JP5229997B2 - Synthetic resin composition - Google Patents

Description

  The present invention relates to a synthetic resin composition, and more particularly to a synthetic resin composition having excellent crystallization temperature, heat resistance, molding processability, and the like.

  Generally, when molding is performed with synthetic resin alone, the heat resistance and impact resistance of the molded product are low.For example, when it is used as a packaging container, it may be deformed when hot water or a microwave oven is used. End up. Among synthetic resins, polyester resins (particularly lactic acid polymers) have the advantage of a high melting point of 140 to 180 ° C. and a high elastic modulus, such as automobile interior materials, electrical / electronic product housings, parts, etc. Although it is highly expected as a molding material and packaging material, it has a problem that the crystallization rate is extremely slow and the heat resistance of the molded product is poor.

  As a method of improving the heat resistance of a molded product, generally known is a method of cooling a molded product slowly over time in mold cooling during molding, or highly crystallizing a molded product by annealing after molding. It has been.

  Further, a method is known in which a crystal nucleating agent is added to a synthetic resin to promote crystallization of the synthetic resin and improve the heat resistance of the molded product.

For example, Patent Documents 1 to 6 below describe adding an additive such as a crystal nucleating agent to a lactic acid-based polymer. Specifically, Patent Document 1 discloses that trimesic acid tris (t-butylamide), 1,4-cyclohexanedicarboxylic acid dianilide, 2,6-naphthalenedicarboxylic acid dicyclohexylamide, N, N for polylactic acid resins. Amide compounds such as' -dibenzoyl-1,4-diaminocyclohexane and N, N'-dicyclohexanecarbonyl-1,5-diaminonaphthalene have been proposed. Patent Document 2 discloses that as a nucleating agent for aliphatic polyester, fine particles of inorganic compounds such as talc, boron nitride, calcium titanate, titanium oxide, silica, zinc oxide, calcium carbonate, sodium salt of saccharin, sodium benzoate. In addition, fine particles of organic compounds such as polybutylene terephthalate and polypropylene having a melting point higher than that of polylactic acid have been proposed. Furthermore, Patent Document 3 discloses a polycomplex capable of forming a stereocomplex composed mainly of polylactic acid composed of poly-L-lactic acid mainly composed of L-lactic acid and poly-D-lactic acid mainly composed of D-lactic acid. As crystal nucleating agents for lactic acid-based polymers, phosphate ester metal salts and hydrous magnesium silicate have been proposed. Furthermore, Patent Document 4 proposes adding an amidocarbonylphenol compound to polylactic acid. Furthermore, Patent Document 5 proposes that an aromatic urea compound is contained in polylactic acid capable of producing a stereocomplex crystal. Furthermore, Patent Document 6 proposes that polylactic acid contains a melamine compound salt.
Japanese Patent Laid-Open No. 10-87975 JP 2003-073533 A JP 2003-192894 A JP 2004-323742 A JP 2005-187630 A JP 2005-272679 A

  However, in the mold cooling of the molding process, the method of slowly cooling the molded product over time is not practical because it requires a long cooling process during the molding process. The method of highly crystallizing by annealing treatment has a drawback that it easily deforms with the crystallization of the molded product, and is insufficient as a method for improving heat resistance.

  In addition, the method of adding an additive such as a crystal nucleating agent to the lactic acid-based polymer described in Patent Documents 1 to 6 is not satisfactory for the effect of improving the crystallization temperature of the lactic acid-based polymer, and is a method for improving heat resistance. It was still insufficient.

  Accordingly, an object of the present invention is to solve the above-mentioned problems of the prior art, and to provide a synthetic resin composition having a high crystallization temperature and excellent heat resistance and molding processability.

  As a result of intensive studies to solve the above problems, the present inventors have found that the above object can be achieved by using a synthetic resin composition containing a compound having a specific sulfohydrazide structure. The present invention has been completed.

で表されるスルホヒドラジド構造の化合物０．０１〜１０質量部を含有してなることを特徴とするものである。 That is, the synthetic resin composition of the present invention has the following formula with respect to 100 parts by mass of the synthetic resin:

It contains 0.01 to 10 parts by mass of a compound having a sulfohydrazide structure represented by the formula:

  In the synthetic resin composition of the present invention, the synthetic resin is preferably a polyester resin, and particularly preferably a lactic acid-based polymer.

  According to the present invention, it is possible to provide a synthetic resin composition having a high crystallization temperature and excellent heat resistance and molding processability by blending a synthetic resin with a compound having a sulfohydrazide structure as a crystal nucleating agent. It has become possible.

The synthetic resin composition of the present invention will be described in detail below.
Examples of the synthetic resin used in the synthetic resin composition of the present invention include α-olefin polymers such as polypropylene, high density polyethylene, low density polyethylene, linear low density polyethylene, polybutene-1, and poly-3-methylpentene. Or ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-methyl acrylate copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-vinyl alcohol copolymer, ethylene -Polyolefins such as propylene copolymer and copolymers thereof, polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene, polyvinylidene fluoride, chlorinated rubber, vinyl chloride-vinyl acetate copolymer, vinyl chloride- Ethylene copolymer, salt Vinyl-vinylidene chloride copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-acrylic acid ester copolymer, vinyl chloride-maleic acid ester copolymer, vinyl chloride-cyclohexyl maleimide copolymer Halogen-containing resins such as petroleum resin, coumarone resin, polystyrene, polyvinyl acetate, acrylic resin, styrene and / or α-methylstyrene and other monomers (for example, maleic anhydride, phenylmaleimide, methyl methacrylate, butadiene) , Acrylonitrile, etc.) (for example, AS resin, ABS resin, MS resin, MBS resin, heat-resistant ABS resin, etc.), polymethyl methacrylate, polyvinyl alcohol, polyvinyl formal, polyvinyl butyral, polyethylene terephthalate and polybutylene te Polyester resins such as phthalate and polylactic acid, polyamide resins such as polyphenylene oxide, polycaprolactam and polyhexamethylene adipamide, polycarbonate, polycarbonate / ABS resin, branched polycarbonate, polyacetal, polyphenylene sulfide, polyurethane, triacetyl cellulose, cycloolefin, Thermosetting resins such as thermoplastic resins such as fiber resins and blends thereof, phenol resins, urea resins, melamine resins, epoxy resins, and unsaturated polyester resins can be given. Furthermore, elastomers such as isoprene rubber, butadiene rubber, acrylonitrile-butadiene copolymer rubber, and styrene-butadiene copolymer rubber may be used. Further, it may be polymerized by adding the ultraviolet absorbent of the present invention to a monomer having an ethylenically unsaturated bond. These synthetic resins may be used alone or in combination of two or more.

  Among these, as the synthetic resin in the synthetic resin composition of the present invention, polyester resins such as polymethyl methacrylate, polyvinyl alcohol, polyvinyl formal, polyvinyl butyral, polyethylene terephthalate and polybutylene terephthalate, and lactic acid-based polymers are preferably used. Preferably, a lactic acid polymer is used.

  Examples of the lactic acid-based polymer in the present invention include polylactic acid homopolymers, polylactic acid copolymers, and blend polymers of polylactic acid homopolymers and polylactic acid copolymers. Moreover, as long as the effect of this invention is not impaired, the blend polymer which mainly has a lactic acid-type polymer may be sufficient.

  The weight average molecular weight (Mw) of such a lactic acid-based polymer is usually 50,000 to 500,000, preferably 100,000 to 250,000 in terms of polystyrene by gel permeation chromatography analysis. When the weight average molecular weight is less than 50,000, it is difficult to obtain practically required physical properties, and when the weight average molecular weight exceeds 500,000, moldability may be easily deteriorated.

  The constituent molar ratio (L / D) of the L-lactic acid unit and the D-lactic acid unit in the lactic acid-based polymer is not particularly limited, and can be selected from the range of 100/0 to 0/100. However, in order to obtain a polylactic acid resin composition having a high melting point, in order to obtain a polylactic acid resin composition having an L-lactic acid unit or a D-lactic acid unit of 75 mol% or more and a higher melting point. It is preferable that 90 mol% or more of any one of L-lactic acid units and D-lactic acid units is contained.

  Furthermore, the lactic acid-based polymer in the present invention is preferably one that is copolymerized with a lactic acid monomer or lactide and another copolymerizable component. Examples of other components include dicarboxylic acids having two or more ester bond-forming functional groups, polyhydric alcohols, hydroxycarboxylic acids, lactone acids, and various polyesters, polyethers, polycarbonates, and the like comprising these as constituent components. It is done.

  Examples of the dicarboxylic acid include succinic acid, adipic acid, azelaic acid, sebacic acid, terephthalic acid, and isophthalic acid.

  Examples of the polyhydric alcohol include aromatic polyhydric alcohols such as those obtained by addition reaction of bisphenol with ethylene oxide, ethylene glycol, propylene glycol, butanediol, hexanediol, octanediol, glycerin, sorbitan, trimethylolpropane. And aliphatic polyhydric alcohols such as neopentyl glycol, ether glycols such as diethylene glycol, triethylene glycol, polyethylene glycol, and polypropylene glycol.

  Furthermore, examples of the hydroxycarboxylic acid include glycolic acid, hydroxybutyric acid, hydroxybutylcarboxylic acid, hydroxypentanoic acid, hydroxycaproic acid, and hydroxyheptanoic acid.

  Furthermore, examples of the lactone acid include glycolide, ε-caprolactone glycolide, ε-caprolactone, ε-propiolactone, δ-butyrolactone, β-butyrolactone, γ-butyrolactone, pivalolactone, and δ-valerolactone.

  The lactic acid-based polymer in the present invention is not particularly limited in the synthesis method, and can be synthesized by a conventionally known method, for example, by direct dehydration condensation from a lactic acid monomer or ring-opening polymerization of a lactic acid cyclic dimer lactide. can do.

  When performing direct dehydration condensation, any lactic acid of L-lactic acid, D-lactic acid, DL-lactic acid, and a mixture thereof may be used. Moreover, when performing ring-opening polymerization, you may use any lactide of L-lactide, D-lactide, DL-lactide, meso-lactide, and these mixtures.

  The catalyst used in the polymerization reaction for obtaining the lactic acid-based polymer is not particularly limited, but a known catalyst for lactic acid polymerization can be used. Examples of the catalyst include tin lactate, tin tartrate, dicaprylate, dilaurate, tin dipalmitate, tin distearate, tin dioleate, α-naphthoate, β-naphthoate, and octylate. Tin compounds such as powder tin, tin oxide, zinc dust, zinc halide, zinc oxide, organic zinc compounds, titanium compounds such as tetrapropyl titanate, zirconium compounds such as zirconium isopropoxide, antimony trioxide, etc. Examples thereof include antimony compounds, bismuth compounds such as bismuth (III) oxide, and aluminum compounds such as aluminum oxide and aluminum isopropoxide.

  Among these, a catalyst made of tin or a tin compound is particularly preferable from the viewpoint of activity. The amount of the catalyst used is, for example, about 0.001 to 5 parts by mass with respect to 100 parts by mass of lactide when ring-opening polymerization is performed.

  The polymerization reaction can be usually performed at 100 to 220 ° C. in the presence of the catalyst, although it varies depending on the type of the catalyst. For example, it is also preferable to perform the two-stage polymerization described in JP-A-7-247345.

  The blend polymer mainly composed of the lactic acid-based polymer includes, for example, a polylactic acid homopolymer and / or a polylactic acid copolymer, and an aliphatic polyester other than the lactic acid-based polymer (hereinafter simply referred to as “aliphatic polyester”) And a mixture obtained by mixing and melting. Blending the aliphatic polyester is preferable because flexibility and impact resistance can be imparted to the molded product. The mixing ratio in the blend polymer is usually about 10 to 100 parts by mass of the aliphatic polyester with respect to 100 parts by mass of the polylactic acid homopolymer and / or polylactic acid copolymer.

  The aliphatic polyester may be a single polymer or a composite of two or more polymers. Examples of the polymer include a polymer composed of an aliphatic carboxylic acid and an aliphatic alcohol, and an aliphatic hydroxycarboxylic acid polymer obtained by ring-opening polymerization of a cyclic anhydride such as ε-caprolactone. Examples of a method for obtaining these polymers include a direct polymerization method for directly polymerizing to obtain a high molecular weight product, and an indirect polymerization method for obtaining a high molecular weight product with a chain extender after polymerization to the extent of an oligomer. The aliphatic polyester may be a copolymer or a mixture with other resins as long as it is a polymer mainly composed of the aliphatic monomer component.

  The aliphatic polyester is preferably a polymer composed of an aliphatic dicarboxylic acid and an aliphatic diol. Examples of the aliphatic dicarboxylic acid include succinic acid, adipic acid, suberic acid, sebacic acid, dodecanoic acid, and anhydrides and derivatives thereof. Examples of the aliphatic diol include ethylene glycol and butanediol. , Glycol compounds such as hexanediol, octanediol and cyclohexanedimethanol, and derivatives thereof. The aliphatic dicarboxylic acid and the aliphatic diol are preferably monomers having 2 to 10 carbon atoms alkylene or cycloalkylene. The aliphatic polyester is preferably produced by polycondensation of monomer components selected from these aliphatic dicarboxylic acids and aliphatic diols. In addition, two or more of the aliphatic dicarboxylic acids and the aliphatic diols may be used.

  In addition, for the purpose of providing a branch in the polymer used as the aliphatic polyester for improving the melt viscosity, a trifunctional or higher polyfunctional carboxylic acid, alcohol or hydroxycarboxylic acid is used as a monomer component constituting the polymer. It doesn't matter. When these polyfunctional monomer components are used in a large amount, the resulting polymer has a cross-linked structure and may not be thermoplastic, or even a thermoplastic may produce a microgel partially having a highly cross-linked structure. . Therefore, these polyfunctional monomer components are used in such a small amount that they do not greatly affect the chemical and physical properties of the polymer. As the polyfunctional monomer component, malic acid, tartaric acid, citric acid, trimellitic acid, pyromellitic acid, pentaerythritol, trimethylolpropane, or the like can be used.

  Among the methods for producing the polymer used as the aliphatic polyester, the direct polymerization method selects a monomer component and obtains a high molecular weight product while removing water contained in the monomer component or generated during the polymerization. Is the method. In the indirect polymerization method, a monomer component is selected, polymerized to an oligomer level, and then a small amount of chain extender such as hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, etc. for the purpose of increasing molecular weight. This is a method of increasing the molecular weight using a diisocyanate compound. In addition to these methods, a method of obtaining an aliphatic polyester carbonate using a carbonate compound may be used.

  In the polylactic acid-based resin composition of the present invention, the lactic acid-based polymer may be blended with a general-purpose resin other than the lactic acid-based polymer, if necessary, for improving impact strength. As the general-purpose resin, an elastic resin such as an ethylene-propylene copolymer rubber or an ethylene-propylene-diene copolymer is preferable.

  The synthetic resin composition of the present invention contains a compound having a sulfohydrazide structure represented by the following general formula (1) or (2) as a crystal nucleating agent for the synthetic resin.

Examples of the optionally substituted alkyl group having 1 to 10 carbon atoms represented by A and R in the general formulas (1) and (2) include a methyl group, Ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, isobutyl group, amyl group, isoamyl group, tert-amyl group, hexyl group, 2-hexyl group, 3-hexyl group, heptyl Group, 2-heptyl group, 3-heptyl group, isoheptyl group, tertiary heptyl group, n-octyl group, isooctyl group, tertiary octyl group, 2-ethylhexyl group, nonyl group, isononyl group, dodecyl group and the like. . —CH ₂ — in the alkyl group may be substituted with —O—, —CO—, —COO— or —OCO—, and the hydrogen atom in the alkyl group is a halogen atom, alkenyl group, alkenyl It may be substituted with an oxy group, an alkanoyloxy group, an alkoxycarbonyl group, a nitrile group or a cyano group.

  Examples of the optionally substituted cycloalkyl group having 3 to 6 carbon atoms represented by A and R in the general formulas (1) and (2) include a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group. And a hydrogen atom in the saturated carbocycle is a halogen atom, an alkyl group, an alkoxy group, an alkenyl group, an alkenyloxy group, an alkoxyalkyl group, an alkanoyloxy group, an alkoxycarbonyl group, a nitrile group, or a cyano group. May be substituted.

  Examples of the optionally substituted aryl group having 6 to 20 carbon atoms represented by A and R in the general formulas (1) and (2) include a phenyl group, 3,4,5-trimethoxyphenyl. Group, 4-tert-butylphenyl group, biphenyl group, naphthyl group, anthracene group, phenanthrene group and the like, and the hydrogen atom in the aromatic ring is a halogen atom, alkyl group, alkoxy group, alkenyl group , An alkenyloxy group, an alkoxyalkyl group, an alkanoyloxy group, an alkoxycarbonyl group, a nitrile group or a cyano group.

  Examples of the alkylene group having 1 to 10 carbon atoms which may be substituted or branched and represented by A in the general formulas (1) and (2) include a methylene group, an ethylene group, and propylene. Group, methylethylene group, butylene group, 1-methylpropylene group, 2-methylpropylene group, 1,2-dimethylpropylene group, 1,3-dimethylpropylene group, 1-methylbutylene group, 2-methylbutylene group, 3 -Methylbutylene group, 4-methylbutylene group, 2,4-dimethylbutylene group, 1,3-dimethylbutylene group, pentylene group, hexylene group, heptylene group, octylene group and the like can be mentioned. The hydrogen atom in the alkylene group may be substituted with a halogen atom, an alkyl group, an alkoxy group, an alkenyl group, an alkenyloxy group, an alkoxyalkyl group, an alkanoyloxy group, an alkoxycarbonyl group, a nitrile group or a cyano group.

  Examples of the optionally substituted arylene group having 6 to 20 carbon atoms represented by A in the general formulas (1) and (2) include a 1,4-phenylene group, a 1,3-phenylene group, Examples include 1,5-naphthylene group, 2,6-naphthylene group, 2,6-phenalene group, 1.6-phenanthrene group, 2.7-phenanthrene group, 2,6-anthracene group. The hydrogen atom in the cycloalkylene group may be substituted with a halogen atom, alkyl group, alkoxy group, alkenyl group, alkenyloxy group, alkoxyalkyl group, alkanoyloxy group, alkoxycarbonyl group, nitrile group or cyano group. .

  Examples of the optionally substituted cycloalkylene group having 3 to 6 carbon atoms represented by A in the general formulas (1) and (2) include a 1,2-cyclopropylene group and 1,3-cyclohexane. Examples include a heptylene group and a trans-1,4-cyclohexylene group. The hydrogen atom in the cycloalkylene group may be substituted with a halogen atom, alkyl group, alkoxy group, alkenyl group, alkenyloxy group, alkoxyalkyl group, alkanoyloxy group, alkoxycarbonyl group, nitrile group or cyano group. .

  Specific examples of the compound having a sulfohydrazide structure represented by the above general formula (1) in the present invention include the following compound No. 1-No. 4 is mentioned. However, the present invention is not limited by the following compounds.

  In the synthetic resin composition of the present invention, the compound having a sulfohydrazide structure represented by the general formula (1) or (2) is 0.01 to 10 parts by mass, preferably 100 parts by mass of the synthetic resin. 0.05-5 mass parts, More preferably, 0.1-3 mass parts is mix | blended. When the amount is less than 0.01 part by mass, the effect of addition is insufficient, and when the amount is more than 10 parts by mass, a phenomenon such as ejection of the above compound on the surface of the synthetic resin composition may occur.

  Moreover, as long as it does not impair the effects of the present invention, conventionally known plasticizers, antioxidants, heat stabilizers, light stabilizers, ultraviolet absorbers, pigments, colorants, various fillers, charging Inhibitors, mold release agents, fragrances, lubricants, flame retardants, silicic inorganic additives, foaming agents, fillers, antibacterial agents, antifungal agents, and sulfos represented by the above general formula (1) or (2) You may mix | blend various additives, such as a crystal nucleating agent other than the compound of a hydrazide structure.

  In the synthetic resin composition of the present invention, the method of blending the compound of the sulfohydrazide structure represented by the general formula (1) or (2) with the synthetic resin is not particularly limited, and is conventionally known. It can be done by the method. For example, the synthetic resin powder or pellets and the additive may be mixed by dry blending, or a part of the additive may be preblended and then dry blended with the remaining components. After dry blending, for example, mixing may be performed using a mill roll, a Banbury mixer, a super mixer, or the like, and kneading may be performed using a single screw or twin screw extruder. This kneading is usually performed at a temperature of about 120 to 250 ° C. Moreover, after mixing in a desired ratio together with a granulating aid such as a binder, wax, solvent, silica, etc. in the polymerization step of the synthetic resin, and then granulating to make a one-pack composite additive, A method of adding the one-pack composite additive to the synthetic resin, a method of preparing a master batch containing the compound at a high concentration, and adding the master batch to the synthetic resin can be used.

  When molding the synthetic resin composition of the present invention, extrusion molding, injection molding, blow molding, vacuum molding, compression molding, etc. can be performed, and various molded products such as sheets, bars, bottles, containers, etc. can be easily formed. Can get to.

  Further, the synthetic resin composition of the present invention may be a fiber reinforced plastic by blending glass fibers, carbon fibers, and the like.

  EXAMPLES Hereinafter, although a manufacture example and an Example are given and this invention is demonstrated further more concretely, this invention is not restrict | limited at all by the following Examples. In addition, a manufacture example is a manufacturing method of the synthetic resin composition of this invention, and an Example shows evaluation of the synthetic resin composition of this invention.

[Production example]
A synthetic resin composition obtained by blending 1 part by mass of a test compound described in Table 1 below with 100 parts by mass of a lactic acid-based polymer (LACEA H-100; manufactured by Mitsui Chemicals, Inc.), 90 After drying in an oven at 3 ° C. for 3 hours, pellets were obtained by kneading at a cylinder temperature of 200 ° C. using a single-screw kneading extruder (manufactured by Toyo Seiki Seisakusho; Labo Plast Mill Micro). About the obtained pellet, the following evaluation was implemented after reduced-pressure drying for 8 hours at 90 degreeC. In addition, “Compound No. 3” in the table is the same as the above No. This corresponds to compound 3.

(Crystallization temperature)
The obtained pellets were heated to 200 ° C. at a rate of 50 ° C./min with a differential scanning calorimeter (Diamond DSC; manufactured by Perkin Elmer), held for 5 minutes and then 0 ° C. at a rate of −20 ° C./min. And the crystallization temperature was determined. The results are shown in Table 1 below.

＊１）結晶核剤未配合
＊２）比較化合物１：Ｔａｌｃ Ｐ−６；日本タルク（株）製
＊３）比較化合物２：エチレンビスヒドロキシステアリルアミド：ＫＦトレーディング社製
＊４）結晶化しないため、測定不能。

* 1) Crystal nucleating agent not included * 2) Comparative compound 1: Talc P-6; manufactured by Nippon Talc Co., Ltd. * 3) Comparative compound 2: ethylene bishydroxystearylamide: manufactured by KF Trading * 4) Because it does not crystallize Inability to measure.

  From Table 1 above, the lactic acid polymer not blended with the crystal nucleating agent of Comparative Example 1 cannot be crystallized, and those that are not the synthetic resin compositions of the present invention of Comparative Examples 2 and 3 have a low crystallization temperature. confirmed. On the other hand, it was confirmed that the synthetic resin composition containing the compound of the sulfohydrazide structure of the present invention of Example 1 has a high crystallization temperature and is excellent in promoting crystallization. Furthermore, the synthetic resin composition of the present invention can contribute to the improvement of heat resistance and molding processability of a molded product obtained by molding the synthetic resin composition due to its remarkable improvement in crystallization temperature.

Claims (3)

For 100 parts by mass of the synthetic resin, the following formula:

A synthetic resin composition comprising 0.01 to 10 parts by mass of a compound having a sulfohydrazide structure represented by:   The synthetic resin composition according to claim 1, wherein the synthetic resin is a polyester resin.   The synthetic resin composition according to claim 2, wherein the synthetic resin is a lactic acid-based polymer.