JP2005068249A - Method for producing magnetically-oriented crystalline polymer composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a crystalline polymer material excellent in stiffness and transparency by orienting a polymer composition in which a crystal nucleating agent is added in a given orientation. <P>SOLUTION: A method for producing a crystalline polymer composition that is oriented in a given orientation comprises adding a crystal nucleating agent that is an organic phosphoric acid metal salt represented by general formula (I) to a crystalline polymer material and applying a magnetic field to the crystalline polymer material that is in the molten state to solidify the same. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a method for producing a crystalline polymer composition oriented in a predetermined orientation.

  Until now, a crystalline magnetic composition obtained by adding a crystal nucleating agent to a polymer material is subjected to a nucleating action (epitaxy) from an oriented crystal nucleating agent by applying a predetermined magnetic field while performing heat treatment. It is known that the crystalline polymer chain is crystallized with anisotropy by the growth) to obtain a crystalline polymer composition oriented in a predetermined direction.

  In Patent Document 1 below, a crystalline magnetic composition obtained by adding a crystal nucleating agent to a polymer material is applied with a predetermined magnetic field while being heat-treated, and oriented in a predetermined orientation. A method for producing a crystalline polymer material is disclosed. However, a crystalline polymer material made of a crystalline polymer composition obtained by adding a crystal nucleating agent that induces β crystals as a crystal nucleating agent has a problem that it lacks crystallinity and heat resistance and lacks practicality. there were. In addition, the crystalline polymer material made of a crystalline polymer composition obtained by adding a crystal nucleating agent that induces α crystals has a poor nucleating ability of the crystal nucleating agent, and even if a predetermined magnetic field is applied, There is a problem that the degree of orientation of the crystalline polymer material does not sufficiently increase because the crystallinity of the crystalline polymer does not sufficiently increase.

Japanese Patent Laid-Open No. 2001-253962

  The problem to be solved is that, as described above, even if an attempt is made to orient the crystals of the crystalline polymer composition in a predetermined orientation by applying a magnetic field, the degree of orientation does not increase sufficiently, and rigidity and transparency This means that a crystalline polymer material excellent in physical properties such as the above has not been obtained so far.

  Accordingly, an object of the present invention is to provide a crystalline polymer material having excellent rigidity and transparency by orienting a polymer composition to which a crystal nucleating agent has been added in a predetermined orientation.

  As a result of intensive studies, the inventors of the present invention use an organophosphate metal salt as a crystal nucleating agent, thereby controlling the crystal orientation when a magnetic field is applied, and a crystalline polymer composition having a high degree of orientation. It was found that a product was obtained.

  That is, in the present invention, a crystalline nucleating agent, which is an organophosphate metal salt represented by the following general formula (I), is added to a crystalline polymer material, and a magnetic field is applied while the crystalline polymer material is melted. Thus, the present invention provides a method for producing a crystalline polymer composition oriented in a predetermined orientation, which is characterized by solidifying them.

  The crystalline polymer composition oriented in a predetermined orientation obtained by the production method of the present invention includes a crystalline polymer composition to which a conventional crystal nucleating agent is added and a crystalline polymer composition to which no crystal nucleating agent is added. The orientation of crystals is controlled by the product, and physical properties such as rigidity and transparency of the obtained crystalline polymer composition are improved.

  Hereinafter, a method for producing a crystalline polymer composition oriented in a predetermined orientation according to the present invention will be described in detail based on preferred embodiments thereof.

  In the production method of the present invention, the crystalline polymer composition oriented in a predetermined orientation is 0.005 to 5 parts by mass, preferably 0.03 to 3 parts by mass of the crystal nucleating agent in 100 parts by mass of the crystalline polymer material. After part addition and kneading at 180 to 300 ° C., these were molded at 180 to 300 ° C., and the crystalline polymer material was melted at 180 to 300 ° C. in a magnetic field of 1 to 20 Tesla (T). It is manufactured by holding in a state for 10 to 120 minutes (for example, 60 minutes), cooling while applying a magnetic field, and crystallizing.

  For the kneading, ordinary kneading equipment can be used, and the kneading equipment is not particularly limited as long as the resin composition can be mass-produced economically. Continuous single screw extruder such as screw extruder, twin screw extruder, continuous twin screw extruder, Henschel mixer, flash mixer, continuous paddle mixer, blade type kneader, continuous kneader, pulverizing mixer, SC processor, plast mill , KRC kneader, vacuum kneader, pressure kneader and the like.

  Examples of the molding include blow molding, calender molding, press molding, injection molding, and extrusion molding. In particular, it is preferable to use a method that allows molding while applying a magnetic field under melting conditions.

  Examples of the crystalline polymer material used in the present invention include low density polyethylene, linear low density polyethylene, high density polyethylene, isotactic polypropylene (iPP), syndiotactic polypropylene, and hemiisotactic polypropylene. , Α-olefin polymers such as polybutene-1, poly-3-methyl-1-butene, poly-3-methyl-1-pentene, poly-4-methyl-1-pentene, ethylene / propylene block or random copolymer Polyolefin polymers such as α-olefin copolymers such as polymers; Thermoplastic polymers such as polyethylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate and polycarbonate; Polysulfide polymers such as polyphenylene sulfide; Polycaprolactone, etc. A polylactic acid polymer such as: a linear polyamide polymer such as polyhexamethylene adipamide; a crystalline polystyrene polymer such as syndiotactic polystyrene;

  Among the crystalline polymer materials, polyolefin polymers that have a remarkable effect of using the crystal nucleating agent are preferable, and isotactic polypropylene is particularly preferable.

  In the present invention, an organic phosphate metal salt represented by the above general formula (I) is used as the crystal nucleating agent.

In the general formula (I), examples of the alkyl group having 1 to 4 carbon atoms represented by R ₁ include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl and tert-butyl. Examples of the alkyl group having 1 to 12 carbon atoms represented by ₂ and R ₃ include methyl, ethyl, propyl, butyl, sec-butyl, tert-butyl, amyl, tert-amyl, hexyl, heptyl, octyl, isooctyl, Tertiary octyl, 2-ethylhexyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tertiary dodecyl and the like. Examples of the alkali metal represented by M include lithium, sodium, potassium and the like. Examples of the alkaline earth metal represented include magnesium, calcium, strontium, barium and the like.

  Specific examples of the organophosphate metal salt represented by the general formula (I) include the following compound No. 1-No. 12 is mentioned. However, this invention is not limited at all by the following exemplary compounds.

In the present invention, the organophosphate metal salt is preferably a compound in which R ₁ is hydrogen, R ₂ and R ₃ are tert-butyl groups, and M is an alkali metal or hydroxyaluminum. . 1, no. 2 and no. 7 is preferred.

The organophosphate metal salt represented by the above general formula (I) used in the present invention is, for example, reacted with phosphorous trichloride and a 2,2′-methylenebisphenol derivative and then hydrolyzed to phosphoric acid. It can be produced by forming an ester and then reacting with a metal hydroxide such as sodium hydroxide. Next, after filtering and drying the obtained organophosphate metal salt, it can be pulverized if necessary and used as a crystal nucleating agent.

The addition amount of the organophosphate metal salt represented by the general formula (I) is preferably 0.005 to 5 parts by mass and more preferably 0 to 100 parts by mass of the crystalline polymer material. 0.01-3 parts by mass, most preferably 0.03-3 parts by mass. When the addition amount is less than 0.005 parts by mass, the sufficient addition effect may not be exhibited. When the addition amount exceeds 5 parts by mass, the addition effect cannot be improved and the cost is increased. It is not preferable because it may affect the physical properties of the resulting polymer product.

  In the present invention, the crystalline polymer composition may further contain an aliphatic organic acid metal salt, and a plurality of aliphatic organic acid metal salts may be used in combination.

  The aliphatic organic acid metal salt is a compound having a bond between a carboxylic acid residue of an aliphatic organic acid and a metal, and not all organic acid residues that can be bonded to a metal atom are bonded. Different organic acid residues may be bonded to the metal atom, or crystal water may be contained in the molecular structure. As the aliphatic organic acid metal salt, those represented by the above general formula (II) or (III) are preferable because they have a very small influence on the physical properties of the crystalline polymer material and are easily available.

  In the general formulas (II) and (III), examples of the aliphatic organic acid having 1 to 30 carbon atoms for deriving R include acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, caproic acid, caprylic acid, 2 -Ethylhexanoic acid, pelargonic acid, capric acid, neodecanoic acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, Serotic acid, montanic acid, melissic acid, succinic acid, lindelic acid, tuzuic acid, palmitoleic acid, petrothelic acid, oleic acid, elaidic acid, vaccenic acid, linoleic acid, linoleic acid, γ-linolenic acid, linolenic acid, ricinol Examples include acid, 12-hydroxystearic acid, naphthenic acid, and abietic acid.

  The aliphatic organic acid metal salt, which is solid at 50 ° C., is mixed in advance with the organophosphate metal salt that is a crystal nucleating agent to form a crystal nucleating agent composition, and then added to the crystalline polymer material In this case, it is preferable because particles with the organophosphate metal salt are easily formed and the resulting crystal nucleating agent composition particles are difficult to block.

  In addition, when the above-mentioned aliphatic organic acid metal salt is a fine powdery powder using a pulverizer, a filter, a sieve or the like, the uniformity of the crystalline polymer composition is improved and obtained. This is preferable because the transparency and rigidity of the crystalline polymer composition oriented in a predetermined orientation are increased.

  The aliphatic organic acid metal salt functions as a catalyst deactivator or a dispersant.

  Specific examples of the aliphatic organic acid metal salt represented by the general formula (II) include the following compound No. 13-No. 23. However, this invention is not limited at all by the following exemplary compounds.

  Specific examples of the aliphatic organic acid metal salt represented by the general formula (III) include the following compound No. 24-No. 25. However, this invention is not limited at all by the following exemplary compounds.

  Among the aliphatic organic acid metal salts represented by the general formula (II) or (III), the compound No. 14, no. 16 and no. 20 is preferred.

  The addition amount of the aliphatic organic acid metal salt is preferably 0 to 5 parts by mass, more preferably 0.00025 to 2.5 parts by mass with respect to 100 parts by mass of the crystalline polymer material. Moreover, the addition amount of the aliphatic organic acid metal salt is preferably 0 to 100 parts by mass, more preferably 5 to 100 parts by mass with respect to 100 parts by mass of the organophosphate metal salt represented by the general formula (I). 50 parts by mass.

  In the present invention, if necessary, the crystalline polymer composition further includes an antistatic agent comprising a cationic surfactant, an anionic surfactant, a nonionic surfactant, an amphoteric surfactant, and the like; Flame retardants such as halogen compounds, phosphate ester compounds, phosphate amide compounds, melamine compounds, melamine salt compounds of polyphosphoric acid, fluororesins or metal oxides; hydrocarbons, fatty acids, aliphatic alcohols, Aliphatic ester-based, aliphatic amide-based or metal soap-based lubricants; heavy metal deactivators; hydrotalcites; alkyl alcohols such as lauryl alcohol and stearyl alcohol; organic carboxylic acids; colorants such as dye pigments; Processing aids: fumed silica, fine silica, silica, diatomaceous earth, clay, kaolin, silica gel Silicate additives such as calcium silicate, sericite, kaolinite, flint, feldspar powder, aragonite, attapulgite, talc, mica, minnesotite, pyrophyllite; fillers such as calcium carbonate; pigments; dyes; Antibacterial agents and the like can be used.

  The crystalline synthetic resin composition may include hindered amine light stabilizers (HALS), ultraviolet absorbers, phosphorus-based, phenol-based, sulfur-based antioxidants, and aliphatic monocarboxylic acid alkalis as necessary. Addition of well-known commonly used additives such as metal salts or alkaline earth metal salts can be added to further improve oxidation stability and light stability.

  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 Bis (1-octoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4 Butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, bis (2,2 6,6-tetramethyl-4-piperidyl) bis (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) bis (Tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2-butyl-2- (3,5-ditertiary Butyl-4-hydroxybenzyl) malonate, 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol / diethyl succinate polycondensate, 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- -Morpholino-s-triazine polycondensate, 1,6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-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-triazine-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-triazine -6-ylamino] undecane, 1,6,11-tris [2,4-bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino-s-triazine- 6-ylamino] undecane, 3,9-bis [1,1-dimethyl-2- [tris (2,2,6,6-tetramethyl-4-piperidyloxycarbonyloxy) butylcarbonyloxy] ethyl] -2, 4,8,10-tetraoxaspiro [5.5] undecane, 3,9-bis [1,1-dimethyl-2- [tris (1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl] Oxy) butylcarbonyloxy] ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane and the like.

  Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 5,5′-methylenebis (2-hydroxy-4-methoxybenzophenone). 2-hydroxybenzophenones such as 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-3, 5-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3,5 -Dicumylphenyl) benzotriazole, 2,2'-methylenebis (4-th Octyl-6-benzotriazolylphenol), polyethylene glycol ester of 2- (2-hydroxy-3-tert-butyl-5-carboxyphenyl) benzotriazole, 2- [2-hydroxy-3- (2-acryloyloxy) Ethyl) -5-methylphenyl] benzotriazole, 2- [2-hydroxy-3- (2-methacryloyloxyethyl) -5-tert-butylphenyl] benzotriazole, 2- [2-hydroxy-3- (2- Methacryloyloxyethyl) -5-tert-octylphenyl] benzotriazole, 2- [2-hydroxy-3- (2-methacryloyloxyethyl) -5-tert-butylphenyl] -5-chlorobenzotriazole, 2- [2 -Hydroxy-5- (2-methacryloyloxyethyl) phenyl] benzene Zotriazole, 2- [2-hydroxy-3-tert-butyl-5- (2-methacryloyloxyethyl) phenyl] benzotriazole, 2- [2-hydroxy-3-tert-amyl-5- (2-methacryloyloxy) Ethyl) phenyl] benzotriazole, 2- [2-hydroxy-3-tert-butyl-5- (3-methacryloyloxypropyl) phenyl] -5-chlorobenzotriazole, 2- [2-hydroxy-4- (2- Methacryloyloxymethyl) phenyl] benzotriazole, 2- [2-hydroxy-4- (3-methacryloyloxy-2-hydroxypropyl) phenyl] benzotriazole, 2- [2-hydroxy-4- (3-methacryloyloxypropyl) 2- (2-hydroxypheny) such as phenyl] benzotriazole B) benzotriazoles; 2- (2-hydroxy-4-methoxyphenyl) -4,6-diphenyl-1,3,5-triazine, 2- (2-hydroxy-4-hexyloxyphenyl) -4,6 -Diphenyl-1,3,5-triazine, 2- (2-hydroxy-4-octoxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [ 2-hydroxy-4- (3-C12-13 mixed alkoxy-2-hydroxypropoxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2- Hydroxy-4- (2-acryloyloxyethoxy) phenyl] -4,6-bis (4-methylphenyl) -1,3,5-triazine, 2- (2,4-dihydroxy-3-allylphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4,6-tris (2-hydroxy-3-methyl-4-hexyloxyphenyl) -1,3 2- (2-hydroxyphenyl) -4,6-diaryl-1,3,5-triazines such as 5-triazine; phenyl salicylate, resorcinol monobenzoate, 2,4-ditert-butylphenyl-3,5- Di-tert-butyl-4-hydroxybenzoate, octyl (3,5-di-tert-butyl-4-hydroxy) benzoate, dodecyl (3,5-di-tert-butyl-4-hydroxy) benzoate, tetradecyl (3,5- Ditert-butyl-4-hydroxy) benzoate, hexadecyl (3,5-ditert-butyl-4-hydroxy) benzoate, octadecyl (3,5-ditert Benzoates such as butyl-4-hydroxy) benzoate, behenyl (3,5-ditert-butyl-4-hydroxy) benzoate; 2-ethyl-2′-ethoxyoxanilide, 2-ethoxy-4′-dodecyloxy Substituted oxanilides such as zanilides; cyanoacrylates such as ethyl-α-cyano-β, β-diphenyl acrylate and methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate; various metal salts Alternatively, metal chelates, particularly nickel or chromium salts or chelates may be mentioned.

  Examples of the phosphorus antioxidant include triphenyl phosphite, tris (2,4-ditertiarybutylphenyl) phosphite, tris (2,5-ditertiarybutylphenyl) phosphite, and tris (nonylphenyl). ) Phosphite, tris (dinonylphenyl) phosphite, tris (mono, dimixed nonylphenyl) phosphite, diphenyl acid phosphite, 2,2'-methylenebis (4,6-ditert-butylphenyl) octyl phosphite , Diphenyldecyl phosphite, diphenyloctyl phosphite, di (nonylphenyl) pentaerythritol diphosphite, phenyl diisodecyl phosphite, tributyl phosphite, tris (2-ethylhexyl) phosphite, tridecyl phosphite, trilauryl phosphite , Dibutyl acid phosphite, dilauryl acid phosphite, trilauryl trithiophosphite, bis (neopentylglycol) 1,4-cyclohexanedimethyldiphosphite, bis (2,4-ditert-butylphenyl) pentaerythritol di Phosphite, bis (2,5-ditert-butylphenyl) pentaerythritol diphosphite, bis (2,6-ditert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4-dic (Milphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tetra (C12-15 mixed alkyl) -4,4'-isopropylidene diphenylphosphite, bis [2,2'-methylenebis (4,6- Diamylphenyl)], isop Pyridene diphenyl phosphite, tetratridecyl 4,4'-butylidenebis (2-tert-butyl-5-methylphenol) diphosphite, hexa (tridecyl) 1,1,3-tris (2-methyl-5-tert Tributyl-4-hydroxyphenyl) butane triphosphite, tetrakis (2,4-ditert-butylphenyl) biphenylene diphosphonite, tris (2-[(2,4,7,9-tetrakis tert-butyldibenzo [ d, f] [1,3,2] dioxaphosphin-6-yl) oxy] ethyl) amine, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2 -Butyl-2-ethylpropanediol, 2,4,6-tritert-butylphenol monophosphite and the like.

  Examples of the phenol-based antioxidant include 2,6-ditert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, stearyl (3,5-ditert-butyl-4- Hydroxyphenyl) propionate, distearyl (3,5-ditert-butyl-4-hydroxybenzyl) phosphonate, tridecyl 3,5-ditert-butyl-4-hydroxybenzylthioacetate, thiodiethylenebis [(3,5 -Di-tert-butyl-4-hydroxyphenyl) propionate], 4,4'-thiobis (6-tert-butyl-m-cresol), 2-octylthio-4,6-di (3,5-di-tert-butyl) -4-hydroxyphenoxy) -s-triazine, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), bis [3,3-bi (4-hydroxy-3-tert-butylphenyl) butyric acid] glycol ester, 4,4′-butylidenebis (2,6-ditert-butylphenol), 4,4′-butylidenebis (6-tert-butyl- 3-methylphenol), 2,2′-ethylidenebis (4,6-ditert-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, bis [2-tert-butyl-4-methyl-6- (2-hydroxy-3-tert-butyl-5-methylbenzyl) phenyl] terephthalate, 1,3,5-tris (2,6-dimethyl-3-hydroxy -4-tert-butylbenzyl) isocyanurate, 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, 1,3,5-tris [(3,5-ditert-butyl-4-hydroxyphenyl) propionyloxyethyl] Isocyanurate, tetrakis [methylene-3- (3 ′, 5′-ditert-butyl-4′-hydroxyphenyl) propionate] methane, 2-tert-butyl-4-methyl-6- (2-acroyloxy- 3-tert-butyl-5-methylbenzyl) phenol, 3,9-bis [2- (3-tert-butyl-4-hydroxy-5-methylhydrocinnamoyloxy) -1,1-dimethylethyl] -2 , 4,8,10-tetraoxaspiro [5.5] undecane, triethylene glycol bis [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate] And the like.

  Examples of the sulfur-based antioxidant include dialkylthiodipropionates such as dilauryl, dimyristyl, myristyl stearyl, and distearyl esters of thiodipropionic acid, and polyols such as pentaerythritol tetra (β-dodecyl mercaptopropionate). [Beta] -alkyl mercaptopropionic acid esters.

  In addition, as a method of adding these additives used as necessary to the crystalline polymer material, a method of adding them separately from the crystal nucleating agent or the crystal nucleating agent composition; A method of mixing with the crystal nucleating agent composition and adding it; a granulating aid such as a binder, wax, solvent, silica, etc., which is used as necessary, with the crystal nucleating agent or the crystal nucleating agent composition. For example, after mixing in a desired ratio with an agent in advance, granulation is performed to form a one-pack composite additive, and the one-pack composite additive is added.

  The crystalline polymer composition oriented in a predetermined orientation obtained by the production method of the present invention includes, for example, automotive resin parts such as bumpers, dashboards, and instrument panels; household appliances such as refrigerators, washing machines, and vacuum cleaners. Resin parts for products; Household items such as tableware, buckets, bathing articles; Resin parts for connection such as connectors; Miscellaneous goods such as toys; Medical molded products such as medical packs, syringes, catheters, and medical tubes; Wall materials Building materials such as floor materials, window frames and wallpaper; wire covering materials; agricultural materials such as houses and tunnels; molded products including films and sheets such as food packaging materials such as wraps and trays;

  The crystalline polymer composition oriented in a predetermined orientation obtained by the production method of the present invention has an orientation degree determined by a method using the half-value width of the azimuth intensity distribution of the diffraction peak described in detail in the examples in the range of 0. It is preferably 3 or more, particularly 0.5 or more.

  Hereinafter, the present invention will be described in more detail with reference to examples, comparative examples, and evaluation examples. However, the present invention is not limited by the following examples.

[Examples 1 to 5 and Comparative Examples 1 to 5] Preparation of Film-like Crystalline Polymer Composition Sample iPP ([η] = 1.6, Mn = 60000, Mw = 303000, the same applies hereinafter) to 100 parts by mass A crystal nucleating agent and an aliphatic organic acid metal salt are blended in the proportions shown in [Table 1], and kneaded for 10 minutes at 280 ° C. and 80 rpm using a microkneading extruder (manufactured by Imoto Seisakusho). The pellet which consists of a conductive polymer composition was obtained. The obtained pellets were made into a film having a thickness of 100 μm over 5 minutes at 280 ° C. using a desktop test press (manufactured by Tester Sangyo Co., Ltd.). The obtained film was heated at 5 ° C./min in a magnetic field of 8 T by a self-made magnetic field heat treatment apparatus using a refrigerator-cooled superconducting magnet HF-10 (manufactured by Sumitomo Heavy Industries, Ltd.). After holding at 60 ° C. for 60 minutes, the temperature was lowered at 5 ° C./min to obtain a film-like crystalline polymer composition sample. About the obtained film-form crystalline polymer composition sample, the Haze value and dynamic viscoelasticity were measured. The haze value was measured according to JIS K 7105, and the dynamic viscoelasticity was measured as follows. These measurement results are shown in [Table 1] together with the melting point of the crystalline polymer composition.

(Measurement of dynamic viscoelasticity)
A specimen having a width of 5 mm and a length of 25 mm was cut out from the obtained film-like crystalline polymer composition sample, and the frequency was 110 Hz and the temperature was 110 K using a dynamic viscoelasticity measuring device DVE-V4 (manufactured by Rheology). For 15 minutes, the temperature was raised from 110 K to the melting point of the sample at 2 K / min, and E ′ (storage modulus) at 296 K was measured.

[Evaluation Example 1] Evaluation by Polarization Microscope To 100 parts by mass of iPP, ADK STAB NA-11 (Compound No. 2, particle size: 5 to 10 μm, manufactured by Asahi Denka Kogyo Co., Ltd.) or ADK STAB NA-11 UH (Compound No. 2, Particle size: 4 to 7 μm, 2 parts by mass of Asahi Denka Kogyo Co., Ltd.) is blended and crystallized by kneading for 10 minutes at 280 ° C. and 80 rpm using a microkneading extruder (manufactured by Imoto Seisakusho) Each functional polymer composition was obtained. Each of the crystalline polymer compositions in a state of being heated to a melting point or higher and melted under a condition of 45 ° with respect to the quadruple, crossed Nicols, color plate, and magnetic field was observed with a polarizing microscope. A polarizing micrograph of a crystalline polymer composition prepared using ADK STAB NA-11 is shown in FIG. 1 (a), and a polarizing micrograph of a crystalline polymer composition prepared using ADK STAB NA-11UH [ FIG. 1] (b) shows. [FIG. 1] As is clear from (a) and [FIG. 1] (b), in any crystalline polymer composition, the b-axis, which is the normal to the [010] plane of the crystal nucleating agent, is a magnetic field. It was confirmed that it was vertically oriented.

[Evaluation Example 2] Evaluation by wide-angle X-ray diffraction Compound No. 1 was added to 100 parts by mass of iPP. A film-like crystalline polymer composition sample A was obtained in the same manner as in the above example except that a pellet made of a crystalline polymer composition containing 2 parts by mass of 2 (Adeka Stub NA-11) was used. . Further, a film-like crystalline polymer composition sample B was obtained in the same manner as in the above example except that the pellet was used and the heat treatment was performed outside the magnetic field by the magnetic field inside / outside heat treatment apparatus. Also, a film-like crystalline polymer composition sample C was obtained in the same manner as in the above example except that pellets consisting only of iPP were used.
Using a wide-angle X-ray diffractometer M18XHF22 (manufactured by Mac Science), exposure was performed at 50 kV 90 mA for 1 hour, and diffraction intensity data was measured for each of the film-like crystalline polymer composition samples A to C. The analysis of the measurement result was performed according to the method of the literature (Polymer 42 (2001) 9627-9431).
The film-like crystalline polymer composition sample A obtained by heat treatment in a magnetic field has an azimuth intensity distribution on the [040] plane as shown in FIG. It was confirmed that the crystalline polymer was oriented in the directions of 90 ° and 270 °, that is, the magnetic field direction. On the other hand, the film-like crystalline polymer composition sample B obtained by heat treatment outside the magnetic field has a Laue photograph as shown in FIG. 2 (b), and the orientation of the crystalline polymer is It was not seen and showed random orientation. The film-like crystalline polymer composition sample C to which no crystal nucleating agent was added also showed no random orientation due to the magnetic field.

[Evaluation Example 3] Evaluation of degree of orientation Compound No. 1 was added to 100 parts by mass of iPP. Except that 1 part by mass, 2 parts by mass or 3 parts by mass of 2 (Adekastab NA-11) was blended, film-like crystalline polymer composition samples having different crystal nucleating agent addition amounts were obtained in the same manner as in the above Examples. Each was created. The degree of orientation was determined for each of the obtained film-like crystalline polymer composition samples. As a simple method for quantifying the degree of orientation of the crystal nucleating agent, a method using the half-value width of the azimuthal intensity distribution of the diffraction peak was adopted, and the value obtained by the following [Equation 1] was taken as the degree of orientation. The results are shown in FIG.

(Equation 1)
S = (180−hw ₀₄₀ ) / 180
(Where hw ₀₄₀ represents the full width at half maximum in the azimuth intensity distribution of the [040] plane of iPP.)

  As apparent from [Table 1] above, a film-like crystalline polymer composition sample to which an organophosphate metal salt represented by the above general formula (I) and optionally an aliphatic organic acid metal salt are added ( Examples 1 to 5) were obtained by adding α-nucleating agent di (t-butylbenzoic acid) aluminum or β-crystal nucleating agent 2,6-naphthylene di (cyclohexylamide) (Comparative Examples 1-2). As compared with the sample in which no crystal nucleating agent was added (Comparative Example 3), the Haze value was small and E ′ was large. Further, the magnetic field treatment (Example 1) had a smaller haze value and a larger E 'than the magnetic field treatment not performed (Comparative Example 4). That is, the crystalline polymer composition oriented in a predetermined orientation obtained by the production method of the present invention has an α crystal nucleating agent, a β crystal nucleating agent added, a crystal nucleating agent not added, or Compared to those without magnetic field treatment, the transparency and rigidity were high. When di (t-butylbenzoic acid) aluminum is used, the magnetic field treatment (Comparative Example 1) is sufficiently improved in rigidity compared to the one not subjected to the magnetic field treatment (Comparative Example 5). There wasn't.

  Further, as is clear from [FIG. 1] to [FIG. 4], the film-like crystalline polymer composition sample obtained by the production method of the present invention is obtained by the crystal nucleus in the crystalline polymer composition by a magnetic field. The agent was oriented in a certain direction, and as a result, the crystalline polymer material was oriented in a certain direction and had a high degree of orientation (Evaluation Examples 1 to 3).

  From the above results, according to the production method of the present invention, the crystalline polymer composition is magnetically added by adding the organophosphate metal salt represented by the above general formula (I) to the crystalline polymer material. It is clear that the orientation of crystals is controlled by this, and a crystalline polymer composition having high transparency and rigidity can be obtained.

FIG. 1 (a) shows compound No. 1 having a particle size of 5 to 10 μm in Evaluation Example 1. 2 shows a polarizing microscope photograph in a molten state of the crystalline polymer composition prepared using No. 2, and FIG. 2 shows a polarizing microscope photograph in a molten state of a crystalline polymer composition prepared using 2. 2A shows a Laue photograph of the film-like crystalline polymer composition sample A prepared in the magnetic field in Evaluation Example 2, and FIG. 2B is prepared in the evaluation example 2 outside the magnetic field. 2 shows a Laue photograph of the film-like crystalline polymer composition sample B. FIG. 3 shows the azimuthal intensity distribution of the [040] plane of iPP in the film-like crystalline polymer composition sample A prepared in the magnetic field in Evaluation Example 2. 4 shows the compound No. in the film-like crystalline polymer composition sample prepared in Evaluation Example 3. 2 shows the relationship between the blending amount of 2 and the degree of orientation of the [040] plane of iPP.

Claims (6)

A crystal nucleating agent, which is an organophosphate metal salt represented by the following general formula (I), is added to the crystalline polymer material, and the crystalline polymer material is solidified by applying a magnetic field in a molten state. A method for producing a crystalline polymer composition oriented in a predetermined orientation.
  2. The method for producing a crystalline polymer composition according to claim 1, wherein the crystalline polymer material is a polyolefin polymer.   The method for producing a crystalline polymer composition according to claim 2, wherein the polyolefin polymer is isotactic polypropylene. The crystalline polymer composition according to any one of claims 1 to 3, wherein an aliphatic organic acid metal salt represented by the following general formula (II) or (III) is further added to the crystalline polymer material. Production method.
  The amount of the organophosphate metal salt added to 100 parts by mass of the crystalline polymer material is 0.005 to 5 parts by mass, The production of the crystalline polymer composition according to any one of claims 1 to 4. Method.   The method for producing a crystalline polymer composition according to claim 4, wherein a mass ratio (the former: the latter) of the organophosphate metal salt to the aliphatic organic acid metal salt is 100: 0 to 100.