RU2793134C1 - Dispersed crystallization germ, polymer composition, its production method and molded product - Google Patents

Abstract

FIELD: polymer materials.

SUBSTANCE: invention relates to methods for modification of polymer materials. A dispersed crystallization germ is proposed, containing a compound of the formula (1), where a content of phosphate ions in the dispersed crystallization germ is equal to or exceeds 5 ppm and equal to or less than 8000 ppm of the weight of the compound represented by the formula (1). A polymer composition for the production of molded products, containing the specified polymerization germ, a method for the production of a polymer composition, and a molded product obtained using a composition are also proposed.

EFFECT: use of the proposed dispersed polymerization germ allows for an increase in the reliability of its supply and improvement of a color tone of a molded product.

9 cl, 1 tbl, 16 ex

Description

FIELD OF TECHNOLOGY

[0001]

The present invention relates to a dispersed crystallization nucleus, a polymer composition, a method for its production, and a molded article.

BACKGROUND OF THE INVENTION

[0002]

As a method for modifying a polymeric material, a method of adding a crystallization nucleus or a crystallization accelerator is known. As such kind of technology, for example, the technology disclosed in Patent Document 1 is known. polyolefin (claim 1 of patent document 1, etc.). In the document, a salt of a phosphoric acid ester is given as the seed of crystallization (item 0014 of Quote 1).

RELEVANT DOCUMENT

PATENT DOCUMENT

[0003]

[Patent Document 1] Japanese Patent Unexamined Publication No. 2017-149962

SUMMARY OF THE INVENTION

[0004]

However, as a result of research by the inventors of the present invention, in the nucleation plant described in Patent Document 1, it was determined that there is room for improvement in terms of feeding reliability and color tone of a molded article obtained by molding a polyolefin-based resin when this the seed is added to the polyolefin resin.

[0005]

As a result of the study conducted by the authors of the present invention, the following conclusion was reached.

Ordinary particulate seed is added to the thermoplastic resin and melt-kneaded into particles and used in the process of heating and molding the thermoplastic resin. However, there was a concern that the feed reliability would deteriorate due to the influence of different physical properties of the particulate nucleation powder. If the feed reliability deteriorates, the production reliability during the molding process deteriorates.

[0006]

As a result of research considering such circumstances, it has been found that it is possible to improve the supply reliability by making the dispersed crystallization nucleus contain phosphate ions. However, it has been understood that in the case where the particulate nucleation contains an excessive amount of phosphate ions, when the particulate nucleation is added to a thermoplastic resin, additives other than the particulate nucleation contained in the polyolefin-based resin react with phosphate. -ions, and as a result, the molded article obtained by molding the polyolefin-based resin is colored.

The present inventors further conducted research based on this discovery, and found that it is possible to improve the feed reliability and suppress coloration of a molded article obtained by molding a polyolefin resin when added to a polyolefin resin by setting the content of phosphate ions in the dispersed nucleation in the corresponding range of numerical values, and thereby completed the present invention.

[0007]

According to the present invention, a particulate seed is provided, comprising at least one compound represented by the following general formula (1),

where the phosphate ion content of the particulate seed obtained by the following measurement procedure is equal to or greater than 5 ppm and equal to or less than 8000 ppm based on the weight of the compound represented by the following general formula (1).

(measurement method)

1. The content of the dispersed crystallization nucleus is measured.

2. 100 parts by mass of xylene, 18 parts by mass of isopropyl alcohol, and 20 parts by mass of pure water with respect to 3 parts by mass of the compound represented by the general formula (1) are added to the particulate seed to obtain a mixture solution in a container.

3. The resulting mixture solution is stirred at room temperature for 15 minutes under the influence of ultrasonic waves.

4. Then the container is kept for 30 minutes to separate the organic layer and the aqueous layer.

5. The water layer in the container is fractionated and the water is completely distilled off.

6. 10 parts by mass of a 30 mmol/L aqueous potassium hydroxide solution based on 3 parts by mass of the compound represented by the general formula (1) was added to the residue in the container, and stirred for 15 minutes under ultrasonic waves.

7. Then, the liquid in the container is filtered with a 0.45 μm membrane filter to obtain a filtrate, and then the phosphate ion concentration in the filtrate is quantified by ion chromatography.

8. Based on the phosphate ion concentration in the filtrate, calculate the phosphate ion content (ppm) based on the weight of the compound represented by the general formula (1).

In the general formula (1), R ¹ to R ⁴ each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 9 carbon atoms, and R ⁵ represents a hydrogen atom or an alkyl group of 1 to 4 atoms carbon, m is 1 or 2, and in the case where m is 1, M ¹ is a hydrogen atom, an alkali metal atom, or Al(OH) ₂ , and in the case where m is 2, M ¹ is an atom alkaline earth metal, Al(OH) or Zn.

[0008]

In addition, according to the present invention, there is provided a resin composition obtained by incorporating a particulate seed into a polyolefin resin.

[0009]

In addition, according to the present invention, there is provided a method for producing a resin composition, comprising adding a dispersed nucleating agent to a polyolefin resin.

[0010]

In addition, according to the present invention, a molded article obtained using the resin composition is provided.

[0011]

According to the present invention, there is provided a dispersed nucleation nucleus excellent in feed reliability and capable of sufficiently suppressing coloration of a molded article obtained by molding a polyolefin resin when added to a polyolefin resin, a resin composition thereof, a production method thereof, and a molded article. .

DESCRIPTION OF OPTIONS FOR IMPLEMENTATION

[0012]

Describes the dispersed seed of crystallization according to the present variant of the method of implementation.

The dispersed crystallization nucleus contains an aromatic metal salt of a phosphoric acid ester. As the aromatic metal salt of the phosphoric acid ester, the compound represented by the following general formula (1) is used. The connection may be used alone, or two or more of them may be used by combining together.

[0013]

[0014]

(In the general formula (1), R ¹ to R ⁴ each independently represents a hydrogen atom or a straight chain or branched alkyl group having 1 to 9 carbon atoms, and R ⁵ represents a hydrogen atom or an alkyl group of 1 to 4 carbon atoms, M ¹ is 1 or 2, in the case where M is 1, M 1 is a hydrogen atom, an alkali metal atom, or Al(OH) ₂ , and in the case where M is 2, M ¹ is an alkaline earth atom metal, Al(OH) or Zn.)

[0015]

Examples of alkyl groups having 1 to 9 carbon atoms represented by R ¹ , R ² , R ³ and R ⁴ in the following general formula (1) include methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, t-butyl group, isobutyl group, amyl group, isoamyl group, t-amyl group, hexyl group, cyclohexyl group, heptyl group, isoheptyl group and t-heptyl group.

[0016]

In the following general formula (1), examples of the alkali metal atom represented by M ¹ include sodium (Na), potassium (K), lithium (Li), and the like. Among them, sodium and lithium are preferable because the nucleating effect of the nucleating component is remarkable, and sodium is particularly preferable.

[0017]

Examples of the alkaline earth metal atom designated M ¹ in the general formula (1) include beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), and radium (Ra), and among them, magnesium and calcium are preferred because the nucleation effect of the nucleation components is remarkable.

[0018]

Among the compounds represented by the general formula (1), the compound in which M is 1 is preferable. In addition, the compound in which R ¹ , R ² , R ³ and R ⁴ has one group selected from the group consisting of methyl group, an ethyl group, a sec-butyl group and a t-butyl group, a compound in which R ¹ , R ² , R ³ and R ⁴ has one group selected from the group consisting of a methyl group and a t-butyl group is more preferred , and a compound in which R ¹ , R ² , R ³ and R ⁴ have a tert-butyl group is particularly preferred. Further, a compound in which R ⁵ is a hydrogen atom or a methyl group is preferred, and a compound in which R ⁵ is a hydrogen atom is particularly preferred.

[0019]

As the compound represented by the general formula (1), one or two or more compounds represented by any of the chemical formulas (2) to (15) are preferably included. Among them, from the point of view of improving the physical properties of the resin, the compound represented by any of the chemical formulas (2) to (8) is preferable, the compound represented by any of the chemical formulas (5) to (8) is more preferable, even more preferable is the compound represented by any of the chemical formulas (5) or (7), and the compound represented by the chemical formula (5) is particularly preferred. From the point of view of increasing transparency, the compound represented by any of the chemical formulas (9) to (15) is preferable, the compound represented by any of the chemical formulas (9) to (12) is more preferred, the compound represented by any of the chemical formulas is even more preferred. formula (9) or (12), and the compound represented by the chemical formula (12) is particularly preferred.

[0020]

[0021]

As a method for producing the compound represented by the general formula (1), phosphorus trichloride (or phosphorus oxychloride) is reacted with 2,2'-alkylidenephenol, and then hydrolysis is carried out depending on the need to obtain cyclic acid phosphate. Subsequently, the cyclic acid phosphate is reacted with a metal hydroxide such as sodium hydroxide and potassium hydroxide, and the resulting reagent is suitably purified (filtered, etc.) and dried to obtain a compound (an aromatic metal salt of a phosphoric acid ester). In addition, the aromatic metal salt of the phosphoric acid ester can be synthesized by a known method in the related art and used as a compound.

In addition, the resulting compound is dissolved in a solvent, reacted with other metal hydroxides such as lithium hydroxide, or reacted with any salt of aluminum, zinc and an alkaline earth metal atom, and the resulting reagent is purified and dried to obtain another compound.

[0022]

The particulate seed of the present embodiment is obtained by pulverizing the obtained compound using appropriate pulverizing means, depending on the need. In a dispersed crystallization nucleus, large particles can be removed by sifting with a sieve with a given mesh size. In addition, the dispersed seed may include one or two or more powdered compounds. For example, two or more compounds having different particle diameter distributions or classified two or more compounds can be combined and mixed with each other in an appropriate proportion to obtain a dispersed seed.

[0023]

Examples of grinding apparatus include mortar, ball mill, rod mill, tube mill, cone mill, vibrating ball mill, Hyswing ball mill, roller mill, pin mill, hammer mill, attritor mill, whirlpool mill, jet mill, microfine mill , ultrafine mill, beacon mill, micro atomizer, colloid mill, premier colloid mill, micro mill, Charlotte colloid mill, rotary grinder, dry medium, agitated medium and the like. These grinding devices may be used alone, or two or more may be used in combination, and these devices are appropriately selected depending on the type of raw material powders to be crushed, the grinding time, and the like.

[0024]

The particulate seed of the present embodiment may only consist of the compound represented by the general formula (1), or may contain other components within the range of achieving the object of the present invention. Examples of other components include a nucleating agent other than the compound represented by the general formula (1), a fatty acid metal salt, a silicic acid-based inorganic additive component, hydrotalcites, and the like. The connection may be used alone, or two or more of them may be used by combining together.

The particulate seed of the present embodiment preferably contains a fatty acid metal salt in addition to the compound represented by the general formula (1). In this case, the dispersibility of the particulate seed in the polyolefin resin becomes excellent. In addition, the particulate seed of the present embodiment preferably contains a silicic acid-based inorganic additive in addition to the compound represented by the general formula (1). In this case, the nucleating action of the particulate seed becomes even more excellent.

[0025]

Examples of the nucleating agent other than the compound represented by the general formula (1) include metal carboxylates such as sodium benzoate, aluminum salt of 4-tert-butyl benzoate, sodium adipate, and disodium bicyclo[2.2.1]heptane-2,3-dicarboxylate and cyclohexane calcium 1,2-dicarboxylate, polyol derivatives such as dibenzylene sorbitol, bis(methylbenzylidene)sorbitol, bis(3,4-dimethylbenzylidene)sorbitol, bis(p-ethylbenzylene)sorbitol and bis(dimethylbenzylidene)sorbitol, 1,2,3- trideoxy-4,6:5,7-o-bis(4-propylbenzylidene)nonitol, amide compounds such as N,N',N"-tris[2-methylcyclohexyl]-1,2,3-propanetricarboxamide, N, N',N"-tricyclohexyl-1,3,5-benzenetricarboxamide, N,N'-dicyclohexylnaphthalene dicarboxamide, 1,3,5-tri(dimethylisopropylamino)benzene, and the like. Among them, metal carboxylates are particularly preferred. Further, among the metal carboxylates, sodium benzoate and aluminum salt of 4-tert-butyl benzoate are preferred, and sodium benzoate is particularly preferred.

[0026]

As the fatty acid metal salt, salts containing the compound represented by the following general formula (16) are preferable.

[0027]

[0028]

In the general formula (16), R ⁶ is a straight or branched aliphatic group containing 9 to 30 carbon atoms, M is a metal atom, and n is an integer from 1 to 4, which is an integer corresponding to the valency of M's metal atoms.

[0029]

In the general formula (16), R ⁶ is a straight or branched aliphatic group having 9 to 30 carbon atoms, examples of which include an alkyl group and an alkenyl group having 9 to 30 carbon atoms, and it may be substituted by a hydroxyl group.

[0030]

Examples of fatty acids forming fatty acid metal salts include saturated fatty acids such as capric acid, 2-ethylhexanoic acid, undecylic acid, lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, margaric acid, stearic acid, non-adecylic acid, arachidic acid, cheikosylic acid, behenic acid, tricosylic acid, lignoceric acid, cerotic acid, montanonic acid and melissa acid, straight chain acid. unsaturated fatty acids such as 4-decenoic acid, 4-dodecenoic acid, palmitoleic acid, α-linolenic acid, linoleic acid, ɤ-linolenic acid, stearidonic acid, petroselic acid, oleic acid, elaidic acid, vaccenic acid, eicosapentaenoic acid, docosapentaenoic acid; and docosahexaenoic acid; and the like.

In a fatty acid metal salt, the aliphatic group represented by R ⁶ preferably has 10 to 21 carbon atoms. As the fatty acid constituting the fatty acid metal salt, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid and 12-hydroxystearic acid are particularly preferable.

[0031]

Examples of the metal atom designated M include alkali metal, magnesium, calcium, strontium, barium, titanium, manganese, iron, zinc, silicon, zirconium, yttrium, barium, hafnium, and the like. Among them, alkali metals such as sodium, lithium and potassium are preferred, sodium and lithium are more preferred, and lithium is particularly preferred because its crystallization temperature is high.

[0032]

Examples of silicic acid based inorganic additives include colloidal silica, fumed silica, quartzite, diatomaceous earth, clay, kaolin, silica gel, calcium silicate, sericite, kaolinite, flint, feldspar flour, vermiculite, attapulgite, talc, mica, minnesotite, pyrophyllite and the like, and among them, those whose particle structure is a layered structure and those whose silicon content is 15% by mass or more are preferable. Examples of the preferred inorganic additive thereto include sericite, kaolinite, talc, mica, minnesotite, pyrophyllite and the like, talc and mica are more preferred, and talc is particularly preferred.

[0033]

Hydrotalcites can be natural products or synthetic products and can be used regardless of the presence or absence of surface treatment or the presence or absence of water of crystallization. Examples of hydrotalcites include basic carbonate represented by the following general formula.

M _x Mg _y Al _z CO ₃ (OH) _{xp + 2y + 3z-2} nH ₂ O

In the general formula, M represents an alkali metal or zinc, X represents a number from 0 to 6, y represents a number from 0 to 6, z represents a number from 0.1 to 4, p represents the valence of M, and n represents a number from 0 to 100 crystallization water.

[0034]

The particulate seed containing other components is a particulate seed composition containing a compound represented by the general formula (1), and is obtained by transformation so that it contains one or more aromatic phosphate esters selected from the group consisting of other metal salts, fatty acid metal salts, inorganic silicic acid additives and hydrotalcites, preferably one or more selected from the group consisting of fatty acid metal salts, talc, mica and hydrotalcites.

Such a dispersed seed is obtained, for example, by carrying out a pulverization treatment by an appropriate combination of pulverizing agents in the presence of a compound represented by the general formula (1) and other components. In addition, pulverizing means, screening means, mixing method and the like can be used.

[0035]

The particulate seed of the present embodiment acts as a seed and a transparency agent added in the molding process of a polyolefin resin, and can provide an improvement (modifying effect) such as crystallization temperature, thermal denaturation temperature, bending modulus, hardness, transparency etc. In addition, the properties of the molding cycle can be improved and productivity can be increased.

[0036]

The particulate seed of the present embodiment is obtained by the following measurement technique, and is characterized in that the content of phosphate ions (PO ₄ ^3- ) in the particulate seed is equal to or greater than 5 ppm to 8000 ppm by weight of the compound represented by the total formula (1).

(measurement method)

1. The content of the dispersed crystallization nucleus is measured.

2. 100 parts by mass of xylene, 18 parts by mass of isopropyl alcohol, and 20 parts by mass of pure water with respect to 3 parts by mass of the compound represented by the general formula (1) are added to the particulate seed to obtain a mixture solution in a container.

3. The resulting mixture solution is stirred at room temperature for 15 minutes under the influence of ultrasonic waves.

4. The container is then allowed to stand for 30 minutes to separate the organic layer and the aqueous layer.

5. The water layer in the container is fractionated and the water is completely distilled off.

6. 10 parts by weight of a 30 mmol/L potassium hydroxide aqueous solution with respect to 3 parts by weight of the compound represented by the general formula (1) are added to the residue in the container, and stirred for 15 minutes under ultrasonic waves.

7. Then, the liquid in the container is filtered with a 0.45 μm membrane filter to obtain a filtrate, and then the concentration of phosphate ions (PO ₄ ^3- ) in the filtrate is quantified by ion chromatography.

8. Based on the concentration of phosphate ions in the filtrate, the content of phosphate ions (ppm) based on the mass of the compound represented by the general formula (1) is calculated.

[0037]

The content of the compound represented by the general formula (1) in the particulate solid nucleation can be calculated from the use amount of the compound represented by the general formula (1) in the production of the particulate nucleation, and can be determined by the method of analyzing the organic component in the particulate nucleation with using a known method such as HPLC and GC, analyzing an inorganic component using a known method such as an ICP emission analysis, and combining the results of the analysis of the organic component and the results of the analysis of the inorganic component, and the like.

[0038]

In the measurement procedure 1, the amount of the particulate seed to be measured can be appropriately determined according to the content of the compound represented by the general formula (1) in the particulate seed, and, for example, in the case where the content of the compound represented by the general formula ( 1) in 1 g of particulate nucleation is A(g), the amount of particulate nucleation to be measured may be 2×A(g) to 4×A(g).

[0039]

In addition, in the measurement procedure 3, if an insoluble substance is present after stirring the mixture solution, the insoluble substance can be removed by a method such as filtration.

[0040]

According to the conclusions of the inventors of the present invention, it has been found that by using the phosphate ion content of the particulate nucleation as a guide, both the reliability of the particulate nucleation supply and the hue of the molded article obtained by molding the polyolefin-based resin can be properly controlled. , to which a dispersed crystallization nucleus is added. That is, it has become apparent that by setting the phosphate ion content at a predetermined level or more, the reliability of supplying the dispersed crystallization nucleus can be improved, and by setting the phosphate ion content at a predetermined level or less, coloring of a molded article obtained by molding a resin can be suppressed. polyolefin-based by adding a dispersed seed of crystallization to the polyolefin-based resin.

[0041]

By improving the reliability of supplying the dispersed crystallization nucleus, it is possible to improve the reliability of the resin molding process using the dispersed crystallization nucleus. Meanwhile, it is expected that the allowable range of physical properties of the particulate nucleation powder will be extended when used in a molding process or when used in a nucleation and a transparency agent.

In addition, by using a particulate nucleating agent capable of sufficiently suppressing coloration of a molded article obtained by molding a polyolefin-based resin by adding the particulate nucleating material to a polyolefin-based resin, a molded article having an excellent color tone can be obtained.

[0042]

In the present embodiment, the lower limit value of the phosphate ion content is equal to or greater than 5 ppm, preferably equal to or greater than 10 ppm, and even more preferably equal to or greater than 15 ppm based on the mass of the compound represented by the general formula (1 ). Due to this, it is possible to increase the reliability of supplying the dispersed crystallization nucleus.

[0043]

The upper limit of phosphate ions is equal to or less than 8000 ppm, preferably equal to or less than 1000 ppm, more preferably equal to or less than 500 ppm, even more preferably equal to or less than 200 ppm, and even more preferably equal to or less than 100 ppm based on the weight of the compound represented by the general formula (1). As a result, by adding the particulate seed to the thermoplastic resin, coloring of a molded article obtained by molding the thermoplastic resin can be suppressed.

[0044]

In the present embodiment, it is possible, for example, to control the content of phosphate ions by appropriately selecting the kind or amount of mixing of each component contained in the particulate seed, the method for synthesizing and preparing the particulate seed, and the like. Among them, for example, the use of trisodium phosphate anhydride in the stages of filtration, washing, purification, grinding, separation and mixing, as well as the stage of preparation of a dispersed crystallization nucleus, etc. are given as a constituent element for setting the content of phosphate ions in the desired range of numerical values.

[0045]

The dispersed seed of crystallization may contain an aliphatic amine.

An aliphatic amine is a compound in which one to three ammonia hydrogen atoms have been replaced by a hydrocarbon group. A portion of the hydrocarbon group may be substituted with an oxygen atom and the like. Examples of the hydrocarbon group include an alkyl group and an alcohol hydroxyl group.

[0046]

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

The number of carbon atoms of the hydrocarbon group in the aliphatic amine is 1 to 6, preferably 2 to 5, and more preferably 2 to 4, for example. Feed reliability can be improved by selecting appropriate carbon atoms.

[0047]

As the aliphatic amine, for example, amines such as aliphatic primary amines such as methylamine, ethylamine, propylamine, isopropylamine, butylamine, isobutylamine, t-butylamine, amylamine, hexylamine, palmitylamine, ethylenediamine and monoethanolamine; aliphatic secondary amines such as dimethylamine, diethylamine, dipropylamine, dibutylamine, diamylamine and diethanolamine; aliphatic tertiary amines such as dimethylamine, diethylamine, dipropylamine, dibutylamine, diamylamine and diethanolamine, trimethylamine, triethylamine, tripropylamine, tributylamine, triamylamine, N,N-dimethylamine and the like. Among them, from the point of view of the reliability of obtaining a dispersed crystallization nucleus, one or more aliphatic amines selected from the group consisting of triethylamine, diethylamine, butylamine and ethanolamine are preferable.

[0048]

The resin composition of the present embodiment is a resin composition containing a particulate seed in a polyolefin resin.

[0049]

The method for adding the particulate seed to the polyolefin resin is not particularly limited, and the method generally used can be applied as is. For example, a method of dry-mixing together a powdered polyolefin resin product or beads and a powdered particulate nucleation product can be used.

[0050]

The polymer composition can be used in various forms. For example, the form may be any of a pellet form, a granule form, and a powder form. From the point of view of ease of handling, the pellet form is preferred.

[0051]

Examples of the polyolefin-based resin include an α-olefin polymer such as polypropylene, high density polyethylene, low density polyethylene, straight chain low density polyethylene, polybutene-1, poly3-methylpentene, poly4-methylpentene, ethylene/propylene block, and random copolymer, etc.

[0052]

Further, the resin composition of the present embodiment may contain a resin component such as isoprene rubber, butadiene rubber, and a thermoplastic elastomer.

[0053]

The resin composition of the present embodiment preferably contains a polypropylene-based resin which exhibits remarkably the effect of using the particulate seed of the present embodiment. Examples of the polypropylene-based resin include polypropylene, ethylene/propylene block or random copolymer, α-olefin/propylene block other than ethylene, random copolymer, and the like.

[0054]

The polypropylene-based resin can be used regardless of extreme viscosity, isometric pentad fraction, density, molecular weight distribution, melt flow rate, hardness, and the like. For example, a polypropylene-based resin can also be appropriately used as described in Japanese Unexamined Patent Publication No. 63-37148, Japanese Unexamined Patent Publication No. 63-37152, Japanese Unexamined Patent Publication No. 63-90552, Japanese Unexamined Patent Publication No. 63-210152 , Japanese Unexamined Patent Publication No. 63-213547, Japanese Unexamined Patent Publication No. 63-243150, Japanese Unexamined Patent Publication No. 63-243152, Japanese Unexamined Patent Publication No. 63-260943, Japanese Unexamined Patent Publication No. 63-260944, Japanese Unexamined Patent Publication No. 63-264650, Japanese Unexamined Patent Publication No. 1-178541, Japanese Unexamined Patent Publication No. 2-49047, Japanese Unexamined Patent Publication No. 2-102242, Japanese Unexamined Patent Publication No. 2-251548, Japanese Unexamined Patent Publication No. 2-279746, Japanese Unexamined Patent Publication No. 3-195751 and the like.

[0055]

The content of the particulate seed may generally be in the range of 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 polyolefin resin. As a result, a polyolefin-based resin modification effect can be sufficiently obtained.

[0056]

The resin composition of the present embodiment may contain an additive such as an antioxidant, a photostabilizer, an ultraviolet absorber, a pigment, a filler, a plasticizer, an epoxy compound, a foaming agent, an antistatic agent, a fire retardant, a lubricant, a heavy metal inert agent, hydrotalcites, a carboxylic acid, a dye , silicic acid additive and processing aid. The connection may be used alone, or two or more of them may be used by combining together.

Examples of the antioxidant include a phosphorus-based antioxidant, a phenol-based antioxidant, a thioether-based antioxidant, and the like.

Examples of the antistatic agent include a low molecular weight antistatic agent containing a cationic surfactant, an anionic surfactant, a nonionic surfactant, an amphoteric surfactant and the like, and a high molecular weight antistatic agent containing a block polymer having an ionomer or polyethylene glycol. as a hydrophilic part, and the like.

Examples of the flame retardant include a halogen-based compound, a phosphoric acid ester, a phosphate amide compound, a melamine-based compound, a melamine salt polyphosphate compound, a fluorine resin, a metal oxide, and the like.

Examples of the lubricant include hydrocarbon lubricant, fatty acid lubricant, aliphatic alcohol lubricant, aliphatic ester lubricant, aliphatic amide lubricant, metallic soap lubricant and the like.

Examples of the silicic acid additive include colloidal silica, fumed silica, quartzite, diatomaceous earth, clay, kaolin, silica gel, calcium silicate, sericite, kaolinite, flint, feldspar flour, vermiculite, attapulgite, talc, mica, minnesotite, pyrophyllite etc.

[0057]

The content of the additive in the resin composition is preferably 0.001 to 10 parts by weight, for example, relative to 100 parts by weight of the polyolefin resin. By setting the additive content within such a range of numerical values, the effect of the additive is improved.

[0058]

The resin composition can be used in a molded product such as injection molded product, fiber, flat yarn, biaxially stretched film, uniaxially stretched film, non-stretched film, sheet, thermoformed product, extrusion blown product, injection blown product, injection stretch blown product, profiled extrusion molded product, rotationally molded product, and the like. Among them, injection molded product, film, sheet and thermoformed product are preferable as the molded product.

[0059]

The method for producing a molded article of the present embodiment includes the step of molding a resin composition based on various molding methods. With this, you can get a molded product.

The molding method is not particularly limited, and examples thereof include an injection molding method, an extrusion molding method, a blow molding method, a rotational molding method, a vacuum molding method, an inflation molding method, a calendar molding method, a wet molding method, a dip molding method, a foaming method, and the like. Among them, injection molding method, extrusion molding method and blow molding method are preferable.

[0060]

The polymer composition can be used for various purposes such as building materials, agricultural materials, components for vehicles such as cars, trains, ships, aircraft and the like, packaging materials, various goods, toys, household appliances, medical supplies and the like. . Specifically, examples thereof include automotive components such as a bumper, dashboard, dashboard, battery box, trunk, door panel, door trim, fender lining, and the like; resin components for household appliances such as a refrigerator, washing machine, vacuum cleaner, and the like; household items such as dishes, bottle caps, buckets, bathing items, etc.; resin components for connection such as a connector and the like; miscellaneous goods such as toys, storage containers, synthetic paper, etc.; medical molded articles such as medical packaging, syringe, catheter, medical tube, syringe preparation, infusion solution bag, reagent container, drug container, medical device packaging and the like; building materials such as wall material, floor material, window frame, wallpaper, windows, and the like; wire coating materials; agricultural materials such as house, pipeline, flat yarn and the like; industrial materials such as tray, bucket, sharpening tape, liquid crystal protection tape, pipe, modified silicone resin for sealing material, and the like; food packaging materials such as a wrapper, tray, cup, film, bottle, lid, storage container, and the like; other 3D printer materials, battery release film and the like. In addition, the polymer composition can be used in cases where various post-processing is performed, for example, in cases where radiation sterilization is performed, for example, for medical applications and food packaging, in cases where low-temperature plasma treatment is performed after molding, and the like to improve surface properties such as coating properties, or the like. Among them, the resin composition is preferably used in automotive components, household products, and food packaging materials.

[Examples]

[0061]

Hereinafter, the present invention will be described in detail with reference to examples. However, the present invention is not limited to the descriptions of the examples.

[0062]

<Compound Synthesis>

(Dispersed seed of crystallization 1)

42.5 g of 2,2'-methylenebis[4,6-bis(1,1-dimethylethyl)]phenol, 16.1 g of phosphorus oxychloride and 2.4 g of triethylamine were placed and stirred at 50° C. for 3 hours. Then, an aqueous solution of 4 g of sodium hydroxide and methanol was placed and stirred at room temperature for 1 hour to obtain a suspension. The resulting suspension was filtered and the filtrate was washed with water until a white solid was obtained. 500 ml of pure water and 50 mg of a dispersant (ADEKA COL EC-8600 manufactured by ADEKA Corporation) were added to the resulting white solid, and the mixture was stirred at room temperature for 1 hour to obtain a suspension. The resulting suspension was filtered and the filtrate was washed with water until a white solid was obtained. The resulting white solid was dried under reduced pressure to give 42.1 g of a white particulate product represented by Compound No. 1. The white particulate product was designated as particulate seed 1.

[0063]

[0064]

(Dispersed seed of crystallization 2)

25.4 g (0.05 mol) of white powders obtained in <synthesis of compound No. 1> was dissolved in methanol, an aqueous solution of 1.2 g (0.05 mol) of lithium hydroxide was added thereto, and the obtained product was stirred at room temperature. temperature for 1 hour to obtain a suspension. The resulting suspension was filtered and the filtrate was washed with water until the pH reached 8 to give a white solid. The resulting white solid was dried under reduced pressure and then pulverized in a dry agitation mill to obtain 20.5 g of a white particle product represented by Compound No. 2. This white particle product was designated as particulate seed 2.

[0065]

[0066]

(Dispersed seed of crystallization 3)

10.2 g (0.02 mol) of the white powders obtained in <synthesis of compound No. 1> were dissolved in methanol, and an aqueous solution of 2.41 g (0.01 mol) of aluminum sulfate was added dropwise while stirring at 40°C . After completion of the addition, the reaction mixture was heated and stirred under reflux with methanol for 4 hours. After completion of heating and stirring, the reaction mixture was cooled to room temperature to obtain a suspension. The resulting suspension was filtered and the filtrate washed several times with water until a white solid was obtained. The resulting white solid was dried under reduced pressure and then ground with a pin mill to obtain 9.63 g of a white particle product represented by Compound No. 3. This white particle product was designated as dispersed seed 3.

[0067]

[0068]

(Dispersed seed of crystallization 4)

135 g of particulate seed 1 and 15 g of particulate seed 2 were uniformly mixed to obtain 150 g of particulate seed 4.

[0069]

(Dispersed seed of crystallization 5)

135 g of particulate seed 1 and 15 g of sodium benzoate (product name ORGATER MI.NA.08 manufactured by ADEKA POLYMER ADDITVES EUROPE) were uniformly mixed to obtain 150 g of particulate seed 4.

(Dispersed seed of crystallization 6)

135 g of particulate seed 1 and 15 g of lithium myristate were uniformly mixed to obtain 150 g of particulate seed 4.

[0070]

(Dispersed seed of crystallization 7)

135 g of particulate seed 1 and 15 g of talc (product name: MICRO ACE P-4 manufactured by Nippon Talc Co., Ltd.) were uniformly mixed to obtain 150 g of particulate seed 4.

[0071]

(Examples 1 to 16, Comparative Examples 1 to 2)

A predetermined amount of trisodium phosphate anhydride was added to the obtained particulate seeds 1-7 to obtain the particulate seeds of Examples 4-16 and Comparative Example 2 having a phosphate ion content as shown in Table 1. Then, by mixing a predetermined amount of the particulate seed 1 and the particulate seed of Example 4, the particulate seed of Examples 1 to 3 and Comparative Example 1 were obtained having a phosphate ion content as shown in Table 1.

[0072]

The content of phosphate ions (PO ₄ ^3- ) in the particulate nuclei of crystallization of examples 1-16 and comparative examples 1 and 2 was determined using the following measurement procedure.

[0073]

<Phosphate ion measurement>

1. As a sample, the obtained dispersed crystallization nucleus was measured in a 250 ml plastic bottle. Here, the measured amount of the particulate seed was set so that the loaded amount of the compound represented by the general formula (1) was 3 g.

2. 100 g of xylene, 18 g of isopropyl alcohol and 20 g of pure water were added to a plastic bottle to form a mixture solution in a container.

3. The resulting mixture solution was stirred at room temperature for 15 minutes under ultrasonic waves, the mixture solution was filtered, and only the filtrate was returned to the container.

4. The container was allowed to stand for 30 minutes to separate the organic layer and the aqueous layer.

5. The aqueous layer in the container was fractionated and transferred to a 500 ml oblong flask, and the water was completely distilled off using a rotary evaporator.

6. After adding 10 ml of a 30 mmol/L potassium hydroxide aqueous solution to the residue in a 500 ml oblong flask, the oblong flask was tightly capped with a ball stopper and stirred for 15 minutes under ultrasonic waves.

7. The liquid in the 500 ml oblong flask was filtered using a 0.45 μm membrane filter to obtain a filtrate, and then the phosphate ion concentration in the filtrate was quantified by ion chromatography based on the following measurement conditions. The phosphate ion species for the targets was PO ₄ ^3- . The concentration (ppm) of phosphate ions was measured using three targets, and the average of the three measured values was obtained.

8. Based on the concentration of phosphate ions in the filtrate, the content (ppm) of phosphate ions based on the weight of the compound represented by the general formula (1) was calculated.

(Measurement conditions)

Measuring device: ICS-2100 ion chromatograph (manufactured by Thermofischer Scientific Co., Ltd.)

Column: Dionex IonPac AS19 (manufactured by Thermofischer Scientific Co., Ltd.)

Detector: Conductivity detector

Elution conditions: 1.0 mmol/l aqueous potassium hydroxide solution (0 minutes) → 60.0 mmol/l aqueous potassium hydroxide solution (35 minutes). The concentration of the aqueous potassium hydroxide solution was changed as follows.

0 minutes to 1 minute: Gradient from 1.0 mmol/L to 10.0 mmol/L.

From 1 minute to 10 minutes: a constant level of 10.0 mmol/l.

10 minutes to 15 minutes: gradient from 10.0 mmol/L to 60.0 mmol/L.

From more than 15 minutes to 35 minutes: a constant level of 60.0 mmol/L.

Flow rate: 1.0 ml/min

Sample injection volume: 25 µl

Column temperature: 35°C

[0074]

The content of phosphate ions of particles of dispersed crystallization nuclei from 1 to 7, measured on the basis of <Phosphate ion content measurement>, was always less than 0.5 ppm.

[0075]

[Table 1]

Comparative Example 1 Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Dispersed crystallization nucleus 1 1 1 1 1 2 3 1 1 1 Content of phosphate ions
(×1000ppm) 0.0007 0.005 0.02 0.05 0.1 0.1 0.1 0.2 0.5 1 Unloading time (s) 56 23 20 20 19 20 18 20 21 20 Thermal staining index ΔT (%) < 0.1 0.1 0.1 0.1 0.1 0.1 0.3 0.2 0.2 0.3 Feed reliability X

The degree of coloration of the molded product

[Table 1 continued]

Example 10 Example 11 Example 12 Example 13 Example 14 Example 15 Example 16 Comparative Example 2 Dispersed crystallization nucleus 1 1 1 4 5 6 7 1 Content of phosphate ions
(×1000ppm) 2 5 8 0.05 0.02 0.02 0.02 10 Unloading time (s) 18 20 18 22 21 23 22 21 Thermal staining index ΔT (%) 0.4 0.5 0.5 0.1 0.1 0.1 0.1 2.1 Feed reliability

The degree of coloration of the molded product

X

[0076]

The dispersed seed of the Examples and Comparative Examples were evaluated based on the following evaluation parameters.

[0077]

<Feed Security>

Using a powder property evaluation device (MT-02 multi-tester manufactured by Seishin Enterprise Co., Ltd.), the resulting dispersed crystallization seed was introduced into the feeder of the powder property evaluation device per 10 g, and the discharge time during vibration was measured under the condition of the vibration width of the feeder 1 .0 mm. Each particulate seed was measured using three samples, and the average of the three measurement values was set as the discharge time t (s) and used as a feed reliability index. The result is shown in Table 1. The pass and fail criteria for feed reliability are as follows.

Pass: t is equal to or less than 30 seconds

Failure: t is more than 30 seconds

[0078]

<Colour Degree of Molded Product>

The heat coloring index ΔT was calculated by the following method and used as an index for judging the degree of coloring of a molded article obtained by molding a thermoplastic resin when a dispersed seed was added to the polyolefin-based resin.

1 g of the obtained particulate seed and 1 g of a phenol-based antioxidant (ADEKA STUB AO-60 manufactured by ADEKA Corporation) were measured and mixed while grinding using a mortar.

1 g of the resulting mixture was measured, transferred to a glass tube and heated in air at 230° C. for 5 minutes using a block bath.

The heated mixture was allowed to cool to room temperature, 5 ml of solvent was added and the mixture was stirred for 15 minutes while adding ultrasonic waves. The solvent was further added to the solution after cooling to obtain 10 ml of the solution, and then the solution was filtered to obtain a filtrate. This filtrate was used as a test solution.

Here, the following solvent was used as the solvent.

Dispersed seeds 1 and 4-7, Examples 1-4 and 7-16, Comparative Examples 1 and 2: Methanol/toluene mixed solvent=1/4 (mass ratio)

Dispersed seed 2, Example 5: mixed solvent of methanol/toluene=1/1 (mass ratio)

Dispersed seed 3, Example 6: toluene

The resulting test solution was filtered with a 0.45 μm membrane filter, and then the transmittance (%) at a wavelength of 450 mn was measured with an ultraviolet visible spectrophotometer (V-750 manufactured by JASCO Corporation).

[0079]

ΔT (%) was calculated by the following formula and evaluated based on the following evaluation criteria. The results of ΔT measurement are shown in Table 1.

Concerning Examples 1-4, 7-12 and Comparative Examples 1 and 2

Thermal staining index formula: ΔT (%)=transmittance (%) of each sample solution at 450 nm wavelength - transmittance (%) of dispersed seed 1 sample solution at 450 nm wavelength.

Regarding example 5

Thermal staining index formula: ΔT (%)=transmittance (%) of sample solution at 450 nm - transmittance (%) of dispersed seed 2 sample solution at 450 nm.

Regarding example 6

Thermal staining index formula: ΔT (%)=transmittance (%) of sample solution at 450 nm - transmittance (%) of dispersed seed 3 sample solution at 450 nm.

Regarding example 13

Thermal staining index formula: ΔT (%)=transmittance (%) of sample solution at 450 nm - transmittance (%) of dispersed seed 4 sample solution at 450 nm.

Regarding example 14

Thermal staining index formula: ΔT (%)=transmittance (%) of sample solution at 450 nm - transmittance (%) of dispersed seed 5 sample solution at 450 nm.

Regarding example 15

Thermal staining index formula: ΔT (%)=transmittance (%) of sample solution at 450 nm wavelength - transmittance (%) of dispersed seed 6 sample solution at 450 nm wavelength.

Regarding example 16

Thermal staining index formula: ΔT (%)=transmittance (%) of sample solution at 450 nm - transmittance (%) of dispersed seed 7 sample solution at 450 nm.

[0080]

The pass and miss criteria for the degree of coloration of a molded article obtained by molding a polyolefin resin when a dispersed seed was added to the polyolefin resin were as follows.

Suitable: ΔT equal to or less than 1.0%

Unsuitable: ΔT greater than 1.0%

[0081]

<Transparency properties>

Composition obtained by mixing 0.1 mass parts of the obtained particulate seed of each example with 100 mass parts of polypropylene using a Henschel mixer for 1 minute and extrusion processed at a temperature of 230°C and 150 rpm to obtain a pellet. The haze (haze value: %) of a 1 mm thick injection molded sample obtained at 200° C. was measured based on JIS K7136.

[0082]

The particulate seeds of Examples 1 to 16 were superior in feed reliability compared to the particulate seeds of Comparative Example 1. In addition, the particulate seeds of Examples 1 to 16 have a significantly lower heat staining index ΔT than the particulate seeds of Comparative Example 2, and it was found that by adding the particulate nuclei of examples 1 to 16 to the polyolefin-based resin, it was found that the color of a molded article obtained by molding a thermoplastic resin can be sufficiently suppressed.

In addition, the dispersed nuclei of Examples 1 to 16 had a small haze value in the range where there were no problems with their practical use.

Such dispersed seeds of examples can improve the clarity of the polyolefin resin. Therefore, it has been found that the particulate seed can be suitably used as a seed and a transparency enhancer.

[0083]

Priority is claimed from Japanese Patent Application No. 2020-045090, filed March 16, 2020, the contents of which are hereby incorporated by reference.

Claims (29)

1. Dispersed crystallization embryo, containing: at least one compound represented by the following general formula (1), where the phosphate ion content of the particulate seed obtained by the following measurement procedure is equal to or greater than 5 ppm and equal to or less than 8000 ppm based on the weight of the compound represented by the following general formula (1), (measurement method) 1) measure the dispersed crystallization nucleus, 2) 100 parts by mass of xylene, 18 parts by mass of isopropyl alcohol, and 20 parts by mass of pure water with respect to 3 parts by mass of the compound represented by the general formula (1) are added to the particulate seed to obtain a mixture solution in a container, 3) the resulting mixture solution is stirred at room temperature for 15 minutes under the influence of ultrasonic waves, 4) then the container is kept for 30 minutes to separate the organic layer and the aqueous layer, 5) the water layer in the container is extracted and the water is completely distilled off, 6) 10 parts by mass of a 30 mmol/L aqueous solution of potassium hydroxide based on 3 parts by mass of the compound represented by the general formula (1) is added to the residue in the container, and stirred for 15 minutes while being exposed to ultrasonic waves, 7) The liquid in the container is then filtered using a membrane filter with a pore size of 0.45 µm to obtain a filtrate, and then the concentration of phosphate ions in the filtrate is quantified by ion chromatography, 8) Based on the concentration of phosphate ions in the filtrate, calculate the content of phosphate ions (ppm) based on the mass of the compound represented by the general formula (1),

where in the general formula (1) R ¹ -R ⁴ each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 9 carbon atoms, and R ⁵ represents a hydrogen atom or an alkyl group with 1 to 4 atoms carbon, m is 1 or 2, and in the case where m is 1, M ¹ is a hydrogen atom, an alkali metal atom or Al(OH) ₂ , and in the case where m is 2, M ¹ is an alkaline earth atom metal, Al(OH) or Zn. 2. The dispersed seed of crystallization according to claim 1, where the compound contains one, or two, or more compounds represented by the following chemical formulas (2) - (15)

3. Dispersed crystallization germ according to claim 1, additionally containing: aliphatic amine. 4. Dispersed crystallization germ according to claim 1, additionally containing: at least one component selected from the group consisting of a nucleating agent other than the compound represented by the general formula (1), a fatty acid metal salt, and an inorganic silicic acid additive component. 5. Polymer composition for obtaining molded products, containing: a polyolefin-based resin containing a dispersed seed according to any one of claims 1 to 4. 6. Polymer composition according to claim 5, wherein the polyolefin resin comprises a polypropylene resin. 7. Polymer composition according to claim 5, wherein the content of the particulate seed is equal to or greater than 0.001 mass parts and equal to or less than 10 mass parts with respect to 100 mass parts of the polyolefin resin. 8. A method for producing a polymer composition, including: adding a particulate seed according to any one of claims 1 to 4 to the polyolefin resin. 9. Molded product obtained using the polymer composition according to claim 5.