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 福田拓也 横田悠里 于 2019-01-28 设计创作，主要内容包括：本发明的颗粒状成核剂为含有给定的芳香族磷酸酯金属盐的颗粒状成核剂，其满足如下特性：该颗粒状成核剂中的脂肪族胺的含量以该颗粒状成核剂整体的质量基准计为3ppm以上且190ppm以下。(The granular nucleating agent of the present invention is a granular nucleating agent containing a given aromatic phosphoric ester metal salt, which satisfies the following characteristics: the content of the aliphatic amine in the particulate nucleating agent is 3ppm or more and 190ppm or less based on the mass of the entire particulate nucleating agent.)

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

the content of the aliphatic amine in the granular nucleating agent obtained by the measurement in step A shown below is 3ppm to 190ppm based on the mass of the whole granular nucleating agent,

step A:

4g of a granular nucleating agent prepared from glass and having an outer diameter of 30mm and a length of 200mm was put in a test tube for introducing the granular nucleating agent;

introducing argon gas into the test tube for introducing a granular nucleating agent at a rate of 37mL/min for 5 minutes, and then heating the test tube for introducing a granular nucleating agent at 180 ℃ for 2 hours under an argon gas atmosphere while introducing argon gas at a rate of 37 mL/min;

collecting a gas generated by heating in 6mL of 600mg/L methanesulfonic acid aqueous solution in a test tube made of glass and having an outer diameter of 15mm and a length of 150mm, and preparing a measurement sample by holding 10mL of the methanesulfonic acid aqueous solution in 600mg/L methanesulfonic acid aqueous solution;

determining the concentration of the aliphatic amine in the resulting determination sample using ion chromatography;

calculating the content of the aliphatic amine in ppm based on the mass of the whole granular nucleating agent based on the obtained measurement value,

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, M represents 1 or 2, and when M is 1, M¹Represents a hydrogen atom or an alkali metal atom, and M is 2¹Represents a group IIA element, Al (OH) or Zn.

2. The particulate nucleating agent according to claim 1,

the aliphatic amine contains an amine compound having 1 to 3 monovalent groups having 1 to 6 carbon atoms bonded to a nitrogen atom.

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

the aliphatic amine contains an alkylamine or an alkanolamine.

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

the aliphatic amine contains more than one selected from triethylamine, diethylamine, butylamine and ethanolamine.

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

the compound contains one or more compounds represented by the following chemical formulas (2) to (13):

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

7. The resin composition according to claim 6, wherein the thermoplastic resin contains a crystalline polymer.

8. The resin composition according to claim 7, wherein the crystalline polymer comprises a polyolefin polymer.

9. The resin composition according to any one of claims 6 to 8,

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.

10. The resin composition according to any one of claims 6 to 9,

the resin composition is in the form of pellets.

11. A molded article obtained by using the resin composition according to any one of claims 6 to 10.

12. A method for producing a molded article using the resin composition according to any one of claims 6 to 10.

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 nucleating agent (hereinafter, a crystal nucleating agent, a crystal promoter, a clearing agent, and the like are collectively referred to as "nucleating agent") is added to a thermoplastic polymer (claim 1 and the like of patent document 1). In this document, a phosphate salt is exemplified as a nucleating agent (paragraph 0014 of patent document 1).

Disclosure of Invention

Technical problem to be solved by the invention

However, the results of the studies conducted by the present inventors have revealed that: the nucleating agent described in patent document 1 has room for improvement in feed stability and odor properties.

Means for solving the problems

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

A general granular nucleating agent is added as a powder or granule to a thermoplastic resin and melt-kneaded, and is used for thermoforming of the thermoplastic resin. However, the feed stability may be lowered due to various powder physical properties of the particulate nucleating agent. When the feeding stability is lowered, the production stability of the molding process is lowered.

As a result of the study according to such a situation, it was found that: by including the aliphatic amine in the particulate nucleating agent, the feed stability can be improved. However, it can be seen that: when the aliphatic amine is contained in an excessive amount, the odor increases during storage, and handling becomes difficult.

As a result of further studies based on such findings, it has been found that the feed stability can be improved and the odor can be reduced by setting the content of the aliphatic amine in the particulate nucleating agent within an appropriate numerical range, and the present invention has been completed.

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

the content of the aliphatic amine in the particulate nucleating agent obtained by the measurement in step a shown below is 3ppm or more and 190ppm or less based on the mass of the entire particulate nucleating agent.

(step A)

4g of the granular nucleating agent was put into a test tube (outer diameter: 30 mm. times. length: 200mm) for introducing the granular nucleating agent made of glass.

After introducing argon gas at 37mL/min for 5 minutes, the granular nucleating agent-introducing test tube was heated at 180 ℃ for 2 hours under an argon atmosphere while introducing argon gas at 37 mL/min.

The vapor generated by heating was collected in 6mL of 600mg/L methanesulfonic acid aqueous solution in a test tube for collection made of glass (outer diameter 15 mm. times. length 150 mm). The aqueous methanesulfonic acid solution was made 10mL with 600mg/L aqueous methanesulfonic acid solution to prepare a measurement sample.

The concentration of the aliphatic amine in the obtained measurement sample was measured using ion chromatography.

Based on the obtained measurement values, the content (ppm) of the aliphatic amine based on the whole mass of the particulate nucleating agent was calculated.

(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, M¹Represents a hydrogen atom or an alkali metal atom, and M is 2¹Represents a group IIA element, Al (O)H) Or Zn. )

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

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

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

Effects of the invention

According to the present invention, there are provided a particulate nucleating agent excellent in charge stability and low odor, a resin composition using the same, a molded article, and a method for producing the same.

Drawings

The above objects, and other objects, features and advantages will be further apparent from the following description of preferred embodiments and the accompanying drawings.

Fig. 1 is a diagram for explaining an outline of a method for measuring the amount of amine.

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, M¹Represents a hydrogen atom or an alkali metal atom, and M is 2¹Represents 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 metals represented include: sodium (Na), potassium (K), lithium (Li), and the like.

As M in the above general formula (1)¹The group IIA element represented by the formula (I) includes beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba) and radium (Ra), and among them, a compound of magnesium and calcium is preferable because of its remarkable nucleating effect of the nucleating agent component.

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 R⁴A compound having one group selected from 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 (13). Among them, the compounds represented by any of chemical formulas (2) to (6) are 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 (13) is preferable.

As a method for producing the compound represented by the above general formula (1), for example, phosphorus trichloride (or phosphorus oxychloride) is reacted with 2, 2' -alkylene phenol, and then hydrolyzed to a cyclic acid phosphate ester as necessary. 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 a salt of any of aluminum, magnesium and group IIA elements, 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 by an appropriate pulverizing means 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 (14), for example.

In the above general formula (14), 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 and corresponds to the valence of the metal atom of M.

In the above general formula (14), R⁶Examples of the aliphatic group having 9 to 30 carbon atoms and having a straight chain or a branched chain include an alkyl group and an alkenyl group 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, and melissic acid, and 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 means and pulverizing the compound represented by the above general formula (1) and other components in the coexistence thereof. In addition, the above-mentioned pulverizing means, sieving, mixing method and the like may be used.

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

The granular nucleating agent of the present embodiment has a characteristic that the content of the aliphatic amine in the granular nucleating agent, which is obtained by the measurement in step a shown below, is 3ppm or more and 190ppm or less based on the mass of the whole granular nucleating agent.

(outline of step A)

The granular nucleating agent was heated at 180 ℃ for 2 hours in an argon atmosphere, and the generated vapor was trapped in an aqueous methanesulfonic acid solution.

Next, the concentration of the aliphatic amine in the methanesulfonic acid aqueous solution was measured by ion chromatography, and based on the obtained measurement value, the content (ppm) of the aliphatic amine with respect to the entire granular nucleating agent as a mass standard was calculated.

According to the knowledge of the inventor, the following results are found: the feed stability and odor properties of the particulate nucleating agent can be appropriately controlled by using the content of the aliphatic amine in the particulate nucleating agent as an index. Namely, it was found that: the feed stability of the particulate nucleating agent can be improved by setting the content of the aliphatic amine to a given value or more, and the odor of the particulate nucleating agent can be reduced by setting the content of the aliphatic amine to a given value or less.

By improving the feeding stability of the particulate nucleating agent, the production stability of the molding process of the resin using the particulate nucleating agent can be improved. Therefore, in applications to molding and processing, or in applications of nucleating agents and clarifying agents, it is expected that the allowable width of the powder physical properties of the granular nucleating agent will be widened.

Further, by realizing a granular nucleating agent having excellent low odor properties, the workability in storage or molding of the granular nucleating agent can be improved. This improves the operability of the granular nucleating agent during the production, packaging, transportation, storage, and molding of the granular nucleating agent.

Further, the present inventors found that: the content of the aliphatic amine in the particulate nucleating agent can be stably evaluated by using a heating temperature higher than the boiling point of the aliphatic amine as a measurement condition of the aliphatic amine and appropriately selecting the heating time.

The measured amount of the aliphatic amine also increased by increasing the heating time, but the saturated amount was exhibited for a while after 2 hours, and thereafter the measured amount was increased again after 2.5 hours. It was found that, since 2.5 hours later, the measurement of impurities was started in addition to the measurement of aliphatic amine, and the amount of impurities measured was increased. The impurities are presumed to be decomposition products of the aliphatic amine.

Therefore, by setting the heating time to 2 hours, it is possible to measure a sufficient amount of the aliphatic amine to be measured close to the saturated amount while suppressing the detection of impurities not to be measured. Further, it was found that the reproducibility of the content of the aliphatic amine was also excellent by setting such measurement conditions.

Specific examples of the above-described step a are shown below.

4g of the granular nucleating agent was put into a test tube (outer diameter: 30 mm. times. length: 200mm) for introducing the granular nucleating agent made of glass.

After introducing argon (Ar) gas under a condition of 37mL/min for 5 minutes in a test tube for introducing a granular nucleating agent, the test tube for introducing a granular nucleating agent was heated at 180 ℃ for 2 hours while introducing argon gas of 37mL/min (under an argon atmosphere).

The vapor generated by heating was trapped in 6mL of 600mg/L methanesulfonic acid aqueous solution in a test tube for trapping made of glass (outer diameter 15 mm. times. length 150 mm). The 6mL of the methanesulfonic acid aqueous solution was adjusted to 10mL with 600mg/L of the methanesulfonic acid aqueous solution, and a measurement sample was prepared.

The concentration and type of the aliphatic amine in the measurement sample obtained by the ion chromatography measurement.

Based on the obtained measurement values, the content (ppm) of the aliphatic amine based on the mass of the entire granular nucleating agent was calculated.

According to the findings of the present inventors, by appropriately selecting the test tube size, the amount of the particulate nucleating agent, and the type, concentration, and amount of the capturing solution, and controlling the argon flow rate, heating time, and heating temperature, it is possible to suppress variations in the detected amount of the aliphatic amine. However, it is considered that the fluctuation of the aliphatic amine capturing efficiency can be suppressed by setting the flow rate of argon gas at the time of capturing the volatile matter to a predetermined amount or more.

In the present embodiment, the lower limit of the content of the aliphatic amine is, for example, 3ppm or more, preferably 4ppm or more, and more preferably 5ppm or more, based on the mass of the entire particulate nucleating agent. Thereby, the feed stability of the particulate nucleating agent can be improved. Although the detailed mechanism is not clear, it is considered that the aliphatic amine in the particulate nucleating agent improves the smoothness of the powder and granules, and therefore, clogging at the time of feeding is suppressed and the feeding stability is improved.

The upper limit of the content of the aliphatic amine is, for example, 190ppm or less, preferably 180ppm or less, and more preferably 150ppm or less, based on the mass of the entire particulate nucleating agent. Thus, a granular nucleating agent having excellent low odor properties can be realized.

The aliphatic amine is a compound in which 1 to 3 hydrogen atoms of ammonia are substituted with a hydrocarbon residue R, and R is a hydrocarbon group or a substituted hydrocarbon group. Part of the hydrocarbon group may be substituted with an oxygen atom or the like. Such an aliphatic amine is different from an aromatic amine in that all R groups do not have aromatic groups.

The aliphatic amine may be any of primary amine, secondary amine, and tertiary amine.

The aliphatic amine may contain an amine compound having 1 or more and 3 or less monovalent groups having 1 to 6 carbon atoms bonded to a nitrogen atom. That is, the number of carbon atoms of the hydrocarbon residue R in the aliphatic amine is, for example, 1 to 6, preferably 2 to 5, and more preferably 2 to 4. By selecting the appropriate number of carbon atoms, feed stability can be improved.

Examples of the hydrocarbon residue or substituted hydrocarbon residue represented by R include an alkyl group and an alcoholic hydroxyl group.

Examples of the aliphatic amine include primary aliphatic amines such as methylamine, ethylamine, propylamine, isopropylamine, butylamine, isobutylamine, tert-butylamine, pentylamine, hexylamine, palmitylamine, ethylenediamine and monoethanolamine, secondary aliphatic amines such as dimethylamine, diethylamine, dipropylamine, dibutylamine, dipentylamine and diethanolamine, and tertiary aliphatic amines such as trimethylamine, triethylamine, tripropylamine, tributylamine, tripentylamine and N, N-dimethylamine.

The above-mentioned aliphatic amine preferably contains, for example, an alkylamine or an alkanolamine. Thereby, the feed stability and the low odor property can be improved. Among them, from the viewpoint of production stability of the granular nucleating agent, the aliphatic amine preferably contains at least one selected from the group consisting of triethylamine, diethylamine, butylamine, and ethanolamine.

In the present embodiment, the content of the aliphatic amine can be controlled by appropriately selecting, for example, the kind and the amount of each component contained in the particulate nucleating agent, the synthesis and the production method of the particulate nucleating agent, and the like. Among them, for example, the use of an aliphatic amine or the like as an element for setting the content of the aliphatic amine in a desired numerical range in the filtration, washing, purification step, pulverization, classification, and mixing step, and the preparation step of the particulate nucleating agent is mentioned.

The method for producing the granular nucleating agent of the present embodiment may include the steps of: preparing a granular nucleating agent; a step of obtaining the content of the aliphatic amine based on the mass of the whole granular nucleating agent from the obtained granular nucleating agent based on the step a; selecting a granular nucleating agent having the aliphatic amine content within the above numerical range as a non-defective product. Thus, a granular nucleating agent having excellent feed stability and low odor can be realized.

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 and 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, 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, and crystalline polystyrene 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 polypropylene-based resin such as a crystalline α -olefin polymer, particularly polypropylene, an ethylene/propylene copolymer, and a mixture of these propylene polymers with other α -olefin polymers is used, and 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, those disclosed in Japanese patent application laid-open Nos. 63-37148, 63-37152, 63-90552, 63-210152, 63-213547, 63-243150, 63-243152, 63-260943, 63-260944, 63-264650, 1-178541, 2-49047, 2-102242, 2-251548, 892-853, and 195751 may be preferably used.

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, for example, 0.001 to 10 parts by weight based on 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.