阅读说明：本技术 颗粒状成核剂、树脂组合物、成型品及其制造方法 (Granular nucleating agent, resin composition, molded article, and method for producing same ) 是由 堀越隆裕 横田悠里 于 2019-02-07 设计创作，主要内容包括：本发明的颗粒状成核剂为含有由给定的式表示的芳香族磷酸酯金属盐的颗粒状成核剂,将该颗粒状成核剂的最大粒径记为D<Sub>max</Sub>、将该颗粒状成核剂的分散度记为D<Sub>p</Sub>时,满足80μm≤D<Sub>max</Sub>≤300μm、且1.0％≤D<Sub>p</Sub>≤27.0％。(The granular nucleating agent of the present invention is a granular nucleating agent containing an aromatic phosphoric ester metal salt represented by the given formula, and the maximum particle diameter of the granular nucleating agent is represented by D max The degree of dispersion of the particulate nucleating agent was denoted as D p When the thickness is 80 μm or less, D max Less than or equal to 300 mu m and less than or equal to 1.0 percent of D p ≤27.0％。)

1. A granular nucleating agent comprising a compound represented by the following general formula (1),

the particle size distribution of the granular nucleating agent was measured by a laser diffraction particle size distribution measuring method in a dry manner, and when the maximum particle size of the granular nucleating agent was recorded as D_maxThe degree of dispersion of the particulate nucleating agent measured in accordance with the following procedure was denoted as D_pWhen the temperature of the water is higher than the set temperature,

D_maxsatisfies the following formula (A), and D_pSatisfies the following formula (B),

80μm≤D_maxless than or equal to 300 mu m DEG.formula (A),

1.0％≤D_pless than or equal to 27.0 percent of the formula (B),

the method comprises the following steps:

preparing a given amount of a particulate nucleating agent as a sample; the sample is put into the cylinder from a height of 60cm, and the sample is dropped in the cylinder along the vertical direction; then, the amount of sample remaining on the watch glass set at the drop site thereof was measured; the amount of the sample to be put and the amount of the sample remaining in the petri dish were used to determine the degree of dispersion based on the following formula,

dispersion degree [ (amount of sample put-amount of sample remaining on the watch glass)/amount of sample put ] × 100,

wherein the unit of the dispersion degree is percent, the unit of the input sample amount and the sample amount remained on the surface dish is gram,

in the general formula (1), R¹～R⁴Each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 9 carbon atoms, R⁵Represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and m represents 1 or 2; when M is 1, M¹Represents a hydrogen atom, Al (OH)₂Or an alkali metal atom; when M is 2, M¹Represents a group IIA element, Al (OH) or Zn.

2. A granular nucleating agent comprising a compound represented by the following general formula (1),

the particle size distribution of the granular nucleating agent was measured by a laser diffraction particle size distribution measuring method in a dry manner, and when the maximum particle size of the granular nucleating agent was recorded as D_maxWhen the volume average particle diameter is MV,

D_maxsatisfies the following formula (A), and MV satisfies the following formula (C),

80μm≤D_maxless than or equal to 300 mu m DEG.formula (A),

MV is more than or equal to 5 mu m and less than or equal to 100 mu m DEG.formula (C),

in the general formula (1), R¹～R⁴Each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 9 carbon atoms, R⁵Represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and m represents 1 or 2; when M is 1, M¹Represents a hydrogen atom, Al (OH)₂Or an alkali metal atom; when M is 2, M¹Represents a group IIA element, Al (OH) or Zn.

3. The particulate nucleating agent according to claim 1 or 2,

the aspect ratio of the granular nucleating agent is 1.5 to 10.

4. The particulate nucleating agent according to any one of claims 1 to 3,

the compound contains one or more compounds represented by the following chemical formulas (2) to (15):

5. a resin composition comprising a thermoplastic resin and the particulate nucleating agent according to any one of claims 1 to 4.

6. The resin composition according to claim 5, wherein,

the thermoplastic resin contains a crystalline polymer.

7. The resin composition according to claim 6, wherein,

the crystalline polymer contains a polyolefin polymer.

8. The resin composition according to any one of claims 5 to 7, wherein,

the content of the particulate nucleating agent is 0.001 parts by weight or more and 10 parts by weight or less with respect to 100 parts by weight of the thermoplastic resin.

9. The resin composition according to any one of claims 5 to 8, wherein the resin composition is in a granular form.

10. A molded article obtained by using the resin composition according to any one of claims 5 to 9.

11. A process for producing a molded article, which comprises using the resin composition according to any one of claims 5 to 9.

Technical Field

The present invention relates to a particulate nucleating agent, a resin composition, a molded article, and a method for producing the same.

Background

As a technique for modifying a polymer material, a technique of adding a crystal nucleating agent or a crystal promoter is known. As such a technique, for example, a technique described in patent document 1 is known. Patent document 1 describes that a crystal nucleating agent having an average particle diameter of 0.001 to 3.0 μm (hereinafter, nucleating agents such as crystal nucleating agents and crystal promoters are collectively referred to as "nucleating agents") is added to crystalline polylactic acid (claims 1 and 3 of patent document 1).

Disclosure of Invention

Problems to be solved by the invention

However, the present inventors have found, as a result of their studies, that: the nucleating agent described in patent document 1 has room for improvement in terms of dust workability and transparency.

Means for solving the problems

The present inventors have conducted studies and, as a result, have obtained the following findings.

A typical nucleating agent is a powder or granule (granular nucleating agent) obtained by mixing (kneading) and drying each raw material component, and then pulverizing the mixture as necessary. The granular nucleating agent is melt-kneaded with a thermoplastic resin such as a crystalline polymer and used for thermoforming of the thermoplastic resin.

In mass production of granular nucleating agents, it is known that when the scale of the granular nucleating agents is expanded from the laboratory scale, further improvement of dust workability such as handling properties under various use environments such as transportation, kneading and storage is required for the granular nucleating agents. Such dust workability is required not only in the production, transportation, and storage of the granular nucleating agent, but also in the production of a mixed product (composition) or a thermoplastic resin using the granular nucleating agent, and mass production thereof.

From the viewpoint of improvement of transparency, such dust workability becomes a great problem as the particle diameter of the particulate nucleating agent becomes smaller. Therefore, a method of changing the pulverization conditions for making the particles smaller to relatively mild conditions has been studied. However, in some cases, large particles are mixed in the particulate nucleating agent, and thus the transparency may be reduced.

The present inventors have conducted studies based on such a development situation, and as a result, they found that: the dust characteristics of the granular nucleating agent are controlled by mild pulverization conditions to improve dust workability, and coarse particles are retained by a grid sifter ( panel), whereby the transparency can be improved. Further intensive research results show that: the present inventors have found that dust workability and transparency can be stably evaluated by using as an index the degree of dispersion and the maximum particle diameter of a particulate nucleating agent, and that dust workability and transparency can be improved by controlling the upper limit of the degree of dispersion and the upper limit of the maximum particle diameter to be not more than given values, and have completed the present invention.

According to the present invention, there is provided a granular nucleating agent comprising a compound represented by the following general formula (1),

the particle size distribution of the granular nucleating agent was measured by a laser diffraction particle size distribution measuring method in a dry manner, and the maximum particle size of the granular nucleating agent was recorded as D_maxThe degree of dispersion of the particulate nucleating agent measured in accordance with the following procedure was denoted as D_pWhen the temperature of the water is higher than the set temperature,

D_maxsatisfies the following formula (A), and D_pSatisfies the following formula (B).

80μm≤D_maxLess than or equal to 300 mu m, formula (A)

1.0％≤D_pLess than or equal to 27.0 percent, formula (B)

(step)

A given amount of the particulate nucleating agent was prepared as a sample. The sample was put into the cylinder from a height of 60cm, and the sample was dropped in the vertical direction inside the cylinder. Then, the amount of the sample remaining on the watch glass set at the drop point thereof was measured. The amount of the sample to be charged and the amount of the sample remaining in the petri dish were used to determine the degree of dispersion (%) based on the following formula.

Dispersion (%) (value [ (amount of sample put (g) — amount of sample remaining in the petri dish (g))/amount of sample put (g) ] × 100

(in the above general formula (1), R¹～R⁴Each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 9 carbon atoms, R⁵Represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, M represents 1 or 2, and when M is 1, M is¹Represents a hydrogen atom, Al (OH)₂Or an alkali metal atom, M is 2, M¹Represents a group IIA element, Al (OH) or Zn. )

The present inventors have conducted studies based on such a development situation, and as a result, they have found that: by appropriately adjusting the particle size distribution in the particulate nucleating agent, the dust characteristics can be controlled. Further intensive research results show that: as the particle size distribution, the maximum particle diameter D is appropriately controlled within a given range of the volume average particle diameter MV_maxThe upper and lower limits of (b) are such that the dust workability is improved and the desired transparency is obtained, and the present invention has been completed.

According to the present invention, there is provided a granular nucleating agent comprising a compound represented by the above general formula (1),

the particle size distribution of the granular nucleating agent was measured by a laser diffraction particle size distribution measuring method in a dry manner, and the maximum particle size of the granular nucleating agent was recorded as D_maxWhen the volume average particle diameter is MV,

D_maxsatisfies the following formula (A), and MV satisfies the following formula (C).

80μm≤D_maxLess than or equal to 300 mu m, formula (A)

MV not less than 5 mu m and not more than 100 mu m, formula (C)

Further, according to the present invention, there is provided a resin composition comprising a thermoplastic resin and the above-mentioned particulate nucleating agent.

Further, the present invention provides a molded article using the resin composition.

Further, according to the present invention, there is provided a method for producing a molded article, wherein the molded article is produced using the resin composition.

Effects of the invention

According to the present invention, there are provided a granular nucleating agent excellent in dust workability and transparency, and a resin composition and a molded article using the granular nucleating agent, and a method for producing the same.

Detailed Description

The granular nucleating agent of the present embodiment will be explained.

The granular nucleating agent contains an aromatic phosphoric ester metal salt. The aromatic phosphoric acid ester metal salt is a compound represented by the following general formula (1). These compounds may be used alone, or 2 or more kinds may be used in combination.

In the above general formula (1), R¹～R⁴Each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 9 carbon atoms, R⁵Represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, M represents 1 or 2, and when M is 1, M is¹Represents a hydrogen atom, Al (OH)₂Or an alkali metal atom, M is 2, M¹Represents a group IIA element, Al (OH) or Zn.

As R in the above general formula (1)¹、R²、R³And R⁴Examples of the alkyl group having 1 to 9 carbon atoms include: methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, isobutyl, pentyl, isopentyl, tert-pentyl, hexyl, cyclohexyl, heptyl, isoheptyl, tert-heptyl.

In the above general formula (1), as M¹The alkali metal includes sodium (Na), potassium (K), lithium (Li), and the like.

As M in the above general formula (1)¹As the group IIA element, beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba) and radium (Ra) are mentioned, among which those of magnesium and calciumThe element is preferable because the nucleating agent component has a remarkable nucleating agent effect.

Among the compounds represented by the above general formula (1), compounds in which m is 1 are preferred. In addition, R is preferred¹、R²、R³And R⁴Is a compound selected from one of methyl, ethyl, sec-butyl and tert-butyl. In addition, R is particularly preferred⁵A hydrogen atom or a methyl group.

The compound represented by the general formula (1) preferably contains one or more compounds represented by any one of the following chemical formulae (2) to (15). Among them, the compound represented by any one of chemical formulas (2) to (6) is preferable from the viewpoint of improving the physical properties of the resin. From the viewpoint of improving transparency, the compound represented by any one of chemical formula (7) to chemical formula (15) is preferable.

As a method for producing the compound represented by the above general formula (1), for example, phosphorus trichloride (or phosphorus oxychloride) and 2, 2' -alkylene phenol are reacted, and then hydrolyzed as necessary to give a cyclic acid phosphate. Next, the cyclic acidic phosphate ester is reacted with a metal hydroxide such as sodium hydroxide or potassium hydroxide, and the obtained reaction product is appropriately purified (filtered, etc.) and dried, whereby the above-mentioned compound (aromatic phosphate ester metal salt) is obtained. In addition, the aromatic phosphoric acid ester metal salt can be synthesized by a conventionally known method and used as the above compound.

The obtained compound is dissolved in a solvent, reacted with other metal hydroxide such as lithium hydroxide or reacted with any salt of aluminum, magnesium or group IIA element, and the obtained reaction product is purified and dried to obtain other compounds.

The granular nucleating agent of the present embodiment is obtained by pulverizing the obtained compound with an appropriate pulverizing device as needed. In the granular nucleating agent, coarse particles can be excluded by sieving with a sieve of a given mesh size. The granular nucleating agent may contain 1 or 2 or more kinds of powdery compounds. For example, the above-mentioned granular nucleating agent can be obtained by mixing 2 or more compounds having different particle size distributions or 2 or more compounds having been classified in an appropriate ratio.

Examples of the above-mentioned pulverizing apparatus include: mortar, ball mill, rod mill, tube mill, conical ball mill, vibratory ball mill, hessmen centrifugal ball mill (Hyswing ball mill), roller mill, pin mill, hammer mill, roller mill, jet mill (jet mill), micronizer, nanomiller (nano mill), marjie mill (majac mill), micro atomizer, colloid mill, pre-mor mill, micronizer, charlotte colloid mill, rotary cutter, dry media agitator mill, and the like. These pulverizers may be used singly or in combination of 2 or more, and are appropriately selected depending on the kind of raw material powder to be pulverized, the pulverization time, and the like.

The granular nucleating agent of the present embodiment may be composed of only the compound represented by the above general formula (1), or may contain other components within a range in which the object of the present invention is achieved. Examples of the other components include: aromatic phosphate metal salts other than the compound represented by the general formula (1), fatty acid metal salts, silicic acid-based inorganic additive components, hydrotalcites, and the like. These compounds may be used alone, or 2 or more kinds may be used in combination.

The fatty acid metal salt preferably contains a compound represented by the following general formula (16), for example.

In the above general formula (16), R⁶Represents a linear or branched aliphatic group having 9 to 30 carbon atoms, M represents a metal atom, and n represents an integer of 1 to 4 corresponding to the valence of the metal atom of M.

In the above general formula (16), R⁶As straight-chain or branched carbon atomsThe aliphatic group having 9 to 30 carbon atoms includes alkyl and alkenyl groups having 9 to 30 carbon atoms, and these groups may be substituted with a hydroxyl group.

Examples of the aliphatic group having 9 to 30 carbon atoms include: saturated fatty acids such as capric acid, 2-ethylhexanoic acid, undecanoic acid, lauric acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, stearic acid, nonadecanoic acid, arachidic acid, heneicosanoic acid, behenic acid, tricosanoic acid, lignoceric acid, cerotic acid, montanic acid, melissic acid, etc.; linear unsaturated fatty acids such as 4-decenoic acid, 4-dodecenoic acid, palmitoleic acid, α -linolenic acid, linoleic acid, γ -linolenic acid, stearidonic acid, petroselinic acid, oleic acid, elaidic acid, 11-octadecenoic acid, eicosapentaenoic acid, docosapentaenoic acid, and docosahexaenoic acid.

The fatty acid metal salt is preferably R⁶The aliphatic group is a compound having 10 to 21 carbon atoms, and lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, and 12-hydroxystearic acid are particularly preferable.

Examples of the metal atom represented by M include: alkali metals, magnesium, calcium, strontium, barium, titanium, manganese, iron, zinc, silicon, zirconium, yttrium, barium, hafnium, or the like. Among them, alkali metals such as sodium, lithium, and potassium are preferable, and sodium and lithium are particularly preferably used because they increase the crystallization temperature.

Examples of the silicic acid-based inorganic additive component include: fumed silica, fine particle silica, diatomaceous earth, clay, kaolin, silica gel, calcium silicate, sericite, kaolinite, flint, feldspar powder, vermiculite, attapulgite, talc, mica, steatite, pyrophyllite, and the like, and among them, a substance having a layered structure in a particle structure and a silicon content of 15 mass% or more is preferable. Preferable examples of the inorganic additive include sericite, kaolinite, talc, mica, iron talc, and pyrophyllite, and talc and mica are more preferable.

The hydrotalcite may be a natural product or a synthetic product, and may be used without depending on the presence or absence of surface treatment or the presence or absence of crystal water. Examples thereof include basic carbonates represented by the following general formula.

M_xMg_yAl_zCO₃(OH)_xp+2y+3z-2·nH₂O

(in the above formula, M represents an alkali metal or zinc, X represents a number of 0 to 6, y represents a number of 0 to 6, z represents a number of 0.1 to 4, p represents the valence of M, and n represents a number of 0 to 100 of crystal water.)

The particulate nucleating agent containing the other component is a particulate nucleating agent composition containing a compound represented by the general formula (1), and may be configured to contain one or more selected from other aromatic phosphoric acid ester metal salts, fatty acid metal salts, silicic acid-based inorganic additive components, and hydrotalcites, and preferably one or more selected from fatty acid metal salts, talc, mica, and hydrotalcites.

Such a granular nucleating agent can be obtained, for example, by appropriately combining the above-mentioned pulverizing apparatus and pulverizing the compound represented by the above general formula (1) and other components in the coexistence thereof. In addition, the above-mentioned pulverizing apparatus, sieving, mixing method, and the like may be used.

The granular nucleating agent of the present embodiment functions as a nucleating agent and a transparentizing agent to be added in molding a thermoplastic resin such as a crystalline polymer. In the crystalline polymer, improvements (modification effects) in the crystallization temperature, thermal modification temperature, flexural modulus, hardness, transparency, and the like can be achieved. In addition, molding cyclability can be improved and productivity can be improved.

The granular nucleating agent of the first embodiment contains the compound represented by the above general formula (1), and the particle size distribution of the granular nucleating agent is dry-measured by a laser diffraction particle size distribution measuring method, and the maximum particle size of the granular nucleating agent is represented by D_maxThe degree of dispersion of the particulate nucleating agent measured in accordance with the following procedure was denoted as D_pWhen D is_maxSatisfies the following formula (A), and D_pSatisfies the following formula (B).

80μm≤D_maxLess than or equal to 300 mu m, formula (A)

1.0％≤D_pLess than or equal to 27.0 percent, formula (B)

(step)

A given amount of the particulate nucleating agent was prepared as a sample. The sample was put into the cylinder from a height of 60cm, and the sample was dropped in the vertical direction inside the cylinder. Then, the amount of the sample remaining on the watch glass set at the drop point thereof was measured. The amount of the sample to be charged and the amount of the sample remaining in the petri dish were used to determine the degree of dispersion (%) based on the following formula. Here, the predetermined amount is about 5g, and the dispersion degree may be an average value of 3 measurement values.

Dispersion (%) (value [ (amount of sample put (g) — amount of sample remaining in the petri dish (g))/amount of sample put (g) ] × 100

The present inventors have found the following cases according to their findings. First, from the viewpoint of improvement of the transparency, it is considered that the smaller the particle diameter of the particulate nucleating agent is, the more preferable. However, when a granular nucleating agent having an excessively small particle diameter is used, the dust workability may be lowered. Therefore, in the treatment for forming the granular nucleating agent into small particles, the pulverization conditions are changed to relatively mild conditions. As a result, although the dust workability is improved, large particles may be mixed into the granular nucleating agent, which may reduce the transparency.

Based on the development, the following studies were carried out, and the results were found: the dust characteristics of the granular nucleating agent are controlled by mild pulverization conditions, so that the dust workability is improved, and the transparency can be improved by trapping coarse particles by grid separation.

Further, it was found that: by using the dispersion degree and the maximum particle diameter of the particulate nucleating agent as indexes, the dust workability and the transparency can be stably evaluated, and by controlling the upper limit of the dispersion degree and the upper limit of the maximum particle diameter as indexes to be given values or less, the dust workability and the transparency can be improved.

Here, the explosion index is generally an index for evaluating dust explosiveness of the powder. It is known that even when the explosion index is so low that there is no practical problem, there is room for improvement in workability such as handling of the granular nucleating agent during scale-up.

Moreover, it was found that: by setting the explosion index and the maximum explosion pressure to be low as indices, the dust characteristics at the time of scale-up can be suppressed, and the workability of the granular nucleating agent can be improved.

In addition, by adopting the dry condition, there is no problem such as air bubbles as compared with the wet condition, and therefore, the measurement stability can be improved.

In the first embodiment, the maximum particle diameter D_maxThe upper limit of (B) is 300 μm or less, preferably 295 μm or less, and more preferably 290 μm or less. This improves the transparency of the granular nucleating agent. On the other hand, D_maxThe lower limit of (B) is, for example, 80 μm or more, preferably 83 μm or more, and more preferably 85 μm or more. This can balance the physical properties.

In the first embodiment, the degree of dispersion D_pThe upper limit of (b) is, for example, 27.0% or less, preferably 26.8% or less, and more preferably 26.5% or less. This improves the workability of the granular nucleating agent such as dust workability and workability of the granular nucleating agent during scale-up. On the other hand, D_pThe lower limit of (b) is, for example, 1.0% or more, preferably 3.0% or more, and more preferably 5.0% or more. The balance of the physical properties can be achieved.

The granular nucleating agent of the second embodiment contains a compound represented by the above general formula (1), and the particle size distribution of the granular nucleating agent is dry-measured by a laser diffraction particle size distribution measuring method, and the maximum particle size of the granular nucleating agent is represented by D_maxWhen the volume average particle diameter is MV, D_maxSatisfies the following formula (A), and MV satisfies the following formula (C).

80μm≤D_maxLess than or equal to 300 mu m, formula (A)

MV not less than 5 mu m and not more than 100 mu m, formula (C)

Further, based on the findings of the present inventors, the above-described developments were studied, and as a result, it was found that: by appropriately adjusting the particle size distribution in the particulate nucleating agent, the dust characteristics can be controlled. Further, it was found that: as the particle size distribution, the maximum particle diameter D is appropriately controlled within a given range of the volume average particle diameter MV_maxThe upper and lower limits of (b) can improve the dust workability and can achieve a desired transparency.

In the second embodiment, the volume average particle diameter MV is, for example, 5 to 100 μm, preferably 6 to 95 μm, and more preferably 7 to 90 μm.

In the present specification, "to" includes an upper limit and a lower limit unless otherwise specified.

In the second embodiment, the maximum particle diameter D_maxThe upper limit of (B) is 300 μm or less, preferably 295 μm or less, and more preferably 290 μm or less. On the other hand, D_maxThe lower limit of (B) is, for example, 80 μm or more, preferably 83 μm or more, and more preferably 85 μm or more.

In the granular nucleating agent of the second embodiment, the volume average particle diameter MV is defined as the above range and the maximum particle diameter D is defined as the maximum particle diameter_maxThe upper limit of (D) is set to the above-mentioned value or less, whereby the transparency of the granular nucleating agent can be improved, and the maximum particle diameter D can be adjusted_maxWhen the lower limit of (b) is set to the above range, the dust workability of the granular nucleating agent can be improved, and the workability such as the workability of the granular nucleating agent during scale-up can be improved.

The granular nucleating agent is preferably needle-shaped particles. The aspect ratio of the particulate nucleating agent in this case is, for example, 1.5 or more and 10 or less, preferably 2.0 or more and 8 or less, and more preferably 2.5 or more and 6 or less. By setting the range of the numerical value, the dust characteristics can be suppressed during the molding process of the crystalline polymer, and the dust workability can be improved.

In the present embodiment, the aspect ratio of the particulate nucleating agent is calculated from the average of the major axis and the minor axis by measuring the lengths of the major axis and the minor axis at random for 100 crystals from a photomicrograph.

In the present embodiment, the maximum particle diameter, the dispersibility, the volume average particle diameter, and the aspect ratio of the particulate nucleating agent can be controlled by appropriately selecting, for example, the kind and the amount of each component contained in the particulate nucleating agent, the method for producing the particulate nucleating agent, and the like. Among them, as elements for setting the maximum particle diameter, the degree of dispersion, the volume average particle diameter, and the aspect ratio of the above-mentioned particulate nucleating agent in a desired numerical range, for example, a pulverizing condition such as a pulverizing method and a pulverizing time, a classifying condition such as a trapping of coarse particles, and the like are appropriately selected.

The resin composition of the present embodiment is obtained by adding the above-described particulate nucleating agent to a thermoplastic resin.

The method for adding the particulate nucleating agent to the thermoplastic resin is not particularly limited, and a commonly used method can be directly applied. For example, a method of dry-blending a powder or granules of the thermoplastic resin with a powder of the above-mentioned particulate nucleating agent may be used.

The resin composition may be used in various forms, and may be in the form of, for example, pellets (ペレット), granules, or powder. From the viewpoint of handling properties, the granular form is preferable.

Examples of the thermoplastic resin include: polyolefin-based resins, styrene-based resins, polyester-based resins, polyether-based resins, polycarbonate-based resins, polyamide-based resins, halogen-containing resins, and the like. Among them, crystalline polymers are preferably used.

Further, as examples of the thermoplastic resin, for example, a thermoplastic resin such as a petroleum resin, coumarone resin, polyvinyl acetate, acrylic resin, polymethyl methacrylate, polyvinyl alcohol, polyvinyl formal, polyvinyl butyral, polyphenylene sulfide, polyurethane, cellulose resin, polyimide resin, polysulfone, liquid crystal polymer, or the like, and a mixture thereof can be used.

The thermoplastic resin may be a thermoplastic elastomer such as isoprene rubber, butadiene rubber, acrylonitrile-butadiene copolymer rubber, styrene-butadiene copolymer rubber, polyester elastomer, nitrile elastomer, nylon elastomer, vinyl chloride elastomer, polyamide elastomer, or polyurethane elastomer, or may be used in combination.

The crystalline polymer is not particularly limited, and examples thereof include: polyolefin polymers such as α -olefin polymers including polypropylene, high density polyethylene, low density polyethylene, linear low density polyethylene, polybutene-1, poly-3-methylpentene, poly-4-methylpentene, and ethylene/propylene block or random copolymers; thermoplastic linear polyester polymers such as polyethylene terephthalate, polybutylene terephthalate, and polyhexamethylene terephthalate; polythioether polymers such as polyphenylene sulfide; polylactic acid polymers such as polycaprolactone; linear polyamide polymers such as polyhexamethylene adipamide; crystalline polystyrene-based polymers such as syndiotactic polystyrene.

Among these, polyolefin-based polymers that significantly exert the effect of using the nucleating agent of the present invention are preferable, and polypropylene-based resins such as polypropylene, ethylene/propylene block or random copolymers, α -olefin/propylene block or random copolymers other than ethylene, and mixtures of these propylene-based polymers and other α -olefin polymers are particularly preferable.

The crystalline polymer is useful when a crystalline α -olefin polymer, particularly a polypropylene resin, an ethylene/propylene copolymer, or a polypropylene resin such as a mixture of the propylene polymer and another α -olefin polymer is used. These polypropylene-based resins may be used without being limited to the intrinsic viscosity, isotactic pentad fraction, density, molecular weight distribution, melt flow rate, rigidity and the like, and for example, Japanese patent application laid-open No. 63-37148, Japanese patent application laid-open No. 63-37152, Japanese patent application laid-open No. 63-90552, Japanese patent application laid-open No. 63-210152, Japanese patent application laid-open No. 63-213547, Japanese patent application laid-open No. 63-243150, Japanese patent application laid-open No. 63-243152, Japanese patent application laid-open No. 63-260943, Japanese patent application laid-open No. 63-260944, Japanese patent application laid-open No. 63-264650, Japanese patent application laid-open No. 1-178541, Japanese patent application laid-open No. 2-49047, Japanese patent application laid-open No. 2-102242, Japanese patent application laid-open No. 2-251548, and polypropylene resins described in, for example, Japanese patent application laid-open Nos. H2-279746 and H3-195751.

The content of the particulate nucleating agent is usually 0.001 to 10 parts by weight, preferably 0.005 to 8 parts by weight, and more preferably 0.01 to 5 parts by weight, based on 100 parts by weight of the thermoplastic resin (for example, crystalline polymer). This can sufficiently obtain the effect of modifying the thermoplastic resin, particularly the crystalline polymer.

The resin composition of the present embodiment may contain additives such as antioxidants, light stabilizers, ultraviolet absorbers, pigments, fillers, organotin compounds, plasticizers, epoxy compounds, blowing agents, antistatic agents, flame retardants, lubricants, heavy metal deactivators, hydrotalcites, organic carboxylic acids, colorants, silicic acid additives, and processing aids, if necessary. These may be used alone, or 2 or more of them may be used in combination.

Examples of the antioxidant include: phosphorus antioxidants, phenol antioxidants, thioether antioxidants, and the like.

Examples of the antistatic agent include: cationic surfactants, anionic surfactants, nonionic surfactants, amphoteric surfactants, and the like.

Examples of the flame retardant include: halogen compounds, phosphate ester compounds, phosphoric acid amide compounds, melamine compounds, polyphosphoric acid melamine chloride compounds, fluorine resins, metal oxides, and the like.

Examples of the lubricant include: hydrocarbon series, fatty acid series, aliphatic alcohol series, aliphatic ester series, aliphatic amide series, metal soap series, etc.

Examples of the silicic acid additive include: fumed silica, microparticulate silica, diatomaceous earth, clay, kaolin, silica gel, calcium silicate, sericite, kaolinite, flint, feldspar powder, vermiculite, attapulgite, talc, mica, steatite, pyrophyllite, and the like.

The content of the additive in the resin composition is preferably 0.001 to 10 parts by weight, for example, with respect to 100 parts by weight of the crystalline polymer. By setting the numerical range as described above, the effect of the additive can be improved.

The resin composition can be used in molded articles such as injection molded articles, fibers, untwisted yarns, biaxially stretched films, uniaxially stretched films, unstretched films, sheets, thermoformed articles, extrusion blow molded articles, injection stretch blow molded articles, profile extrusion molded articles, and rotational molded articles. Among them, injection molded articles, films, sheets, and heat molded articles are preferable as molded articles.

The method for producing a molded article according to the present embodiment includes a step of molding the resin composition by various molding methods, and thereby the molded article can be obtained.

The molding method is not particularly limited, and examples thereof include: injection molding, extrusion molding, blow molding, rotational molding, vacuum molding, inflation molding, calendering, slush molding, dip molding, foam molding, and the like. Among them, injection molding, extrusion molding and blow molding are preferable.

The resin composition can be used for various applications such as building materials, agricultural materials, parts for vehicles such as automobiles, trains, ships and airplanes, packaging materials, miscellaneous goods, toys, household electrical appliances and medical products. Specifically, there may be mentioned: automotive parts such as bumpers, fender panels, instrument panels, battery housings, luggage cases, door panels, door trim panels, fender liners, and the like; resin parts for household electrical appliances such as refrigerators, washing machines, and vacuum cleaners; household articles such as tableware, bottle caps, water buckets, bathing articles and the like; resin members for connection such as connectors; miscellaneous goods such as toys, storage containers, synthetic paper, and the like; medical molded articles such as medical bags, syringes, catheters, medical tubes, syringe preparations, infusion bags, reagent containers, containers for oral medicines, and packages for oral medicines; building materials such as wall materials, floor materials, window frames, wall papers, windows, and the like; an electric wire covering material; agricultural materials such as houses, tunnels, flat gauze bags and the like; industrial materials such as modified silicone polymers for goods shelves, drum cans, back-grinding tapes, tapes for liquid crystal protection, pipes, and sealing materials; food packaging materials such as wrap films, trays, cups, films, bottles, lids, and storage containers, 3d printing materials, and battery separators. Further, the present invention can be used for applications in which various post-treatments are performed, for example, applications in which sterilization is performed by radiation, such as medical applications and food packaging applications, or applications in which low-temperature plasma treatment is performed after molding, for the purpose of improving surface properties such as paintability. Among them, it is preferably used for automobile parts, household goods, and food packaging materials.

The embodiments of the present invention have been described above, but these are examples of the present invention, and various configurations other than the above-described configurations can be adopted. The present invention is not limited to the above-described embodiments, and modifications, improvements, and the like within a range in which the object of the present invention can be achieved are included in the present invention.

Hereinafter, examples of the reference modes are attached.

1. A granular nucleating agent comprising a compound represented by the following general formula (1),

the volume average particle diameter of the granular nucleating agent by the laser diffraction particle size distribution measuring method was designated as MV, and the maximum particle diameter was designated as D_maxWhen the temperature of the water is higher than the set temperature,

the particle size distribution of the granular nucleating agent satisfies the following formulas (A) and (B).

5 μm < MV < 100 μm. formula (A)

80μm＜D_max< 300 μm. formula (B)

(in the above general formula (1), R¹～R⁴Each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 9 carbon atoms, R⁵Represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, M represents 1 or 2, and when M is 1, M is¹Represents a hydrogen atom or an alkali metal atom, and when M is 2, M¹Represents a group IIA element, Al (OH) or Zn. )

2. The granular nucleating agent according to 1, wherein,

the aspect ratio of the granular nucleating agent is 1.5 or more and 10 or less.

3. The granular nucleating agent according to 1. or 2, wherein,

the compound contains one or more compounds represented by any one of the following formulas No.1 to No. 12.

4. A crystalline polymer composition comprising a crystalline polymer and the granular nucleating agent described in any one of 1 to 3.

5. The crystalline polymer composition according to claim 4, wherein,

the crystalline polymer contains a polyolefin polymer.

6. The crystalline polymer composition according to 4 or 5, wherein,

the content of the granular nucleating agent is 0.001 to 10 parts by weight based on 100 parts by weight of the crystalline polymer.

7. The crystalline polymer composition according to any one of claims 4 to 6, wherein the crystalline polymer composition is in a granular form.