraction pattern as the synthesis example 1. FIG. The fine particles contained in the obtained white slurry have a major axis of 100 to 800 nm and a minor axis of 10 to 60 nm in transmission electron microscope observation, and an average particle size D ₅₀ by laser diffraction particle size measurement is 397 nm. It was basic cyanuric acid zinc having a specific surface area Sw after drying at 70 ° C. of 54 m ² / g. The results are shown in Table 1.

Example 1
Kneading of 40 mg of basic cyanuric acid zinc powder 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 Nature Works) at 185 ° C. The resin composition was manufactured by putting into a machine (LABO PLASTOMILL made by Toyo Seiki Co., Ltd.) and kneading at 50 rpm for 5 minutes. After cooling, the resin composition is taken out, sandwiched between a Teflon (registered trademark) sheet and a brass plate, and placed in a hot press machine heated to an upper part of 185 ° C. and a lower part of 185 ° C., and 0 mm so that the thickness of the film becomes 0.4 mm. A film was prepared by pressurizing at 5 kgf. 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.). went. The crystallization temperature Tc was measured from the apex of the exothermic peak derived from the crystallization of polylactic acid observed during cooling.

  Further, this film-like sample is cut into small pieces, heated to 100 ° C./min to 200 ° C. and held for 5 minutes, then cooled to 130 ° C. at 200 ° C./min and then held at 130 ° C. for 10 minutes. The measurement (DSC-200 manufactured by Seiko Electronics Co., Ltd.) was performed. The crystallization rate was measured from the time of the peak of the exothermic peak derived from the crystallization of polylactic acid observed at 130 ° C. The results are shown in Table 2. In Table 2, the nucleating agent concentration is described as a mass part of basic cyanuric acid zinc with respect to 100 parts by mass of the resin.

  Moreover, 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 transmittance was determined. Was 24% and haze was 70.

(Example 2)
Operation similar to Example 1 except having used the basic cyanuric-acid zinc 110 degreeC dry powder obtained in the synthesis example 7 instead of the basic cyanuric-acid zinc 110 degreeC dry powder obtained in the synthesis example 9. The crystallization temperature Tc and the crystallization rate of polylactic acid were measured. The results are shown in Table 2. Moreover, when the visible light transmittance and haze of the obtained film were determined by the same method as in Example 1, the visible light transmittance was 52% and the haze was 50.

(Example 3)
Operation similar to Example 1 except having used the basic cyanuric-acid zinc 110 degreeC dry powder obtained in the synthesis example 10 instead of the basic cyanuric-acid zinc 110 degreeC dry powder obtained in the synthesis example 9. The crystallization temperature Tc and the crystallization rate of polylactic acid were measured. The results are shown in Table 2. Moreover, when the visible light transmittance and haze of the obtained film were determined by the same method as in Example 1, the visible light transmittance was 44% and the haze was 57.

Example 4
The crystallization temperature Tc and the crystallization rate of polylactic acid were measured in the same manner as in Example 3 except that the amount of basic cyanuric acid zinc powder obtained in Synthesis Example 10 was 8 mg, except that the amount used was 8 mg. . The results are shown in Table 2. Moreover, when the visible light transmittance and haze of the obtained film were determined in the same manner as in Example 1, the visible light transmittance was 78% and the haze was 21.

(Example 5)
The crystallization temperature Tc and the crystallization rate of polylactic acid were measured in the same manner as in Example 3 except that the amount of basic cyanuric acid zinc powder obtained in Synthesis Example 10 was changed to 80 mg. . The results are shown in Table 2. Moreover, when the visible light transmittance and haze of the obtained film were determined by the same method as in Example 1, the visible light transmittance was 22% and the haze was 80.

(Example 6)
110 mg of basic cyanuric acid zinc powder 36 mg obtained in Synthesis Example 9 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 were 185 ° C. The mixture was placed in a kneader (LABO PLASTOMILL, manufactured by Toyo Seiki Co., Ltd.) 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.

  Further, this film-like sample is cut into small pieces, heated to 100 ° C./min to 200 ° C. and held for 5 minutes, then cooled to 130 ° C. at 200 ° C./min and then held at 130 ° C. for 10 minutes. The measurement (DSC-200 manufactured by Seiko Electronics Co., Ltd.) was performed. 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 2. Moreover, when the visible light transmittance and haze of the obtained film were determined by the same method as in Example 1, the visible light transmittance was 30% and the haze was 85.

(Example 7)
Operation similar to Example 6 except having used the basic cyanuric-acid zinc 110 degreeC dry powder obtained in the synthesis example 7 instead of the basic cyanuric-acid zinc 110 degreeC dry powder obtained in the synthesis example 9. The crystallization temperature Tc and the crystallization rate of polypropylene were measured. The results are shown in Table 2. Moreover, when the visible light transmittance and haze of the obtained film were determined in the same manner as in Example 1, the visible light transmittance was 40% and the haze was 71.

(Example 8)
The same operation as in Example 6 except that the basic zinc cyanurate obtained in Synthesis Example 10 was used in place of the basic zinc cyanurate obtained in Synthesis Example 9 at 110 ° C. The crystallization temperature Tc and the crystallization rate of polypropylene were measured. The results are shown in Table 2. Moreover, when the visible light transmittance and haze of the obtained film were determined by the same method as in Example 1, the visible light transmittance was 38% and the haze was 78.

(Comparative Example 1)
The same operation as in Example 1 was performed except that basic zinc cyanurate was not added to the polylactic acid resin. Moreover, when the visible light transmittance and haze of the obtained film were determined by the same method as in Example 1, the visible light transmittance was 74% and the haze was 22.

(Comparative Example 2)
The same operation as in Example 6 was performed except that basic zinc cyanurate was not added to the polypropylene resin. Moreover, when the visible light transmittance and haze of the obtained film were determined by the same method as in Example 1, the visible light transmittance was 57% and the haze was 31.

  As a result, as shown in Table 2, it was found that by adding basic zinc cyanurate, the crystallization temperature and crystallization speed of the resin are increased, and basic cyanuric acid zinc can be used as a crystal nucleating agent for the resin. It was. Thus, since the crystallization speed of the resin is high, the degree of crystallization of the resin is high, 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. And by crystallizing in a short time, the size of the spherulite becomes small, and a molded product having high rigidity and high transparency can be obtained without adding glass fiber or the like. In addition, since the crystallization temperature of the resin is high, the cooling temperature of the mold can be increased, so that a molded product of the resin can be produced in a short time.

  Further, the basic zinc cyanurate particles of Synthesis Example 7 and Synthesis Example 10 are particles that are significantly smaller than the basic zinc cyanurate particles of Synthesis Example 9, and therefore the basic zinc cyanurate particles of Synthesis Example 7 are used. Example 3 and Example 8 using the basic zinc cyanurate of Example 2 and Example 7 and Synthesis Example 10 were the same as Example 1 and Example 6 using the basic zinc cyanurate particles of Synthesis Example 9. In contrast, the visible light transmittance was high, the haze was low, and the transparency was excellent.

(Synthesis Example 11)
Into a 2-liter plastic container, 1501 g of pure water and 79.7 g of phenylphosphonic acid (manufactured by Nissan Chemical Industries, Ltd.) are also referred to as “PPA” hereinafter, and magnesium carbonate (reagent MgO manufactured by Kanto Chemical Co., Ltd.) with stirring. 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. 6, the 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 3.

(Synthesis Example 12)
The same operation as in Synthesis Example 11 was performed 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 3. Moreover, the photograph observed with the transmission electron microscope is shown in FIG.

(Synthesis Example 13)
After mixing 313 g of the phenylphosphonate magnesium aqueous solution prepared in Synthesis Example 11 and 1160 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., 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 3.

(Synthesis Example 14)
To a 2-liter plastic container, 997 g of pure water and 313 g of magnesium phenylphosphonate aqueous solution obtained in Synthesis Example 11 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 3.

(Synthesis Example 15)
A white slurry having the same operation as in Synthesis Example 12 except that the slurry temperature was changed to 50 ° C., having a pH of 7.7, an electric conductivity of 213 μS / cm, a viscosity of 720 mPa · s, and a solid content of 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 3.

(Synthesis Example 16)
A white slurry having the same operation as in Synthesis Example 12 except that the slurry temperature was changed to 60 ° C., pH 7.6, conductivity 183 μS / cm, viscosity 640 mPa · s, solid content at 110 ° C. when dried at 7.6 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 3.

(Synthesis Example 17)
After mixing 195 g of the phenylphosphonate magnesium aqueous solution prepared in Synthesis Example 11 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., 33.1 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 3.

(Synthesis Example 18)
A SUS kg container with a capacity of 700 liters was charged with 368 kg of pure water, and a disperse blade was dispersed at 500 rpm with a stirrer hyper (Ashizawa Finetech Co., Ltd. hyper) equipped with a 300 mm diameter disper blade. 20.3 kg of Chemical Co., Ltd. (2 types of zinc oxide) was added. The jacket water was heated to raise the temperature of the zinc oxide slurry to 49 ° C. When the zinc oxide slurry on the way reaches 40 ° C, the dispersion speed of the disper blade is increased to 800 rpm and strongly dispersed, while 11.7 kg of cyanuric acid powder (manufactured by Nissan Chemical Industries, Ltd.) is divided into three parts every 30 minutes. It was thrown into. After the cyanuric acid powder was added, the temperature of the slurry was 49 ° C., and the temperature of the jacket water was adjusted so as to maintain this temperature. The molar ratio of zinc oxide / cyanuric acid was 2.75, and the cyanuric acid concentration relative to water was 2.9% by mass. This slurry was strongly dispersed for 9 hours while maintaining the rotational speed of the disperse blades at 800 rpm. As a result, 395 kg of a white slurry having a pH of 7.5, an electric conductivity of 29 μS / cm, a viscosity of 866 mPa · s, and a solid content of 8.3% by mass when dried at 110 ° C. was obtained. When the X-ray powder diffraction analysis was performed about 110 degreeC dry powder of the obtained white slurry, the diffraction peak of basic zinc cyanurate was observed. The fine particles contained in the obtained white slurry are basic cyanuric acid having a major axis of 200 to 800 nm, a minor axis of 20 to 50 nm and a specific surface area Sw after drying at 110 ° C. of 35 m ² / g as observed with a transmission electron microscope. It was zinc.

Magnesium phenylphosphonate prepared in Synthesis Example 11 while charging 589 g of a white slurry with a basic zinc cyanurate conversion concentration of 8.3 mass% obtained in a 1 liter plastic bottle and strongly dispersing at 3200 rpm with a 30 mm diameter disper blade After adding 168 g of the aqueous solution, it was further strongly dispersed for 6 hours. As a result, a slurry having a pH of 8.5, an electrical conductivity of 188 μS / cm, and a viscosity of 840 mPa · s was obtained, and the wet cake obtained by Nutsche filtration using a filter paper (5C Toyo Filter Paper Co., Ltd.) was dried at 110 ° C. Thereafter, the dried cake was pulverized by a home mixer to obtain 56 g of powder having a specific surface area of 35 m ² / g. 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 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 3.

(Synthesis Example 19)
24 kg of pure water and 1.88 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 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 3. Moreover, the photograph observed with the transmission electron microscope is shown in FIG.

(Synthesis Example 20)
After mixing 156 g of the magnesium phenylphosphonate aqueous solution prepared in Synthesis Example 11 and 1233 g of pure water in a 2 liter plastic container, the mixture 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 3.

(Synthesis Example 21)
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 3.

[Crystal Nucleating Agent Evaluation-1]
Example 9
The dried powder (crystal nucleating agent for resin) at 110 ° C. obtained in Synthesis Example 11 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 4. In Table 4, the concentration of the resin crystal nucleating agent is described as part by mass of the resin crystal nucleating agent with respect to 100 parts by mass of the resin.

(Example 10)
Instead of the 110 ° C. dry powder obtained in Synthesis Example 11, the same operation as in Example 9 was carried out except that 0.55 g of the 110 ° C. dry powder obtained in Synthesis Example 12 was used, and the crystallization temperature of polylactic acid Tc and crystallization rate were measured. The results are shown in Table 4.

  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 44% and the haze was 56.

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

(Example 12)
Instead of the 110 ° C. dry powder obtained in Synthesis Example 11, the same operation as in Example 9 was carried out except that 0.55 g of the 110 ° C. dry powder obtained in Synthesis Example 14 was used, and the crystallization temperature of polylactic acid Tc and crystallization rate were measured. The results are shown in Table 4.

(Example 13)
Instead of the 110 ° C. dry powder obtained in Synthesis Example 11, the same operation as in Example 9 was carried out except that 0.55 g of the 110 ° C. dry powder obtained in Synthesis Example 15 was used, and the crystallization temperature of polylactic acid Tc and crystallization rate were measured. The results are shown in Table 4.

(Example 14)
Instead of the 110 ° C. dry powder obtained in Synthesis Example 11, the same operation as in Example 9 was carried out except that 0.11 g of the 110 ° C. dry powder obtained in Synthesis Example 12 was used. Tc and crystallization rate were measured. The results are shown in Table 4.

  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 75% and haze was 24.

(Example 15)
Instead of the 110 ° C. dry powder obtained in Synthesis Example 11, the same operation as in Example 9 was carried out except that 0.55 g of the 110 ° C. dry powder obtained in Synthesis Example 16 was used, and the crystallization temperature of polylactic acid Tc and crystallization rate were measured. The results are shown in Table 4.

(Example 16)
Instead of the 110 ° C. dry powder obtained in Synthesis Example 11, the same operation as in Example 9 was carried out except that 0.55 g of the 110 ° C. dry powder obtained in Synthesis Example 17 was used, and the crystallization temperature of polylactic acid Tc and crystallization rate were measured. The results are shown in Table 4.

(Example 17)
In place of the 110 ° C. dry powder obtained in Synthesis Example 11, the same operation as in Example 9 was carried out except that 0.55 g of the 110 ° C. dry powder obtained in Synthesis Example 18 was used, and the crystallization temperature of polylactic acid Tc and crystallization rate were measured. The results are shown in Table 4.

(Example 18)
Instead of 110 ° C. dry powder obtained in Synthesis Example 11, 110 g of basic cyanuric acid zinc powder obtained in Synthesis Example 19 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 9 was performed except that 0.55 g of this mixed powder was used instead of the 110 ° C. dry powder obtained in Synthesis Example 11, and the crystallization temperature Tc and the crystallization rate of polylactic acid were measured. . The results are shown in Table 4.

  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 40% and the haze was 61.

(Example 19)
5.0 g of zinc phenylphosphonate (trade name Eco Promote manufactured by Nissan Chemical Industries, Ltd.) and 16.9 g of 110 ° C. dry powder of basic cyanuric acid zinc obtained in Synthesis Example 19 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 9 was performed except that 0.55 g of this mixed powder was used instead of the 110 ° C. dry powder obtained in Synthesis Example 11, and the crystallization temperature Tc and the crystallization rate of polylactic acid were measured. . The results are shown in Table 4.

(Example 20)
Instead of the 110 ° C. dry powder obtained in Synthesis Example 11, the same operation as in Example 9 was performed except that 0.55 g of the 110 ° C. dry powder obtained in Synthesis Example 20 was used. Tc and crystallization rate were measured. The results are shown in Table 4.

(Example 21)
In place of the 110 ° C. dry powder obtained in Synthesis Example 11, the same operation as in Example 9 was performed except that the 110 ° C. dry powder obtained in Synthesis Example 21 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.

(Comparative Example 3)
The same operation as in Example 9 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 4.

  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 87% and the haze was 14.

(Comparative Example 4)
In place of the dried powder of 110 ° C. obtained in Synthesis Example 11, zinc phenylphosphonate (trademark Eco Promote, manufactured by Nissan Chemical Industries, Ltd.) was used in the same manner as in Example 9 except that 0.55 g was used. Lactic acid crystallization temperature Tc and crystallization rate were measured. The results are shown in Table 4. Moreover, the result of having observed the said zinc phenylphosphonate 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), it was visible at a wavelength of 550 nm. The light transmittance was 30%, and the haze was 70.

(Comparative Example 5)
In place of the 110 ° C. dry powder obtained in Synthesis Example 11, zinc phenylphosphonate (trade name Eco Promote, manufactured by Nissan Chemical Industries, Ltd.) 0.11 g was used, and the same procedure as in Example 9 was performed to obtain poly Lactic acid crystallization temperature Tc and crystallization rate were measured. The results are shown in Table 4.

  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 60% and the haze was 41.

(Reference Example 1)
Instead of the 110 ° C. dry powder obtained in Synthesis Example 11, the same operation as in Example 9 was carried out except that 0.55 g of the basic zinc cyanurate zinc powder obtained in Synthesis Example 19 was used. The crystallization temperature Tc and crystallization rate of polylactic acid were measured. The results are shown in Table 4.

  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 39% and the haze was 64.

(Reference Example 2)
Instead of the 110 ° C. dry powder obtained in Synthesis Example 11, the same operation as in Example 9 was carried out except that 0.11 g of the basic cyanuric acid zinc 110 ° C. powder obtained in Synthesis Example 19 was used. The crystallization temperature Tc and crystallization rate of polylactic acid were measured. The results are shown in Table 4.

  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.

  As a result, as shown in Table 4, Examples 9 to 21 were more crystalline than Comparative Example 3 in which the resin crystal nucleating agent was not added and Reference Examples 1 and 2 containing only basic zinc cyanurate. It was confirmed that the crystallization temperature was remarkably high, the crystallization rate was remarkably high, and the crystal nucleating agent performance was very excellent.

  Moreover, Examples 9-21 are crystallization temperature and crystallization speed comparable as compared with the comparative examples 4 and 5 which contain only expensive zinc phenylphosphonate, and are more than the metal salt of phenylphosphonic acid. It has also been confirmed that by using a metal salt of phenylphosphonic acid together with low-cost basic zinc cyanurate fine particles, it is possible to achieve both the effect of increasing the crystallization speed and crystallization temperature of the resin and the effect of reducing the cost. It was done.

  Further, when Example 9 and Example 19 having the same components were compared, Example 1 had a higher crystallization rate and crystallization temperature. Therefore, it was found that the crystal nucleating agent performance was superior when the raw materials were reacted as in Example 9, rather than simply mixing basic zinc cyanurate, zinc phenylphosphonate and magnesium hydroxide. It was.

[Crystal Nucleating Agent Evaluation-2]
(Example 22)
36 mg of a basic zinc cyanurate obtained in Synthesis Example 11 (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 5.

(Comparative Example 6)
The same operation as in Example 22 was performed except that the resin nucleating agent was not added, and the crystallization temperature Tc and the crystallization rate of polypropylene were measured. The results are shown in Table 5.

(Comparative Example 7)
Crystallization of polypropylene by performing the same operation as in Example 22 except that zinc phenylphosphonate (trade name Eco Promote, manufactured by Nissan Chemical Industries, Ltd.) was used instead of the 110 ° C. dry powder obtained in Synthesis Example 11. The temperature Tc and the crystallization rate were measured. The results are shown in Table 5.

(Reference Example 3)
Instead of the 110 ° C. dry powder obtained in Synthesis Example 11, the same operation as in Example 22 was carried out except that 36 mg of the basic zinc cyanurate zinc powder obtained in Synthesis Example 19 was used. The crystallization temperature Tc and the crystallization rate were measured. The results are shown in Table 5.

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

  Further, Example 22 is a base having a crystallization temperature and a crystallization rate comparable to those of Comparative Example 7 containing only expensive zinc zinc phenylphosphonate, and lower in cost than the metal salt of phenylphosphonic acid. By using a metal salt of phenylphosphonic acid together with fine zinc cyanurate particles, it is possible to achieve both the effect of increasing the crystallization speed and the crystallization temperature of the resin and the effect of lowering the cost even in polypropylene resin. confirmed.

Claims (10)

  A resin crystal nucleating agent containing basic zinc cyanurate particles is added to a polylactic acid resin or a polyolefin-based resin, which is a crystalline polymer, and molded, thereby forming the resin crystal nucleating agent as a primary resin. A method for promoting crystallization, which comprises promoting crystallization as a crystal nucleus.   It is characterized by increasing the crystallization speed of the resin by adding a resin crystal nucleating agent containing basic zinc cyanurate particles to a polylactic acid resin or a polyolefin-based resin, which is a crystalline polymer. A method for promoting crystallization.   The resin is a polylactic acid resin, and the crystal nucleating agent for the resin is added so that the basic zinc cyanurate particles are 0.01 to 10.0 parts by mass with respect to 100 parts by mass of the polylactic acid resin. The method for promoting crystallization according to claim 1 or 2, wherein:   The resin is a polyolefin resin, and the crystal nucleating agent for the resin is added so that the basic cyanuric acid zinc particles are 0.01 to 10.0 parts by mass with respect to 100 parts by mass of the polyolefin resin. The method for promoting crystallization according to claim 1 or 2, wherein: The polyolefin resin, the crystallization promoting method according to claim 4, characterized in that at least one element selected polypropylene resin and polyethylene resins or al. Said basic cyanuric zinc particles, the average particle diameter _{D 50} measured by a laser diffraction method 80～900Nm, any one of the preceding claims, characterized in that the specific surface area of 20 to 100 m ² / g The method for promoting crystallization according to one item.   The basic cyanuric acid zinc particles contain at least one selected from zinc oxide and basic zinc carbonate, cyanuric acid and water so that the cyanuric acid concentration is 0.1 to 10.0% by mass with respect to water. The method for promoting crystallization according to claim 6, wherein the mixed slurry blended in is produced by wet dispersion using a dispersion medium in a temperature range of 5 to 55 ° C. 7.   The method for promoting crystallization according to claim 1, comprising a metal salt of phenylphosphonic acid.   The metal salt of phenylphosphonic acid is at least one selected from zinc phenylphosphonate, lithium phenylphosphonate, sodium phenylphosphonate, potassium phenylphosphonate, calcium phenylphosphonate, magnesium phenylphosphonate and manganese phenylphosphonate. The method for promoting crystallization according to claim 8, wherein:   A method for producing a molded product, wherein the crystallization is promoted by the crystallization promoting method according to any one of claims 1 to 9 to obtain a molded product.

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