Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/34—Heterocyclic compounds having nitrogen in the ring
  • C08K5/35—Heterocyclic compounds having nitrogen in the ring having also oxygen in the ring
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/20—Compounding polymers with additives, e.g. colouring
  • C08J3/201—Pre-melted polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/05—Alcohols; Metal alcoholates
  • C08K5/053—Polyhydroxylic alcohols
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
  • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds

Definitions

• the present invention relates to a resin composition containing an aromatic polyester, excellent in hydrolysis resistance and fluidity, and having suppressed generation of isocyanate gas during molding.
• Aromatic polyester resins represented by polyethylene terephthalate, polybutylene terephthalate, etc. have excellent mechanical properties, electrical properties, heat resistance, weather resistance, water resistance, chemical resistance, solvent resistance and processability.
• As an engineering plastic it is widely used for various applications such as automobile parts, electric / electronic parts and the like.
• weight reduction of vehicle-mounted parts for the purpose of improving fuel efficiency as part of environmental measures, and resin parts are becoming thinner and lighter.
• the liquidity that can cope with the situation has become important.
• mechanical strength such as tensile strength and wet heat stability such as hydrolysis resistance.
• Aromatic polyester resins are often used for sheet and film applications.
• back sheet film back surface sealing film
• solar power generation solar cell
• hydrolysis resistance is required, such as weather resistance and hydrolysis resistance.
• Aromatic polyester resins are inferior in durability compared to fluorine-based resins and polyethylene-based resins, and various methods have been proposed for improving durability.
• Patent Documents 1 and 2 show that hydrolysis resistance is improved by adding polycarbodiimide to an aromatic polyester resin.
• Patent Document 3 it is known that when a polycarbodiimide compound is used as a terminal blocker for a polymer compound, a significant increase in viscosity is caused by a crosslinking reaction with polyester (Patent Document 3).
• thermoplastic aromatic polyester when a cyclic carbodiimide compound having at least two carbodiimide rings having only one carbodiimide group in one ring is selected as the thermoplastic aromatic polyester, water resistance Although the degree of improvement in decomposability is high, at the same time, a new problem that the melt viscosity increases as compared with the case where a conventionally known polycarbodiimide compound is applied has become apparent.
• JP-A-8-73719 International Publication WO2010 / 018662 Pamphlet
• An object of the present invention is to provide a resin composition that eliminates the problems that the above-mentioned prior art potentially has, contains an aromatic polyester resin, and has both high hydrolysis resistance and moldability. There is to do.
• the present inventors have studied the application of a cyclic carbodiimide compound having at least two carbodiimide rings having only one carbodiimide group in one ring.
• aromatic polyester resins, cyclic In addition to the carbodiimide compound, it has been found that a resin composition capable of achieving the above-mentioned purpose can be obtained by containing a specific polyhydric hydroxyl group-containing compound, and further intensive studies have been made to arrive at the present invention.
• Aromatic polyester resin having a terminal carboxyl group amount of 30 equivalents / ton or less (component A), a cyclic carbodiimide compound having at least two carbodiimide rings having only one carbodiimide group in one ring (component B), and hydroxyl value
• C component polyhydric hydroxyl group-containing compound
• X is a tetravalent group represented by the following formula (i-1).
• Ar 1 to Ar 4 are each independently an orthophenylene group which may be substituted with a substituent, or 1, 2-naphthalene-diyl group.) 5.
• An aromatic polyester resin having a terminal carboxyl group amount of 30 equivalents / ton or less (component A), a cyclic carbodiimide compound having at least two rings having only one carbodiimide group in one ring (component B), and a hydroxyl value of A method for producing a resin composition containing 200 or more polyvalent hydroxyl group-containing compounds (component C), (I) After the aromatic polyester resin (component A) and the polyhydric hydroxyl group-containing compound (component C) are melt-kneaded, a cyclic carbodiimide compound (component B) is added to the resulting mixture and melt-kneaded, or (ii) ) The above production method, wherein a cyclic carbodiimide compound (B component) and a polyvalent hydroxyl group-containing compound (C component) are simultaneously added to an aromatic polyester resin (component A) and melt-kneaded. 14 A molded article comprising the resin composition according to any one of 1 to 12 above.
• the resin composition of the present invention has a high level of hydrolysis resistance and moldability, and generates very little isocyanate gas during molding.
• the resin composition of the present invention can be suitably used as a material for parts exposed to the external environment for a long period of time, for example, a solar cell backsheet or a solar cell module.
• parts that require thin-walled fluidity in injection molding such as various housings, mechanical parts such as gears and gears, electrical and electronic parts such as connectors, construction parts, civil engineering parts, agricultural materials, automobile parts (interior and exterior parts, etc.) ) And materials for daily use.
• the aromatic polyester resin (component A) is a dicarboxylic acid component mainly composed of a dicarboxylic acid compound and / or an ester-forming derivative thereof, and a diol component mainly composed of a diol compound and / or an ester-forming derivative thereof.
• This is a thermoplastic polyester resin obtained by the above reaction, and contains an aromatic compound in at least one of a dicarboxylic acid component or a diol component.
• the dicarboxylic acid component include aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, and aromatic dicarboxylic acids.
• Aliphatic dicarboxylic acids having 4 to 40 carbon atoms such as succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedicarboxylic acid, dotecandicarboxylic acid, hexadecanedicarboxylic acid, dimer acid, etc.
• Examples thereof include aliphatic dicarboxylic acids, preferably aliphatic dicarboxylic acids having 4 to 14 carbon atoms.
• an alicyclic dicarboxylic acid having 4 to 40 carbon atoms such as hexahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, and hymic acid, preferably an alicyclic dicarboxylic acid having 8 to 12 carbon atoms.
• examples include acids.
• aromatic dicarboxylic acids phthalic acid, isophthalic acid, terephthalic acid, methyl isophthalic acid, methyl terephthalic acid, naphthalenedicarboxylic acid such as 2,6-naphthalenedicarboxylic acid, 4,4′-biphenyldicarboxylic acid, 4,4′- Aromatic dicarboxylic acids having 8 to 16 carbon atoms such as diphenoxy ether dicarboxylic acid, 4,4′-dioxybenzoic acid, 4,4′-diphenylmethane dicarboxylic acid, 4,4′-diphenyl ketone dicarboxylic acid, or derivatives thereof Can be mentioned.
• Derivatives include derivatives capable of forming an ester such as lower alkyl esters, aryl esters, and acid anhydrides. These dicarboxylic acid components can be used alone or in combination of two or more. Preferred dicarboxylic acid components include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid. In particular, terephthalic acid and 2,6-naphthalenedicarboxylic acid are preferable.
• the dicarboxylic acid component preferably contains, for example, 50 mol% or more, preferably 80 mol% or more, more preferably 90 mol% or more of aromatic dicarboxylic acid.
• polyvalent carboxylic acid such as trimellitic acid and a pyromellitic acid, or its ester formation derivative (alcohol ester etc.) etc.
• a branched thermoplastic polyester resin can also be obtained.
• the diol component include aliphatic diols, polyoxyalkylene glycols, and alicyclic diols.
• Fatty acids having 2 to 12 carbon atoms such as ethylene glycol, trimethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, neopentyl glycol, hexanediol, octanediol, decanediol as aliphatic diol Diols, preferably aliphatic diols having 2 to 10 carbon atoms.
• the polyoxyalkylene glycol include a glycol having an alkylene group having about 2 to 4 carbon atoms and having a plurality of oxyalkylene units.
• Examples include diethylene glycol, dipropylene glycol, ditetramethylene glycol, triethylene glycol, tripropylene glycol, and polytetramethylene glycol.
• Examples of the alicyclic diol include 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, and hydrogenated bisphenol A.
• aromatic diols such as hydroquinone, resorcinol, bisphenol, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis- (4- (2-hydroxyethoxy) phenyl) propane, and xylylene glycol are used in combination. May be. These diol components can be used alone or in combination of two or more.
• Preferred diol components include alkylene glycols having 2 to 10 carbon atoms such as ethylene glycol, trimethylene glycol, propylene glycol, and 1,4-butanediol.
• the diol component preferably contains, for example, an alkylene glycol having 2 to 10 carbon atoms of 50 mol% or more, preferably 80 mol% or more, more preferably 90 mol% or more.
• a polyol such as glycerin, trimethylolpropane, trimethylolethane, pentaerythritol, or an ester-forming derivative thereof may be used in combination.
• a branched thermoplastic polyester resin can also be obtained.
• an aromatic polyester resin (component A)
• component A As a copolyester in which two or more of the above dicarboxylic acid components and diol components are combined, and other copolymerizable monomers (hereinafter sometimes referred to as copolymerizable monomers)
• a copolyester in which an oxycarboxylic acid component, a lactone component, or the like is combined can also be used.
• the oxycarboxylic acid include oxybenzoic acid, oxynaphthoic acid, hydroxyphenylacetic acid, glycolic acid, oxycaproic acid and other oxycarboxylic acids or derivatives thereof.
• the lactone includes lactones having 3 to 12 carbon atoms such as propiolactone, butyrolactone, valerolactone, caprolactone (eg, ⁇ -caprolactone).
• the proportion of the copolymerizable monomer can be selected, for example, from the range of about 0.01 mol% to about 30 mol%, and is usually about 1 mol% to about 30 mol%, preferably 3 mol%. It is about 25 mol% or less, more preferably about 5 mol% or more and 20 mol% or less.
• the proportion of the homopolyester and the copolyester is such that the proportion of the copolymerizable monomer is 0.1 mol% or more and 30 mol% or less with respect to the total monomers. (Preferably about 1 mol% or more and 25 mol% or less, more preferably about 5 mol% or more and about 25 mol% or less).
• the former / the latter 99/1 to 1/99 (mass ratio)
• it can be selected from the range of about 95/5 to 5/95 (mass ratio), more preferably about 90/10 to 10/90 (mass ratio).
• Preferred aromatic polyester resins include homopolyester or copolyester having an alkylene arylate unit such as alkylene terephthalate or alkylene naphthalate as a main component (for example, about 50 to 100 mol%, preferably about 75 to 100 mol%).
• alkylene arylate unit such as alkylene terephthalate or alkylene naphthalate
• polyester for example, about 50 to 100 mol%, preferably about 75 to 100 mol%).
• Examples of the polyalkylene terephthalate include polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT) and the like, polyalkylene terephthalate having 2 to 4 carbon atoms, 1,4-cyclohexanedimethylene terephthalate ( PCT).
• polyalkylene naphthalate examples include polyalkylene naphthalate having 2 to 4 carbon atoms in the alkylene portion, such as polyethylene naphthalate, polypropylene naphthalate, and polybutylene naphthalate. These can be used alone or in combination of two or more.
• a particularly preferred aromatic polyester resin (component A) is 80 mol% of alkylene arylate units having 2 to 4 carbon atoms in the alkylene moiety such as ethylene terephthalate, trimethylene terephthalate, tetramethylene terephthalate, and tetramethylene-2,6-naphthalate.
• the homopolyester resin or copolyester resin contained above (especially 90 mol% or more) is mentioned.
• polyethylene terephthalate resin, polytrimethylene terephthalate resin, polybutylene terephthalate resin, polytetramethylene-2,6-naphthalene dicarboxylate resin and the like can be mentioned.
• polyethylene terephthalate resin and polybutylene terephthalate resin are preferable, and polybutylene terephthalate resin is particularly preferable.
• the aromatic polyester resin (component A) preferably contains 50% by mass or more of polybutylene terephthalate.
• the terminal carboxyl group amount of the aromatic polyester resin (component A) is 30 equivalents / ton or less.
• a more preferable terminal carboxyl group amount is 25 equivalents / ton or less.
• a cyclic carbodiimide compound (component B) by using a cyclic carbodiimide compound (component B), the hydrolysis resistance of the resin composition can be enhanced.
• the amount of terminal carboxyl groups of the aromatic polyester resin (component A) is too large, the resin composition The hydrolysis resistance of the product is not sufficiently increased. Therefore, the amount of terminal carboxyl groups of the aromatic polyester resin (component A) needs to be 30 equivalents / ton or less.
• the intrinsic viscosity (IV) of the aromatic polyester resin (component A) is preferably 0.6 dL / g or more, and more preferably 0.7 dL / g or more.
• the intrinsic viscosity is preferably 1.3 dL / g or less, and more preferably 1.2 dL / g or less.
• aromatic polyester resins (component A) having different intrinsic viscosities for example, by blending aromatic polyester resins having intrinsic viscosities of 1.5 dL / g and 0.5 dL / g, 0.6-1.
• An intrinsic viscosity of 3 dL / g or less may be achieved.
• Intrinsic viscosity (IV) can be measured in o-chlorophenol or a mixed solvent of phenol / tetrachloroethane (mass ratio 60/40) at a temperature of 35 ° C.
• an aromatic polyester resin having an intrinsic viscosity in such a range When an aromatic polyester resin having an intrinsic viscosity in such a range is used, it is easy to efficiently achieve sufficient hydrolysis resistance and reduction in melt viscosity. If the intrinsic viscosity is too small, there is a possibility that sufficient effect of improving hydrolysis resistance may not be obtained. If the intrinsic viscosity is too large, the melt viscosity at the time of molding becomes high, and in some cases, the resin in the molding die There is a possibility of causing poor flow and poor filling. As the aromatic polyester resin (component A), a commercially available product may be used.
• a dicarboxylic acid component or a reactive derivative thereof, a diol component or a reactive derivative thereof, and a monomer that can be copolymerized, if necessary, are used in a conventional manner. You may use what was manufactured by copolymerization (polycondensation) by the method, for example, transesterification method, direct esterification method, etc.
• the resin composition of the present invention preferably has a terminal carboxyl group amount of 5 equivalents / ton or less. When it is in this range, it has particularly good hydrolysis resistance. Furthermore, the more preferable amount of terminal carboxyl groups is 3 equivalents / ton or less.
• the resin composition of the present invention desirably has a reduced viscosity retention of 50% or more after 100 hours in a pressure cooker test at 121 ° C. and 100% RH (0.2 MPa). If the reduced viscosity retention is 50% or more, the finally obtained film or molded product has sufficient hydrolysis resistance without significantly reducing the mechanical strength.
• the present invention relates to a polybutylene terephthalate resin composition in which polybutylene terephthalate accounts for 50% by mass or more based on the total mass of the aromatic polyester resin (component A), and has a melt viscosity of 300 Pa ⁇ s at a temperature of 260 ° C.
• a polybutylene terephthalate resin composition having a reduced viscosity retention after 100 hours of 80% or more in a pressure cooker test at 121 ° C. and 100% RH (0.2 MPa) is included.
• the polybutylene terephthalate resin composition of the present invention accounts for 50% by mass or more based on the total mass of the component A. In order to exhibit the characteristics of polybutylene terephthalate, it is preferably 90% by mass or more, particularly preferably 95% by mass or more, and most preferably 97.5% by mass or more.
• the resin composition of the present invention preferably has a melt viscosity at a temperature of 260 ° C.
• the resin composition of the present invention contains a cyclic carbodiimide compound (component B) having at least two carbodiimide rings having only one carbodiimide group in one ring with respect to the aromatic polyester resin (component A).
• the “carbodiimide ring” means a compound in which a plurality of atoms are bonded so as to have a ring structure, that is, a so-called cyclic compound, a ring in which only one carbodiimide group exists, and a cyclic carbodiimide compound (component B) )
• the compound having such a structure is particularly effective in improving the wet heat durability of the aromatic polyester resin (component A), and an isocyanate compound is not generated by the end-capping reaction.
• the number of atoms in the cyclic structure constituting the carbodiimide ring is preferably 8 to 50, more preferably 10 to 30, further preferably 10 to 20, and particularly preferably 10 to 15.
• the number of atoms in the ring structure means the number of atoms that directly constitute the ring structure, and is, for example, 8 for an 8-membered ring and 50 for a 50-membered ring. If the number of atoms in the cyclic structure is 8 or more, the cyclic carbodiimide compound (component B) has high stability and is easy to store and use.
• the cyclic carbodiimide compound (component B) having 50 or less atoms can be easily synthesized, so that the cost can be prevented from significantly increasing.
• the molecular weight of the cyclic carbodiimide compound (component B) is preferably 100 to 1,000. If it is 100 or more, the structural stability and volatility of the cyclic carbodiimide compound (component B) are advantageous. On the other hand, if it is 1,000 or less, synthesis in a diluting system is unnecessary for the production of cyclic carbodiimide, and the yield is hardly lowered, which is advantageous in terms of cost.
• the molecular weight of the cyclic carbodiimide compound (component B) refers to the weight average molecular weight when the cyclic carbodiimide compound (component B) has a molecular weight distribution.
• the component B is preferably a cyclic carbodiimide compound in which a plurality of carbodiimide rings are bonded through a spiro bond or a bonding group. In the case of taking such a structure, the effect of improving the wet heat durability of the aromatic polyester resin (component A) can be further enhanced.
• a compound represented by the following formula is preferable.
• X is a tetravalent group represented by the following formula (i-1).
• Ar. 1 ⁇ Ar 4 Each independently represents an orthophenylene group or a 1,2-naphthalene-diyl group which may be substituted with a substituent.
• Specific examples of the cyclic carbodiimide compound (component B) having at least two carbodiimide rings having only one carbodiimide group in one ring can be used in the present application. .
• n is the number of repeating units of the polymer.
• the content of the cyclic carbodiimide compound (component B) in the resin composition is preferably 0.1 to 3 parts by mass, more preferably 0.3 to 2 parts per 100 parts by mass of the aromatic polyester resin (component A). Part by mass, more preferably 0.5 to 1.5 parts by mass. If content of B component is said range, the effect of a carbodiimide can be acquired, without modifying the characteristic of a substrate.
• the polyvalent hydroxyl group-containing compound (component C) is a compound having two or more hydroxyl groups in one molecule.
• the polyvalent hydroxyl group-containing compound (component C) has a hydroxyl value of 200 or more, as will be described later.
• the polyhydric hydroxyl group-containing compound (C component) having a hydroxyl value of 200 or more can be used alone or in combination of two or more. This polyvalent hydroxyl group-containing compound (C component) enhances the fluidity of the resin composition. In general, when a component that enhances fluidity is added to an aromatic polyester resin, even if the fluidity can be improved, deterioration of properties such as mechanical strength and toughness of the aromatic polyester resin itself cannot be avoided.
• the fluidity at the time of melting of the resin composition can be efficiently improved while maintaining the characteristics of the aromatic polyester resin at a high level.
• the polyhydric hydroxyl group-containing compound (C component) having a hydroxyl value of 200 or more promotes the effect of improving the hydrolysis resistance of the resin composition by the B component in the resin composition containing the cyclic carbodiimide compound (B component). Also works as a hydrolysis resistance improver.
• the polyhydric hydroxyl group-containing compound (C component) having a hydroxyl value of 200 or more improves the melt-kneading property by suppressing an increase in the viscosity of the resin composition, and the aromatic polyester resin (A component)
• the polyhydric hydroxyl group-containing compound (C component) having a hydroxyl value of 200 or more is contained in the resin composition, while utilizing the characteristics of the aromatic polyester resin (A component), the fluidity of the resin composition is enhanced.
• the hydrolysis resistance of the resin composition can also be enhanced.
• the polyhydric hydroxyl group-containing compound (C component) having a hydroxyl value of 200 or more a compound produced by a conventionally known method may be used, or a commercially available product may be purchased and used.
• the hydroxyl value of the polyvalent hydroxyl group-containing compound (component C) is 200 or more.
• the preferred hydroxyl number is 250 or more. If the hydroxyl value is 200 or more, the effect of improving the fluidity tends to be further increased.
• the hydroxyl value of the polyvalent hydroxyl group-containing compound (component C) is preferably 1000 or less, more preferably 800 or less, still more preferably 600 or less, and particularly preferably 500 or less.
• the hydroxyl value means that measured by the Japan Oil Chemists 'Society method 2.3.6.2-1996 (pyridine / acetic anhydride method) (standard oil analysis test method established by the Japan Oil Chemists' Society). .
• polyhydric hydroxyl group-containing compound examples include polyhydric alcohols or partial esters thereof.
• the component C is preferably a partial ester of a polyhydric alcohol and a fatty acid having 12 or more carbon atoms.
• examples of the polyhydric alcohol include compounds having two or more hydroxymethyl groups in the same molecule.
• examples include erythritol, dipentaerythritol, tripentaerythritol, and various sorbitols. Those consisting of at least one selected from these can be preferably used, and only one can be used, or two or more can be used in combination.
• the fatty acid of the partial ester of the polyhydric alcohol those having 12 or more carbon atoms are preferable from the viewpoint of fluidity.
• the fatty acid having 12 or more carbon atoms include lauric acid, oleic acid, palmitic acid, stearic acid, 12-hydroxystearic acid, behenic acid, and montanic acid.
• Fatty acids having 12 to 32 carbon atoms are preferred, and fatty acids having 12 to 22 carbon atoms are particularly preferred.
• lauric acid, stearic acid, 12-hydroxystearic acid or behenic acid is particularly preferable. It is preferable to use a fatty acid having 12 or more carbon atoms because the heat resistance of the resin tends to be sufficiently maintained.
• a carbon number of 32 or less is preferable because the effect of improving the fluidity is high.
• a polyhydric hydroxyl group-containing compound (C component) from the viewpoint of imparting fluidity at the time of melting to the resin composition, and maintaining the obtained molded body without substantially reducing the physical properties of the aromatic polyester resin (A component).
• An ether obtained by addition polymerization of alkylene oxide to glycerin fatty acid ester or diglycerin is preferable.
• ethers obtained by addition polymerization of alkylene oxide to glycerin fatty acid ester and diglycerin will be described.
• the glycerin fatty acid ester is an ester composed of glycerin and / or a dehydration condensate thereof and a fatty acid.
• glycerin fatty acid esters those obtained using fatty acids having 12 or more carbon atoms are preferred.
• the fatty acid having 12 or more carbon atoms include lauric acid, oleic acid, palmitic acid, stearic acid, 12-hydroxystearic acid, behenic acid, and montanic acid.
• Fatty acids having 12 to 32 carbon atoms are preferred, and fatty acids having 12 to 22 carbon atoms are particularly preferred.
• Examples of preferred glycerin fatty acid esters include glycerin monostearate, glycerin monobehenate, diglycerin monostearate, triglycerin monostearate, triglycerin stearic acid partial ester, tetraglycerin stearic acid partial ester, decaglycerin lauric acid partial ester Glycerin mono-12-hydroxystearate and the like.
• the ether obtained by addition polymerization of alkylene oxide to diglycerin is obtained by, for example, polyoxypropylene diglyceryl ether obtained by addition polymerization of propylene oxide to diglycerin or addition polymerization of ethylene oxide to diglycerin.
• Polyoxyethylene diglyceryl ether is mentioned. In the present invention, among these ethers, use of polyoxyethylene diglyceryl ether is particularly preferable.
• the content of the polyvalent hydroxyl group-containing compound (component C) in the resin composition is preferably 0.05 to 5 parts by mass, more preferably 0.1 to 100 parts by mass of the aromatic polyester resin (component A). ⁇ 3 parts by mass, more preferably 0.5-2 parts by mass. If the content of the polyvalent hydroxyl group-containing compound is 0.05 parts by mass or more, the effect of improving the fluidity tends to be obtained sufficiently, and if it is 5 parts by mass or less, molding by gas generation during molding is preferable. This is preferable because there is almost no risk of appearance defects and mold contamination.
• the resin composition of the present invention can be produced by melt-kneading an aromatic polyester resin (component A), a cyclic carbodiimide compound (component B), and a polyvalent hydroxyl group-containing compound (component C).
• the addition time of the polyhydric hydroxyl group-containing compound (C component) into the system is important, and the hydroxyl value is 200 or more before adding the carbodiimide compound (B component) to the aromatic polyester resin (A component). If the polyhydric hydroxyl group-containing compound (C component) is not added, the thickening by the carbodiimide compound (B component) occurs before the thickening suppression effect by the C component addition is exhibited.
• a carbodiimide compound (B component) is added and melt-kneaded in the coexistence of an aromatic polyester resin (component A) and a polyvalent hydroxyl group-containing compound (component C), or
• a polyhydric hydroxyl group-containing compound (component C)) and a carbodiimide compound (component B) may be added simultaneously to the aromatic polyester resin (component A) and melt-kneaded.
• the component C is dispersed before the carbodiimide compound (component B) is added.
• kneading a kneading method in a molten state is preferable from the viewpoints of productivity and uniform kneading properties.
• the kneading apparatus is not particularly limited, and conventionally known vertical reaction vessels, mixing tanks, kneading tanks or horizontal uniaxial kneading apparatuses or multiaxial kneading apparatuses, such as uniaxial or multiaxial ruders, A kneader is exemplified.
• the melt kneading time is not particularly specified, and depends on the mixing apparatus and the mixing temperature, but is selected from 0.1 minute to 2 hours, preferably 0.2 minutes to 60 minutes, more preferably 0.2 minutes to 30 minutes.
• the sealing reaction of the carboxyl group of the aromatic polyester resin by the cyclic carbodiimide compound (component B) is possible at room temperature (25 ° C.) to about 300 ° C., but from the viewpoint of reaction efficiency, 50 ° C. to 280 ° C., The range of 100 ° C. to 280 ° C. is more preferable because it is more accelerated.
• the reaction of aromatic polyester resin (component A) is more likely to proceed at the melting temperature, but the reaction is performed at a temperature lower than 300 ° C.
• the sealing reaction proceeds sufficiently quickly without a catalyst, but a catalyst that promotes the sealing reaction can also be used.
• a catalyst the catalyst used when performing sealing reaction using the conventional linear carbodiimide compound is applicable. These can be used alone or in combination of two or more.
• the addition amount of the catalyst is not particularly limited, but is preferably 0.001 to 1 part by mass, and 0.01 to 0.1 part by mass with respect to 100 parts by mass in total of the thermoplastic aromatic polyester and the cyclic carbodiimide.
• the resin composition of the present invention can contain a stabilizer.
• a stabilizer what is used for the stabilizer of a normal thermoplastic resin can be used.
• an antioxidant, a light stabilizer, etc. can be mentioned. By blending these agents, a molded product having excellent mechanical properties, moldability, heat resistance and durability can be obtained.
• the antioxidant include hindered phenol compounds, hindered amine compounds, phosphorus compounds such as phosphite compounds, and thioether compounds.
• hindered phenol compounds examples include n-octadecyl-3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) -propionate, n-octadecyl-3- (3′-methyl-5 ′).
• phosphite compound those in which at least one P—O bond is bonded to an aromatic group are preferable.
• tris (2,6-di-tert-butylphenyl) phosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, bis (2,6-di-tert-butyl) -4-Methylphenyl) pentaerythritol diphosphite, tetrakis (2,6-di-tert-butylphenyl) 4,4'-biphenylene phosphite and the like can be preferably used.
• thioether compounds include dilauryl thiodipropionate, ditridecyl thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate, pentaerythritol-tetrakis (3-lauryl thiopropionate), Pentaerythritol-tetrakis (3-dodecylthiopropionate), pentaerythritol-tetrakis (3-octadecylthiopropionate), pentaerythritol tetrakis (3-myristylthiopropionate), pentaerythritol-tetrakis (3-stearylthio) Propionate) and the like.
• the light stabilizer examples include benzophenone compounds, benzotriazole compounds, aromatic benzoate compounds, oxalic acid anilide compounds, cyanoacrylate compounds, hindered amine compounds, and the like.
• benzophenone compounds include benzophenone, 2,4-dihydroxybenzophenone, 2,2′-dihydroxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2 ′.
• benzotriazole compound examples include 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (3,5-di-tert-butyl-2-hydroxyphenyl) benzotriazole, 2- (3,5- Di-tert-amyl-2-hydroxyphenyl) benzotriazole, 2- (3 ′, 5′-di-tert-butyl-4′-methyl-2′-hydroxyphenyl) benzotriazole, 2- (3,5- Di-tert-amyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (5-tert-butyl-2-hydroxyphenyl) benzotriazole, 2- [2′-hydroxy-3 ′, 5′-bis ( ⁇ , ⁇ -Dimethylbenzyl) phenyl] benzotriazole, 2- [2′-hydroxy-3 ′, 5′-bis ( ⁇ , ⁇ -dimethylben ) Phenyl] -2H- benzotriazole, 2- (4'-oc
• aromatic benzoate compounds examples include alkylphenyl salicylates such as p-tert-butylphenyl salicylate and p-octylphenyl salicylate.
• oxalic acid anilide compounds examples include 2-ethoxy-2′-ethyloxalic acid bisanilide, 2-ethoxy-5-tert-butyl-2′-ethyloxalic acid bisanilide, and 2-ethoxy-3′-. Examples include dodecyl oxalic acid bisanilide.
• Examples of the cyanoacrylate compound include ethyl-2-cyano-3,3′-diphenyl acrylate and 2-ethylhexyl-cyano-3,3′-diphenyl acrylate.
• Examples of hindered amine compounds include 4-acetoxy-2,2,6,6-tetramethylpiperidine, 4-stearoyloxy-2,2,6,6-tetramethylpiperidine, 4-acryloyloxy-2,2,6, 6-tetramethylpiperidine, 4- (phenylacetoxy) -2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 4-methoxy-2,2, 6,6-tetramethylpiperidine, 4-octadecyloxy-2,2,6,6-tetramethylpiperidine, 4-cyclohexyloxy-2,2,6,6-tetramethylpiperidine, 4-benzyloxy-2,2 , 6,6-tetramethylpiperidine, 4-
• a stabilizer component may be used by 1 type and may be used in combination of 2 or more type.
• a hindered phenol compound and / or a benzotriazole compound is preferable as the stabilizer component.
• the content of the stabilizer is preferably 0.01 to 3 parts by mass, more preferably 0.03 to 2 parts by mass, per 100 parts by mass of the aromatic polyester resin (component A).
• the resin composition of the present invention can contain an organic or inorganic crystallization accelerator. By containing the crystallization accelerator, a molded product having excellent mechanical properties, heat resistance, and moldability can be obtained.
• crystallization accelerator used in the present invention, those generally used as crystallization nucleating agents for crystalline resins can be used, and both inorganic crystallization nucleating agents and organic crystallization nucleating agents are used. be able to.
• inorganic crystallization nucleating agents talc, kaolin, silica, synthetic mica, clay, zeolite, graphite, carbon black, zinc oxide, magnesium oxide, titanium oxide, calcium carbonate, calcium sulfate, barium sulfate, calcium sulfide, boron nitride , Montmorillonite, neodymium oxide, aluminum oxide, phenylphosphonate metal salt and the like.
• These inorganic crystallization nucleating agents are treated with various dispersing aids in order to enhance the dispersibility in the composition and its effect, and are highly dispersed in a primary particle size of about 0.01 to 0.5 ⁇ m. Are preferred.
• Organic crystallization nucleating agents include calcium benzoate, sodium benzoate, lithium benzoate, potassium benzoate, magnesium benzoate, barium benzoate, calcium oxalate, disodium terephthalate, dilithium terephthalate, dipotassium terephthalate, Sodium laurate, potassium laurate, sodium myristate, potassium myristate, calcium myristate, barium myristate, sodium octacolate, calcium octacolate, sodium stearate, potassium stearate, lithium stearate, calcium stearate, magnesium stearate , Barium stearate, sodium montanate, calcium montanate, sodium toluate, sodium salicylate, potassium salicylate, salicy Organic carboxylic acid metal salts such as zinc acid, aluminum dibenzoate, ⁇ -naphthoic acid sodium, ⁇ -naphthoic acid potassium, sodium cyclohexanecarboxylic acid and the like
• organic carboxylic acid amides such as stearic acid amide, ethylenebislauric acid amide, palmitic acid amide, hydroxystearic acid amide, erucic acid amide, trimesic acid tris (tert-butylamide), low density polyethylene, high density polyethylene, polyiso Propylene, polybutene, poly-4-methylpentene, poly-3-methylbutene-1, polyvinylcycloalkane, polyvinyltrialkylsilane, high melting point polylactic acid, sodium salt of ethylene-acrylic acid copolymer, sodium of styrene-maleic anhydride copolymer Examples thereof include salts (so-called ionomers), benzylidene sorbitol and derivatives thereof such as dibenzylidene sorbitol.
• the resin composition of the present invention can contain an organic or inorganic filler. By containing the filler component, a molded product having excellent mechanical properties, heat resistance, and moldability can be obtained.
• Organic fillers such as rice husks, wood chips, okara, waste paper ground materials, clothing ground materials, cotton fibers, hemp fibers, bamboo fibers, wood fibers, kenaf fibers, jute fibers, banana fibers, coconut fibers
• Plant fibers such as pulp or cellulose fibers processed from these plant fibers and fibrous fibers such as animal fibers such as silk, wool, angora, cashmere and camel, synthetic fibers such as polyester fibers, nylon fibers and acrylic fibers , Paper powder, wood powder, cellulose powder, rice husk powder, fruit husk powder, chitin powder, chitosan powder, protein, starch and the like.
• powdery materials such as paper powder, wood powder, bamboo powder, cellulose powder, kenaf powder, rice husk powder, fruit husk powder, chitin powder, chitosan powder, protein powder, and starch are preferred. Powder, bamboo powder, cellulose powder and kenaf powder are preferred. Paper powder and wood powder are more preferable. Paper dust is particularly preferable.
• organic fillers may be those directly collected from natural products, but may also be those obtained by recycling waste materials such as waste paper, waste wood and old clothes.
• the wood is preferably a softwood material such as pine, cedar, oak or fir, or a hardwood material such as beech, shii or eucalyptus.
• Paper powder is an adhesive from the viewpoint of moldability, especially emulsion adhesives such as vinyl acetate resin emulsions and acrylic resin emulsions that are usually used when processing paper, polyvinyl alcohol adhesives, polyamide adhesives Those containing hot melt adhesives such as are preferably exemplified.
• the blending amount of the organic filler is not particularly limited, but from the viewpoint of moldability and heat resistance, preferably 100 to 300 parts by mass, more preferably 1 to 300 parts by mass per 100 parts by mass of the aromatic polyester resin (component A) The amount is preferably 5 to 200 parts by mass, more preferably 10 to 150 parts by mass, and particularly preferably 15 to 100 parts by mass.
• the composition of the present invention may contain an inorganic filler. By combining the inorganic filler, a composition having excellent mechanical properties, heat resistance, and moldability can be obtained.
• the inorganic filler used in the present invention a fibrous, plate-like, or powder-like material used for reinforcing ordinary thermoplastic resins can be used.
• layered silicates include smectite clay minerals such as montmorillonite, beidellite, nontronite, saponite, hectorite, and soconite, various clay minerals such as vermiculite, halosite, kanemite, and kenyanite, Li-type fluorine teniolite, Na And swellable mica such as Li-type fluorine teniolite, Li-type tetrasilicon fluorine mica and Na-type tetrasilicon fluorine mica. These may be natural or synthetic.
• smectite clay minerals such as montmorillonite and hectorite
• swellable synthetic mica such as Li type fluorine teniolite and Na type tetrasilicon fluorine mica
• fibrous or plate-like inorganic fillers are preferable, and glass fiber, wollastonite, aluminum borate whisker, potassium titanate whisker, mica, and kaolin, a cation-exchanged layered silicate. Is preferred.
• the aspect ratio of the fibrous filler is preferably 5 or more, more preferably 10 or more, and still more preferably 20 or more.
• Such a filler may be coated or converged with a thermoplastic resin such as an ethylene / vinyl acetate copolymer or a thermosetting resin such as an epoxy resin, or may be treated with a coupling agent such as aminosilane or epoxysilane. May be.
• the content of the inorganic filler is preferably 0.1 to 200 parts by weight, more preferably 0.5 to 100 parts by weight, and further preferably 1 to 50 parts by weight with respect to 100 parts by weight of the aromatic polyester resin (component A). Parts, particularly preferably 1 to 30 parts by mass, most preferably 1 to 20 parts by mass.
• the resin composition of the present invention can contain a release agent.
• the mold release agent used in the present invention those used for ordinary thermoplastic resins can be used.
• the release agent include fatty acid, fatty acid metal salt, oxy fatty acid, paraffin, low molecular weight polyolefin, fatty acid amide, alkylene bis fatty acid amide, aliphatic ketone, and modified silicone. By blending these, a molded product excellent in mechanical properties, moldability, and heat resistance can be obtained.
• a mold release agent may be used alone or in combination of two or more.
• the content of the release agent is preferably 0.01 to 3 parts by mass, more preferably 0.03 to 2 parts by mass with respect to 100 parts by mass of the aromatic polyester resin (component A).
• the resin composition of the present invention can contain an antistatic agent.
• the antistatic agent include quaternary ammonium salt compounds such as ( ⁇ -lauramidopropionyl) trimethylammonium sulfate and sodium dodecylbenzenesulfonate, sulfonate compounds, and alkyl phosphate compounds.
• the antistatic agent may be used alone or in combination of two or more.
• the content of the antistatic agent is preferably 0.05 to 5 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the aromatic polyester resin (component A).
• ⁇ Plasticizer> The resin composition of the present invention can contain a plasticizer.
• plasticizer generally known plasticizers can be used. Only one plasticizer may be used, or two or more plasticizers may be used in combination.
• the content of the plasticizer is preferably 0.01 to 30 parts by mass, more preferably 0.05 to 20 parts by mass, and further preferably 0.1 to 10 parts by mass per 100 parts by mass of the aromatic polyester resin (component A). Part.
• each of the crystallization accelerator and the plasticizer may be used alone, or more preferably used in combination.
• the resin composition of the present invention can contain an impact resistance improver.
• the impact resistance improver is one that can be used to improve the impact resistance of a thermoplastic resin, and is not particularly limited. For example, at least one selected from the following impact resistance improvers can be used.
• impact modifiers include ethylene-propylene copolymers, ethylene-propylene-nonconjugated diene copolymers, ethylene-butene-1 copolymers, various acrylic rubbers, ethylene-acrylic acid copolymers and their Alkali metal salts (so-called ionomers), ethylene-glycidyl (meth) acrylate copolymers, ethylene-acrylate copolymers (for example, ethylene-ethyl acrylate copolymers, ethylene-butyl acrylate copolymers), modified ethylene -Propylene copolymer, diene rubber (eg polybutadiene, polyisoprene, polychloroprene), diene and vinyl copolymer (eg styrene-butadiene random copolymer, styrene-butadiene block copolymer, styrene-butadiene-styrene block copolymer
• various micro structures such as those having a cis structure, a trans structure, etc., a core layer and one or more shell layers covering the core layer, and adjacent layers are composed of heterogeneous polymers.
• a so-called core-shell type multi-layered polymer can also be used.
• the various (co) polymers mentioned in the above specific examples may be any of random copolymers, block copolymers, block copolymers and the like, and can be used as the impact resistance improver of the present invention.
• the content of the impact resistance improver is preferably 1 to 30 parts by mass, more preferably 5 to 20 parts by mass, and still more preferably 10 to 20 parts by mass with respect to 100 parts by mass of the aromatic polyester resin (component A).
• the resin composition of the present invention may contain a thermosetting resin such as a phenol resin, a melamine resin, a silicone resin, and an epoxy resin within a range not departing from the spirit of the present invention.
• the resin composition of the present invention may contain a flame retardant such as bromine, phosphorus, silicone, antimony compound and the like within a range not departing from the spirit of the present invention.
• Colorants containing organic and inorganic dyes and pigments for example, oxides such as titanium dioxide, hydroxides such as alumina white, sulfides such as zinc sulfide, ferrocyanides such as bitumen, and chromium such as zinc chromate Contains acid salts, sulfates such as barium sulfate, carbonates such as calcium carbonate, silicates such as ultramarine, phosphates such as manganese violet, carbon such as carbon black, metal colorants such as bronze powder and aluminum powder, etc. You may let them.
• nitroso type such as naphthol green B, nitro type such as naphthol yellow S, azo type such as naphthol red and chromophthal yellow, phthalocyanine type such as phthalocyanine blue and fast sky blue, and condensed polycyclic color such as indanthrone blue
• An additive such as a slidability improving agent such as an agent, graphite, or a fluorine resin may be added. These additives can be used alone or in combination of two or more.
• a molded article made of the resin composition of the present invention can be molded by injection molding, extrusion molding, vacuum, pressure molding, blow molding or the like.
• the molded article examples include pellets, fibers, fabrics, fiber structures, films, sheets, and sheet nonwoven fabrics.
• the pellet made of the resin composition of the present invention is not limited in its melt molding method, and those produced by a known pellet production method can be suitably used. That is, a method of cutting a resin composition extruded into a strand or a plate shape in the air or in water after the resin is completely solidified or not completely solidified and still in a molten state Are conventionally known, but any of them can be suitably applied in the present invention.
• the cylinder temperature is 230 to 290 ° C.
• the mold temperature is preferably 30 to 120 ° C., more preferably 40 to 110 ° C., from the viewpoint of increasing the crystallization of the molded product and the molding cycle.
• These molded products include various housings, mechanical parts such as gears and gears, electrical and electronic parts such as connectors, building members, civil engineering members, agricultural materials, automobile parts (interior and exterior parts, etc.) and daily parts. Can be mentioned.
• the film and sheet of the present invention are formed by a conventionally known method. For example, in a film or sheet, a molding technique such as extrusion molding or cast molding can be used.
• an unstretched film is extruded using an extruder or the like equipped with a T die, a circular die or the like, and further stretched and heat-treated to form.
• the unstretched film can be used as it is as a sheet.
• a material obtained by melt-kneading the resin composition and the above-described various components in advance can be used, or it can be formed through melt-kneading during extrusion molding.
• an unstretched film with few surface defects can be obtained by blending an electrostatic adhesive such as a sulfonic acid quaternary phosphonium salt into the molten resin.
• an unstretched film can also be cast-molded by melt
• Unstretched film can be uniaxially stretched longitudinally in the direction of mechanical flow and transversely uniaxially stretched in the direction perpendicular to the direction of mechanical flow.
• the biaxial stretching method of roll stretching and tenter stretching, and simultaneous biaxial stretching by tenter stretching A biaxially stretched film can be produced by stretching by a biaxial stretching method using a method such as tubular stretching. Further, the film is usually subjected to a heat setting treatment after stretching in order to suppress heat shrinkability and the like.
• the stretched film thus obtained can be subjected to surface activation treatment such as plasma treatment, amine treatment, and corona treatment by a conventionally known method if desired.
• surface activation treatment such as plasma treatment, amine treatment, and corona treatment by a conventionally known method if desired.
• the film and sheet of the present invention can be used in combination with other types of films and sheets other than a single form. Examples of mixed use include various combinations with films and sheets made of other types of materials, such as lamination and lamination, and combinations with other types of forms such as injection molded articles and fiber structures.
• Measurement conditions were as follows: the temperature was 260 ° C., the shear rate was 1 s ⁇ 1 , the measurement atmosphere was nitrogen, the measurement time was 6 seconds, and the melt viscosity at that time was confirmed.
• Melt viscosity characteristics are obtained by drying a pellet-shaped sample of the resin composition at 140 ° C. for 3 hours and then using Capillograph 1B (manufactured by Toyo Seiki Seisakusho) in accordance with ISO 11443: 2005. Measurement was performed at ⁇ 1 mm ⁇ 20 mmL and a shear rate of 1000 sec ⁇ 1 .
• the numerator was obtained as a reduced viscosity after the sample treatment, and the denominator was obtained as a reduced viscosity before the sample treatment.
• (6) Presence or absence of generation of isocyanate odor When the resin composition was melt-kneaded at 250 ° C. for 5 minutes, it was determined by sensory evaluation whether the measurer felt an isocyanate odor. When no isocyanate odor was felt, “No” was assigned, and when an isocyanate odor was felt, “Yes”. 2.
• the reduced viscosity of the aromatic polyester resin (A1) was 0.84 dl / g (the intrinsic viscosity was 0.69 dL / g).
• Table 1 shows the carboxyl group concentration, melt viscosity, and reduced viscosity retention.
• Cyclic carbodiimide compound (component B) The cyclic carbodiimide compound (component B) was produced by the following method.
• an intermediate product (nitro compound) (0.1 mol), 5% palladium carbon (Pd / C) (2 g), and 400 ml of ethanol / dichloromethane (70/30) were charged into a reaction apparatus equipped with a stirrer.
• the reaction was carried out 5 times, and the reaction was carried out with hydrogen being constantly supplied at 25 ° C., and the reaction was terminated when there was no decrease in hydrogen.
• Pd / C was recovered, and the mixed solvent was removed to obtain an intermediate product (amine body).
• triphenylphosphine dibromide (0.11 mol) and 150 ml of 1,2-dichloroethane were charged and stirred in a reactor equipped with a stirrer, a heating device, and a dropping funnel in an N 2 atmosphere.
• dissolved the intermediate product (amine body) (0.025 mol) and triethylamine (0.25 mol) in 50 ml of 1, 2- dichloroethane was dripped there slowly at 25 degreeC there. After completion of dropping, the reaction was carried out at 70 ° C for 5 hours. Thereafter, the reaction solution was filtered, and the filtrate was separated 5 times with 100 ml of water.
• Polyhydric hydroxyl group-containing compound (C1): pentaerythritol manufactured by Tokyo Chemical Industry Co., Ltd., hydroxyl value 1648
• Polyhydric hydroxyl group-containing compound (C2): Trimethylolethane manufactured by Tokyo Chemical Industry Co., Ltd., hydroxyl value 1401
• Example 1 After 100 parts by mass of the aromatic polyester resin (A1) was vacuum-dried at 110 ° C. for 5 hours, 1 part by mass of the cyclic carbodiimide compound (B1) and 1 part by mass of the polyhydric hydroxyl group-containing compound (C1) having a hydroxyl value of 200 or more were added.
• Example 2 A resin composition (M2) was obtained in the same manner as in Example 1, except that the amount of the polyvalent hydroxyl group-containing compound (C1) was changed from 1 part by mass to 1.5 parts by mass. An isocyanate odor was not felt during the production of the resin composition.
• Table 1 shows the results of the carboxyl group concentration, melt viscosity, reduced viscosity retention ratio and the like of this composition.
• Comparative Example 1 A resin composition (M3) was obtained in the same manner as in Example 1, except that the polyvalent hydroxyl group-containing compound (C1) was not added. An isocyanate odor was not felt during the production of the resin composition.
• Table 1 shows the results of the carboxyl group concentration, melt viscosity, reduced viscosity retention ratio and the like of this composition.
• Example 3 In Example 1, the resin composition (M4) was obtained in the same manner except that (C2) was used instead of (C1) as the polyvalent hydroxyl group-containing compound. An isocyanate odor was not felt during the production of the resin composition.
• Table 1 shows the results of the carboxyl group concentration, melt viscosity, reduced viscosity retention ratio and the like of this composition.
• Comparative Example 2 In Comparative Example 1, the same procedure was performed except that the cyclic carbodiimide compound (B1) as the B component was changed to a polycarbodiimide Sb-P having a linear structure ("STABAXOL (registered trademark) P" manufactured by Rhein Chemie Japan). Thus, a resin composition (M5) was obtained. An isocyanate odor was felt during the production of the resin composition. Table 1 shows the results of the carboxyl group concentration, melt viscosity, reduced viscosity retention ratio and the like of this composition.
• Comparative Example 3 In Comparative Example 1, the same except that the cyclic carbodiimide compound (B1) as the B component was changed to polycarbodiimide LA-1 having a linear structure (“Carbodilite (registered trademark) LA-1” manufactured by Nisshinbo Chemical Co., Ltd.). Thus, a resin composition (M6) was obtained. An isocyanate odor was felt during production of the composition. Table 1 shows the results of the carboxyl group concentration, melt viscosity, reduced viscosity retention ratio and the like of this composition.
• Comparative Example 4 In Comparative Example 1, the same procedure was performed except that the cyclic carbodiimide compound (B1) as the B component was changed to a monocarbodiimide Sb-I having a linear structure (“STABAXOL (registered trademark) I” manufactured by Rhein Chemie Japan). Thus, a resin composition (M7) was obtained. An isocyanate odor was felt during production of the composition. Table 1 shows the results of the carboxyl group concentration, melt viscosity, reduced viscosity retention ratio and the like of this composition.
• Example 5 In Example 1, except that the stearyl alcohol manufactured by Wako Pure Chemical Industries, Ltd., which is a primary alcohol instead of the polyhydric alcohol (C1) as the polyhydric hydroxyl group-containing compound having a hydroxyl value of 200 or more, was used. Similarly, a resin composition (M8) was obtained. No isocyanate odor was felt during the production of the composition. Table 1 shows the results of the carboxyl group concentration, melt viscosity, reduced viscosity retention ratio and the like of this composition. Examples 4 to 13 and Comparative Examples 6 to 15 Hereinafter, the performance when the resin composition of the present application was formed into a molded product was confirmed. 1. Each value in the examples was determined by the following method.
• MV Melt viscosity characteristics
• Intrinsic viscosity Using a mixed solvent of phenol / tetrachloroethane (mass ratio 60/40) and using a Ubbelohde viscosity tube at 35 ° C. according to a conventional method.
• Isocyanate gas generation amount 30 mg of a pellet sample of the resin composition was heated at 280 ° C. for 10 minutes in a heating furnace under a constant air flow (100 ml / min), and the generated isocyanate gas was collected and subjected to gas chromatography. The amount of isocyanate gas generated was measured. The results are shown in Table 2.
• the isocyanate gas generation amount shown in Table 2 is a value per 1 g of the pellet-like sample.
• Aromatic polyester resin (component A) The same aromatic polyester resin (component A) as in Example 1 was used.
• Cyclic carbodiimide compound (component B) As the carbodiimide compound (component B), in addition to the above-described B1, as the B2, an aromatic carbodiimide compound line Chemie Japan Co., Ltd., “STABAXOL (registered trademark)” P400 was used.
• Polyhydric hydroxyl group-containing compound component The following compounds were used as the polyvalent hydroxyl group-containing compound (C component).
• C3 Glycerin mono 12-hydroxystearate (hydroxyl value 420, manufactured by Riken Vitamin Co., Ltd., “Riquemar (registered trademark)” HC-100)
• C4 Triglycerin stearic acid partial ester (hydroxyl value 280, manufactured by Riken Vitamin Co., Ltd., “Riquemar (registered trademark)” AF-70)
• C6 Decaglycerin monolaurate (hydroxyl value 600, manufactured by Riken Vitamin Co., Ltd., “Poem (registered trademark)” L-021)
• C7 Propylene glycol monobehenate (hydroxyl value 145, manufactured by Riken Vitamin Co., Ltd., “Riquemar (registered trademark)” PB-100) (4) Others The following compounds were used as antioxidants.
• E1 Phenolic antioxidant, “Irganox (registered trademark)” 1010 manufactured by BASF Japan Ltd.
• Aromatic polyester resin (A1), cyclic carbodiimide compound (component B), polyvalent hydroxyl group-containing compound (component C) and antioxidant (E1) are weighed in the composition shown in Table 2, then dry blended, and biaxial extrusion Machine (TEX-30 manufactured by Nippon Steel Works, Ltd.) with a cylinder temperature of 260 ° C., a screw speed of 130 rpm, and an extrusion rate of 12 kg / h, melt kneading and cooling the discharged strand-shaped molten resin
• the pellets of the resin composition were obtained by cutting with a pelletizer, and various evaluations were performed.
• Aromatic polyester resin (component A) Polyethylene terephthalate (FK-OM) manufactured by Teijin Ltd. was used as the aromatic polyester resin (component A) (hereinafter sometimes referred to as (A2)).
• the intrinsic viscosity of the aromatic polyester resin (A2) was 0.63 dL / g (reduced viscosity was 0.85 dl / g).
• the carboxyl group concentration was 15 eq / ton
• melt viscosity was implemented at 280 degreeC.
• C1 Pentaerythritol (hydroxyl number 1645, manufactured by Kanto Chemical Co., Inc.)
• C3 Glycerin mono 12-hydroxystearate (hydroxyl value 420, manufactured by Riken Vitamin Co., Ltd., “Riquemar (registered trademark)” HC-100)
• Aromatic polyester resin (A2), cyclic carbodiimide compound (B1), polyhydric hydroxyl group-containing compound (C component) are weighed in the composition shown in Table 3, and Lab Plast Mill (manufactured by Toyo Seiki Seisakusho Co., Ltd.) is used. It was used and melt-kneaded at a resin temperature of 280 ° C.

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