JP5191102B2 - Method for producing high-performance nucleating agent - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyolefin resin composition that has excellent transparency and crystallization temperature. <P>SOLUTION: The nucleating agent has a number-average particle diameter (a) of less than 0.1 &mu;m, and when the wt.% of the nucleating agent to the resin is represented as C<SB>NA</SB>and the nucleation speed I is represented by the following formula (1), the ratio of the I<SB>0</SB>/C<SB>NA</SB>is more than 10<SP>14</SP>(mm<SP>-3</SP>s<SP>-1</SP>). lnI=lnI<SB>0</SB>-(C/&Delta;T) (1) wherein I: nucleating speed of the crystalline resin, I<SB>0</SB>: prefactor, C: a constant determined by experiment; &utri;T: supercooling degree [difference between the equilibrium melting point T<SB>m</SB><SP>0</SP>and crystallization temperature (&deg;K)]; I<SB>0</SB>: The y-intercept when the straight line obtained by plotting lnI to 1/&utri;T is extrapolated to (1/&utri;T)=0, I: the increase of the number of the crystals per the unit volume (1 mm<SP>3</SP>) and the unit time (1 second) when the molten polymer is crystallized. The crystallization is carried out by adding 0.1 pt.wt. of the nucleating agent to 100 pts.wt. of crystallizing resin, a film of 0.1 mm thickness is molten and then cooled down and crystallized at a certain same temperature T. <P>COPYRIGHT: (C)2008,JPO&amp;INPIT

Description

  The present invention relates to a high-performance nucleating agent for crystalline resins and a method for producing the nucleating agent.

  Polyolefin resins are widely used for containers, building materials, automobile parts and the like because of their excellent physical and chemical characteristics and low environmental load characteristics. However, in applications that require high transparency such as containers and films / sheets, and applications that require high strength and high crystallization temperature, improvements in transparency and crystallization temperature are desired.

Conventionally, in order to improve the transparency and physical properties of polyolefin resin, it has been proposed to add organic acid metal salts such as benzoic acid metal salts and aromatic phosphate metal salts, or to add dibenzylidene sorbitol, Improvement of the function of polyolefin resin is achieved.
However, although dibenzylidene sorbitols are excellent in improving transparency, they are less effective in improving strength and heat distortion temperature, and there is a problem of odor due to decomposition. In addition, although the organic acid metal salt is excellent in improving strength and crystallization temperature, it has a high melting point, and since it does not melt at the processing temperature, it is difficult to finely disperse and the effect of improving transparency is small. There are problems that the pulverization is insufficient, or that secondary aggregation causes large particles to cause molding defects.
As a higher-performance nucleating agent for organic acid metal salts, JP 2004-530006 A and JP 2001-507395 A propose metal salts of cycloalkane carboxylic acid and cycloalkene carboxylic acid. Conventionally, improvement in the performance of a nucleating agent based on the structure of the organic acid used has been studied.
Although the performance was improved by selecting the structure of the organic acid and the metal species, the performance improvement effect was limited.

Claims of JP-T-2004-530006 Claims of JP-T-2001-507395

  Therefore, this invention is providing the manufacturing method of the polyolefin resin composition excellent in transparency and crystallization temperature.

As a result of intensive studies in view of the above situation, the present inventors have determined that the fine nucleating agent having a major axis number average particle size (a) of 0.1 mm or less, and the weight percent of the nucleating agent relative to the resin and C _NA, the ratio between the C _NA and I ₀ in equation (1), the nucleating agent is I ₀ / C _NA is 10 ¹⁵ (mm ^-3 s ^-1) or more, excellent performance nucleating agent By adding an aromatic solvent and a polyolefin resin to an organic acid metal salt solution using an alcohol-based solvent, cooling with heating and dissolving, the organic acid metal salt is uniformly contained in the resin as fine crystals. It has been found that the nucleating agent can be produced.

（式中、Ｒ₁は炭素原子数４〜８のアルキル基、Ｒ₂は水素原子または炭素原子数１〜８のアルキル基、Ｒ₃は炭素原子数１〜４のアルキリデン基、Ａは（ｎ＋ｘ）価の金属、ｎは１〜３の整数、及びｘは０〜２の整数を表す。） The present invention has been made based on the above knowledge, and the first invention is a mixture of a polyolefin resin and an organic acid metal salt represented by the following general formula (I), an alcohol solvent and an aromatic solvent. A method for producing a nucleating agent having a number average particle size (a) for crystallization of a polyolefin resin of 0.1 μm or less, wherein the polyolefin resin is precipitated by heating and dissolving in a solvent and then cooling to precipitate the polyolefin resin containing an organic acid metal salt. By providing the above, the above object is achieved.

(Wherein R ₁ is an alkyl group having 4 to 8 carbon atoms, R ₂ is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, R ₃ is an alkylidene group having 1 to 4 carbon atoms, and A is (n + x ) A valent metal, n represents an integer of 1 to 3, and x represents an integer of 0 to 2.)

2nd invention achieves the said objective by providing the manufacturing method of the said nucleating agent whose said alcohol solvent is butanol.

According to a third aspect of the present invention, there is provided a method for producing the nucleating agent using 10 to 500 parts by weight of the alcohol solvent and 5 to 3000 parts by weight of the aromatic solvent with respect to 1 part by weight of the compound of the general formula (I). By providing this, the above-mentioned purpose is achieved.

  By this invention, the manufacturing method of the polyolefin resin composition excellent in transparency and crystallization temperature can be provided.

A preferred embodiment of the present invention will be described in detail.
The expression (1) in the present invention is derived from crystal nucleation theory. From equation (1), the performance of the nucleating agent is determined by two factors, I ₀ and ΔG ^* .
The first factor, I _0, is proportional to the product of the nucleating agent concentration C _NA and the reciprocal of the particle size a ⁻¹ , assuming that the effect of the nucleating agent is determined by the nucleating agent epitaxy. It can be represented by the following formula (2 ′).
I ₀ ∝C _NA a ^-1 (2 ')
Therefore, if the conventional nucleating agent having a number average particle size a of several hundred nm to 1 mm can be dispersed into a resin by making it a nucleating agent having a fine particle size of 100 nm or less, the performance of the nucleating agent is 10 times or more. Can be predicted.
On the other hand, ΔG ^* which is the second factor is determined by Δσ which is an interface free energy including an epitaxy effect of the nucleating agent. Since the crystallization temperature under ordinary polyolefin molding conditions is several tens of degrees lower than the equilibrium melting point, it is considered that the nucleation rate I is determined by two-dimensional nucleation on the nucleating agent. In this case, ΔG ^* is expressed by the following formula (2).
ΔG ^* = 4σσ _e / (Δg−Δσ) (2)
σ: side surface free energy, σ _e : end surface free energy, Δg is melting free energy and is represented by the following formula (3).
Δg = (Δh / T _m ⁰ ) ΔT (3)
Δh: melting enthalpy, T _m ⁰ : Equation (4) is derived from the equilibrium melting point formula (1), and log I is plotted against 1 / ΔT.
log I = log I ₀ −ΔG ^* / kT = log I ₀ −4σσ _e / (kT (Δg−Δσ)) (4)
ΔT in actual molding is 40 to 70K, and when Δg / σ representing the epitaxy ability of the nucleating agent is as small as about 1/10, Δg >> Δσ is satisfied. (Δg−Δσ) can be approximated by Δg. Therefore, the plot of log I with respect to 1 / ΔT is a straight line having a slope asymptotic to the slope of the straight line (−4σσ _e / kTΔg) in the case of having an ideal epitaxial ability of (Δσ / σ) = 0. Even if / σ changes greatly to about 1/10 ± 30%, the slope of the straight line changes only about several percent. From this, it was predicted that “the nucleation rate hardly depends on the magnitude of Δσ / σ when the epitaxy ability (Δσ / σ) of the nucleating agent is as small as about 1/10”.
That is, it was considered that a high-performance nucleating agent can be realized by making the nucleating agent finer and increasing I ₀ than by improving the epitaxy ability by improving the structure of the nucleating agent. However, in the conventional top-down type pulverization method using a pulverizer, I ₀ of the nucleating agent obtained is about 10 ^{12 according to the} experimental results of the inventors in polypropylene. Further, it was predicted that if the particles were simply made into nanoparticles, secondary aggregation occurred and I ₀ did not increase as a result. Therefore, nucleation of a coarse organic acid metal salt compound having a number average particle diameter of several hundred nm to 1 mm can be achieved by establishing a production technique and a fine dispersion technique of an appropriate fine nucleating agent, which is difficult with conventional techniques. If the nucleating agent can be made into a nucleating agent having a fine and uniform size distribution of 100 nanometers or less and dispersed in the resin, it can be predicted that the performance of the nucleating agent can be increased by 10 times or more.
Based on this prediction, the microcrystals of the nucleating agent precipitated from the solution system under the conditions such as the solvent are precipitated and recovered together with the polyolefin, etc., which is not obtained with conventional nucleating agents without secondary aggregation. It has been found that a nucleating agent exhibiting I ₀ can be obtained. Since the nucleating agent has a high I ₀ , a resin composition having a high crystallization temperature and excellent transparency can be provided.

log I ₀ is obtained as a vertical axis log I intercept when a straight line obtained by plotting log I against 1 / ΔT is extrapolated to (1 / ΔT) = 0.

The nucleating agent used in the present invention is not particularly limited as long as it is a compound that does not melt at the processing temperature of the applicable resin and exhibits a nucleating effect. For example, sodium benzoate, p-tert-butylbenzoic acid Aluminum, sodium bis (2,4-ditert-butylphenyl) phosphate, sodium 2,2′-methylenebis (4,6-ditert-butylphenyl) phosphate, 2,2′-methylenebis (4,6- Ditertiary butylphenyl) lithium phosphate, disodium-bicyclo [2,2,1] heptane-2,3-dicarboxylic acid, disodium-bicyclo [2,2,1] heptene-2,3-dicarboxylic acid, etc. Is mentioned. Among these compounds, the organic acid metal salt represented by the general formula (I) is preferable. The nucleating agent comprising these compounds preferably has a number average particle size (a) of 0.1 μm or less, more preferably 0.05 μm. If the number average particle size (a) is larger than 0.1 μm, the surface area of the nucleating agent at the same addition amount becomes small, and the nucleation effect of the present invention cannot be obtained sufficiently, which is not preferable.
In addition, the said number average particle diameter (a) is defined by following formula (5).

（式中、ｘは粒径、ｆ（ｘ）は粒径の数分布関数である。）

(Where x is the particle size and f (x) is the number distribution function of the particle size.)

  The resin to which the nucleating agent of the present invention is applied is not particularly limited as long as it is a crystalline resin. For example, low density polyethylene, linear low density polyethylene, high density polyethylene, isotactic polypropylene, syndiotactic Polypropylene, hemiisotactic polypropylene, cycloolefin polymer, stereoblock polypropylene, polybutene-1, poly-3-methyl-1-butene, poly-3-methyl-1-pentene, poly-4-methyl-1-pentene, etc. Polyolefin polymers such as α-olefin polymers, ethylene / propylene blocks or random copolymers, and other thermoplastic polymers such as polyethylene terephthalate, polybutylene terephthalate, and polyhexamethylene terephthalate. Polymer sulfide polymers such as polyphenylene sulfide; Aliphatic hydroxycarboxylic acid polymers such as polylactic acid and polycaprolactone; Linear polyamide polymers such as polyhexamethylene adipamide; Crystalline polystyrene polymers such as syndiotactic polystyrene Polymers: Condensation polymers such as polyimide, polyamideimide, acrylic acid, methacrylic acid, and nylon are listed.

  Among the above crystalline resins, polyolefin resins that have a remarkable effect of using the nucleating agent of the present invention are suitable, such as polypropylene, ethylene / propylene block or random copolymer, and α-olefin / propylene block other than ethylene. Or, a polypropylene resin such as a random copolymer and a mixture of these propylene polymer and another α-olefin polymer, and polyethylene are particularly suitable.

  The polyolefin resin is a lamella measured by stereoregularity, specific gravity, type of polymerization catalyst, presence / absence or degree of polymerization catalyst removal, degree of crystallization, polymerization conditions such as temperature and pressure, type of crystal, X-ray small angle scattering. The copolymer size, crystal aspect ratio, solubility in aromatic or aliphatic solvents, solution viscosity, melt viscosity, average molecular weight, degree of molecular weight distribution, how many peaks in molecular weight distribution, Although it may be a block or random, a difference in expression of the effect of the invention may occur depending on the blending ratio of each monomer, etc., but it is applicable when any resin is selected.

The amount of the crystalline resin used is preferably 0.01 to 5000 parts by weight, more preferably 0.05 to 1000 parts by weight with respect to 1 part by weight of the nucleating agent of the present invention.
The amount of the alcohol solvent used is preferably 10 to 500 parts by weight, more preferably 20 to 200 parts by weight, per 1 part by weight of the nucleating agent of the present invention. The amount of the aromatic solvent used is preferably 5 to 3000 parts by weight, more preferably 50 to 2000 parts by weight, with respect to 1 part by weight of the nucleating agent of the present invention.

Examples of the alkyl group represented by R ₁ in the general formula (I) include butyl, sec-butyl, tert-butyl, pentyl, tert-pentyl, hexyl, cyclohexyl, heptyl, octyl, isooctyl, and tertiary octyl. Etc.

Examples of the alkyl group represented by R ₂ include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, tert-pentyl, hexyl, cyclohexyl, heptyl, octyl, isooctyl, and tertiary. Examples include octyl.

Examples of the alkylidene group represented by R ₃ include methylene, ethylidene, propylidene, and butylidene.

  Examples of the metal represented by A include alkali metals such as lithium, sodium and potassium, alkaline earth metals such as magnesium, calcium and barium, zinc and aluminum. Alkali metals such as sodium and potassium are preferred because their solubility in a mixed solvent of an alcohol solvent and an aromatic solvent is suitable for the practice of the present invention.

  More specifically, examples of the compound represented by the general formula (I) include the following Nos. 1-6 compounds, etc. are mentioned. However, the present invention is not limited by the following compounds.

  Examples of the alcohol solvent used in the present invention include methanol, ethanol, propanol, isopropanol, butanol, tert-butanol, pentanol, hexanol and the like. Butanol is preferred because it can be heated to a higher temperature in order to dissolve the polyolefin resin in an aromatic solvent and is excellent in the solubility of the organic acid metal salt.

  As the aromatic solvent used in the present invention, benzene, toluene, xylene, ethylbenzene, an industrial mixed solvent, or the like is used. Xylene is preferred because of the solubility of the polyolefin resin, ease of solvent removal, and safety.

  As a specific implementation method of the present invention, an organic acid metal salt is dissolved in an alcohol solvent, an aromatic solvent is added and heated, a polyolefin resin is added and dissolved, and then cooled to precipitate a polyolefin resin. . Since the organic acid metal salt exhibits higher solubility at a low temperature in an alcohol-based solvent, the concentration is preferably close to the saturation concentration at the temperature at which the polyolefin resin is heated and dissolved. Polyolefin resin composition containing fine organic acid metal salt crystals that are considered to exhibit large crystallization effects due to the following mechanism if the concentration is much higher than the saturated concentration, resulting in large crystals. No product is obtained, and if the concentration is too low, the organic acid metal salt is not taken into the precipitated polyolefin resin, and the effect as a nucleating agent is not exhibited.

  When the nucleating agent of the present invention is used for a crystalline resin, other resin additives may be blended, and the other resin additives are not particularly limited, and are phenolic antioxidants and phosphorus antioxidants. Agents, thioether-based antioxidants, amine-based antioxidants, hydroxylamine-based antioxidants, etc .; benzotriazole-based UV absorbers, benzophenone-based UV absorbers, triazine-based UV absorbers, cyanoacrylate-based UV absorbers UV absorbers such as additives; hindered amine stabilizers; acid supplements such as calcium stearate; flame retardants such as halogen flame retardants, phosphorus flame retardants, nitrogen flame retardants, silicon flame retardants, and flame retardant aids Heavy metal deactivators; lubricants; dyes; antistatic agents; antifogging agents; nucleating agents other than metal salts such as benzylidene sorbitol; antibacterial agents, antifungal agents, etc. It is.

  Examples of the phenolic antioxidant include 2,6-ditert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, distearyl (3,5-ditert-butyl-4). -Hydroxybenzyl) phosphonate, 1,6-hexamethylenebis [(3,5-ditert-butyl-4-hydroxyphenyl) propionic acid amide], 4,4'-thiobis (6-tert-butyl-m-cresol ), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 4,4′-butylidenebis (6-tert-butyl) -M-cresol), 2,2'-ethylidenebis (4,6-ditert-butylphenol), 2,2'-ethylidenebis (4-secondarybutyl-6-tert-butylphenol), 1 , 1,3-Tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanate Nurate, 1,3,5-tris (3,5-ditert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (3,5-ditert-butyl-4-hydroxybenzyl)- 2,4,6-trimethylbenzene, 2-tert-butyl-4-methyl-6- (2-acryloyloxy-3-tert-butyl-5-methylbenzyl) phenol, stearyl (3,5-ditert-butyl) -4-hydroxyphenyl) propionate, thiodiethylene glycol bis [(3,5-ditert-butyl-4-hydroxyphenyl) propionate], 1,6-hexamethylene bis [(3 5-di-tert-butyl-4-hydroxyphenyl) propionate], bis [3,3-bis (4-hydroxy-3-tert-butylphenyl) butyric acid] glycol ester, bis [2-tert-butyl-4 -Methyl-6- (2-hydroxy-3-tert-butyl-5-methylbenzyl) phenyl] terephthalate, 1,3,5-tris [(3,5-ditert-butyl-4-hydroxyphenyl) propionyloxy Ethyl] isocyanurate, tetrakis [methyl 3- (3,5-ditert-butyl-4-hydroxyphenyl) propionate] methane, 3,9-bis [1,1-dimethyl-2-{(3-tertiary Butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, Ethylene glycol bis [(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate], vitamin E, and the like, preferably 0.001 to 10 parts by weight with respect to 100 parts by weight of the crystalline resin, More preferably, 0.05 to 5 parts by weight are used.

  Examples of the phosphorus antioxidant include trisnonylphenyl phosphite, tris (2,4-ditert-butylphenyl) phosphite, tris [2-tert-butyl-4- (3-tert-butyl-4). -Hydroxy-5-methylphenylthio) -5-methylphenyl] phosphite, tridecyl phosphite, octyl diphenyl phosphite, di (decyl) monophenyl phosphite, di (tridecyl) pentaerythritol diphosphite, di (nonyl) Phenyl) pentaerythritol diphosphite, bis (2,4-ditert-butylphenyl) pentaerythritol diphosphite, bis (2,6-ditert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis ( 2,4,6-tritert-butylphenyl) pentaerythritol di Sulphite, bis (2,4-dicumylphenyl) pentaerythritol diphosphite, tetra (tridecyl) isopropylidenediphenol diphosphite, tetra (tridecyl) -4,4'-n-butylidenebis (2-tert-butyl- 5-methylphenol) diphosphite, hexa (tridecyl) -1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butanetriphosphite, tetrakis (2,4-ditert-butylphenyl) ) Biphenylene diphosphonite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2,2'-methylenebis (4,6-tert-butylphenyl) -2-ethylhexyl phosphite 2,2'-methylenebis (4,6-tert-butylphenyl) -octadeci Phosphite, 2,2′-ethylidenebis (4,6-ditert-butylphenyl) fluorophosphite, tris (2-[(2,4,8,10-tetrakis tert-butyldibenzo [d, f] [ 1,3,2] dioxaphosphin-6-yl) oxy] ethyl) amine, 2-ethyl-2-butylpropylene glycol and 2,4,6-tritert-butylphenol phosphite.

  Examples of the thioether antioxidant include dialkylthiodipropionates such as dilauryl thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate, and pentaerythritol tetra (β-dodecyl mercaptopropionate). And β-alkyl mercaptopropionic esters of polyols.

  Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 5,5′-methylenebis (2-hydroxy-4-methoxybenzophenone), and the like. 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-ditert-butylphenyl) -5-chlorobenzotriazole 2- (2′-hydroxy-3′-tert-butyl-5′-methylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-dicumylphenyl) benzotriazole, 2,2′-methylenebis (4-tertiary 2- (2′-hydroxyphenyl) benzotriazoles such as octyl-6-benzotriazolyl) phenol, 2- (2′-hydroxy-3′-tert-butyl-5′-carboxyphenyl) benzotriazole; phenyl Salicylate, resorcinol monobenzoate, 2,4-ditert-butylphenyl-3,5-ditert-butyl-4-hydroxybenzoate, 2,4-ditert-amylphenyl-3,5-ditert-butyl-4 -Benzoates such as hydroxybenzoate and hexadecyl-3,5-ditert-butyl-4-hydroxybenzoate; substitution of 2-ethyl-2'-ethoxyoxanilide, 2-ethoxy-4'-dodecyloxanilide and the like Oxanilides; ethyl-α-cyano-β, β-diphenyl acrylate, methyl-2-cyano-3-methyl-3 Cyanoacrylates such as (p-methoxyphenyl) acrylate; 2- (2-hydroxy-4-octoxyphenyl) -4,6-bis (2,4-ditert-butylphenyl) -s-triazine, 2- (2-hydroxy-4-methoxyphenyl) -4,6-diphenyl-s-triazine, 2- (2-hydroxy-4-propoxy-5-methylphenyl) -4,6-bis (2,4-diter And triaryltriazines such as tributylphenyl) -s-triazine.

  Examples of the hindered amine light stabilizer include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2, 2,6,6-tetramethyl-4-piperidylbenzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl ) Sebacate, tetrakis (2,2,6,6-tetramethyl-4-piperidylbutanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidylbutanetetracarboxylate, bis (2, 2,6,6-tetramethyl-4-piperidyl) di (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2, , 6,6-pentamethyl-4-piperidyl) .di (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2 -Butyl-2- (3,5-ditert-butyl-4-hydroxybenzyl) malonate, 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol / diethyl succinate Condensate, 1,6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / dibromoethane polycondensate, 1,6-bis (2,2,6,6-tetramethyl- 4-piperidylamino) hexane / 2,4-dichloro-6-morpholino-s-triazine polycondensate, 1,6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / 2 4- Chloro-6-tert-octylamino-s-triazine polycondensate, 1,5,8,12-tetrakis [2,4-bis (N-butyl-N- (2,2,6,6-tetramethyl- 4-piperidyl) amino) -s-triazin-6-yl] -1,5,8,12-tetraazadodecane, 1,5,8,12-tetrakis [2,4-bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -s-triazin-6-yl] -1,5,8,12-tetraazadodecane, 1,6,11-tris [2 , 4-Bis (N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl) amino) -s-triazin-6-ylaminoundecane, 1,6,11-tris [2, 4-Bis (N-butyl-N- (1,2,2,6,6-pentamethyl And hindered amine compounds such as -4-piperidyl) amino) -s-triazin-6-ylaminoundecane.

  Examples of the flame retardant include halogen flame retardants such as decabromodiphenyl ether and tetrabromobisphenol A, condensation of polyhydric phenols such as triphenyl phosphate, resorcinol and bisphenol A, and monohydric phenols such as phenol and 2,6-xylenol. Phosphoric acid esters; inorganic phosphorus compounds such as red phosphorus and melamine phosphate; nitrogen-containing flame retardants such as melamine cyanurate; inorganic flame retardants such as magnesium hydroxide and aluminum hydroxide; flame retardant aids such as antimony oxide and zirconium oxide Agent: An anti-drip agent such as polytetrafluoroethylene is used.

  Examples of the heavy metal deactivator include 2-hydroxybenzamide-N-1H-1,2,4-triazol-3-yl and dodecanedioic acid bis [2- (2-hydroxybenzoyl) hydrazide]. Can be mentioned.

  Examples of the lubricant include amides such as ethylene bisstearylamide and erucic acid amide, waxes, and fatty acid metal salts such as sodium stearate.

  Other additives may be added in advance in a polyolefin resin solution or an organic acid metal salt solution according to their solubility, or separately dissolved in a solvent to obtain three or more types of solutions, followed by removal. A solvent may be used.

  The polyolefin resin composition using the nucleating agent of the present invention can be used for various applications such as building materials, agricultural materials, automobile parts, packaging materials, sundries, toys, home appliances, and medical instruments. In particular, since it has a high degree of transparency, it can be suitably used for films, sheets, containers, and medical uses such as infusion bags, syringes, and drug-filled syringes, and films for a wide range of uses.

  Hereinafter, the present invention will be described in detail by way of examples. However, the present invention is not limited by the following examples.

(Example 1-1, Comparative example 1-1)
100 mg of an organic acid metal salt (described in Table 1) was dissolved in 20 g of n-butanol at room temperature, 95 g of xylene was added, and the mixture was uniformly irradiated with ultrasonic waves. The mixture was heated to 116 ° C. with stirring in a nitrogen atmosphere, and 10 mg of isotactic polypropylene (weight average molecular weight 300,000, Mw / Mn = 4.7, stereoregularity [mmmm] = 97%) was added and dissolved. While cooling vigorously with an ice bath, the precipitated resin was filtered off and dried under reduced pressure at 40 ° C. to obtain 9.9 mg of resin powder. The obtained resin powder was confirmed to contain 0.1% by weight of organic acid metal salt from the analysis result of phosphorus content. Moreover, the particle diameter of the nucleating agent in the obtained resin powder was determined by X-ray diffraction. Further, the obtained powder was pressed at 230 ° C. for 1 minute to obtain a film having a thickness of 100 μm. The obtained film is crystallized isothermally at various temperatures and observed using an optical microscope (Olympus), and the nucleation rate I is determined by the rate of increase in the number of crystals per unit volume (1 mm ³ ) per unit time (1 second). It was determined. Straight lines when plotted against 1 / [Delta] T the log I as shown in FIG. 1, a log I ₀ the ordinate intercept in 1 / [Delta] T = 0, a nucleating agent concentration C _NA and the ratio I between I _{0 0} / the C _NA was evaluated as a nucleating performance. In addition, using a differential scanning calorimeter (Perkin Elmer: Diamond DSC), the temperature was raised from room temperature to 230 ° C. at 50 ° C./minute, held for 5 minutes, and then cooled at 10 ° C./minute. It was measured as the crystallization temperature Tc of the resin composition. The higher the crystallization temperature, the better the molding cycle. The results are shown in Table 1.

(Comparative Example 1-2)
0.3 g of organic acid metal salt (described in Table 1) was dispersed by irradiating 100 g of xylene with ultrasonic waves, and isotactic polypropylene (weight average molecular weight 300,000, Mw / Mn = 4.7, stereoregularity at 120 ° C. [mmmm] = 97%) 300 mg was added and dissolved. While cooling vigorously with an ice bath, the precipitated resin was filtered off and dried under reduced pressure at 40 ° C. to obtain 299 mg of resin powder. The obtained resin powder was confirmed to contain 0.1% by weight of organic acid metal salt from the analysis result of phosphorus content. The obtained powder was pressed at 230 ° C. for 1 minute to obtain a film having a thickness of 100 μm. The particle size of the organic acid metal salt irradiated with ultrasonic waves in xylene was measured, and the other items were evaluated in the same manner as in Example 1-1. The results are shown in Table 1.

(Comparative Example 1-3)
Isotactic polypropylene (weight average molecular weight 300,000, Mw / Mn = 4.7, stereoregularity [mmmm] = 97%) 100 parts by weight calcium stearate 0.05 parts by weight tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyloxymethyl] methane 0.1 part by weight, tris (2,4-di-tert-butylphenyl) phosphite 0.1 part by weight and organic acid metal salt (Compound No. .1) 0.1 part by weight (the same blending amount as in Example 1-1) was blended and extruded and kneaded at 240 ° C. to obtain pellets. 13 mg of the obtained pellets were pressed at 230 ° C. for 1 minute to obtain a film having a thickness of 100 μm. Evaluation was performed in the same manner as in Example 1-1. The results are shown in Table 1.

  About Example 1-1 and Comparative Example 1-2, the transparency was compared by haze. The results are shown in Table 2.

From Example 1-1 and Comparative Example 1-2 in Table 1, the nucleating agent of the present invention has a nucleation effect of 10 times or more at the same addition amount as compared with the conventional nucleating agent, resulting in high crystals. The nucleating agent having a high I _{0 according} to the present invention from Example 2-1 and Comparative Example 2-2 in Table 2 dispersed the powder of the organic acid metal salt in the polyolefin resin composition. It is clear that the transparency is excellent compared with the conventional polyolefin resin composition, and the nucleating agent of the present invention is an excellent nucleating agent. Further, in Table 1, it is clear from Comparative Example 1-3 that dispersion by melt kneading shows only the same effect as Comparative Example 1-2, and the method of the present invention remarkably exhibits the effect of the nucleating agent. It is clear that this is an excellent technique. In addition, it is estimated that the variation in I ₀ without the addition of the nucleating agent was greatly influenced by the nucleation effect due to a small amount of impurities such as catalyst residues.

FIG. 1 is a plot of the common logarithm of nucleation rate I against 1 / ΔT.

Claims (3)

A polyolefin resin and an organic acid metal salt represented by the following general formula (I) are dissolved by heating in a mixed solvent of an alcohol solvent and an aromatic solvent, and then cooled to contain the organic resin metal salt. A method for producing a nucleating agent having a number average particle diameter (a) for crystallization of polyolefin resin of 0.1 μm or less.

(Wherein R ₁ is an alkyl group having 4 to 8 carbon atoms, R ₂ is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, R ₃ is an alkylidene group having 1 to 4 carbon atoms, and A is (n + x ) A valent metal, n represents an integer of 1 to 3, and x represents an integer of 0 to 2.) The process according to claim 1, wherein said alcohol solvent is butanol. The production method according to claim 1 or 2, wherein 10 to 500 parts by weight of the alcohol solvent and 5 to 3000 parts by weight of the aromatic solvent are used with respect to 1 part by weight of the organic acid metal salt.

Images