Classifications

• • 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
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
  • C08J5/10—Reinforcing macromolecular compounds with loose or coherent fibrous material characterised by the additives used in the polymer mixture
• • 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
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
  • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
  • C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
• • 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
  • C08K5/10—Esters; Ether-esters
  • C08K5/101—Esters; Ether-esters of monocarboxylic acids
  • C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
• • 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
  • C08K7/00—Use of ingredients characterised by shape
  • C08K7/02—Fibres or whiskers
  • C08K7/04—Fibres or whiskers inorganic
  • C08K7/14—Glass
• • 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
• • 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
  • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
  • C08K13/04—Ingredients characterised by their shape and organic or inorganic ingredients
• • 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
  • C08K2201/00—Specific properties of additives
  • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K

Definitions

• the present invention relates to a polybutylene terephthalate resin composition and a thin-walled molded article that are excellent in mechanical strength, impact strength, and fluidity and have little warping deformation. More specifically, the present invention relates to a polybutylene terephthalate resin composition and a thin-walled molded article that are optimal for molded articles such as switches and capacitors, and electrical and electronic parts. Background art
• Crystalline thermoplastic polyester resins such as polyalkylene terephthalate resins, are excellent in mechanical properties, electrical properties, other physical and chemical properties, and have good processability. It is used for a wide range of applications such as parts.
• Such crystalline thermoplastic polyester resins are used alone in various molded products, but depending on the application field, various reinforcing agents and additives may be blended for the purpose of improving their properties, particularly mechanical properties. Has been done. In fields where high mechanical strength and rigidity are required, it is well known to use fibrous reinforcing agents such as glass fibers and carbon fibers.
• a crystalline thermoplastic polyester resin containing a general fibrous reinforcing agent has improved mechanical strength and impact strength, but has a large shrinkage anisotropy generated during the solidification process during molding such as injection molding. As a result, there is a problem that warpage deformation of the molded product becomes remarkably large. For this reason, polybutylene terephthalate resin containing a general fibrous reinforcing agent has been considered difficult to apply to thin plate-shaped molded products.
• An object of the present invention is to provide a polybutylene terephthalate resin composition having excellent mechanical strength and impact strength, little warpage deformation and improved fluidity (melt fluidity), and a molded product thereof.
• the present inventors have achieved the above object by combining a polybutylene terephthalate resin with a glass fiber having a flat cross-sectional shape and a specific glycerin fatty acid ester.
• the present inventors have found that a resin composition that can be obtained is obtained, and have completed the present invention.
• the present invention (A) For 100 parts by weight of polybutylene terephthalate resin, (B) 40 to 140 parts by weight of glass fiber having a flat cross-sectional shape, (C) Polybutylene comprising glycerin and / or a dehydrated condensate thereof and a fatty acid having 12 or more carbon atoms, and 0.05 to 5 parts by weight of a glycerin fatty acid ester having a hydroxyl value measured by the method described herein of 200 or more.
• a terephthalate resin composition and a thin molded article comprising the same.
• the polybutylene terephthalate resin composition of the present invention is excellent in mechanical strength and impact strength, has little warpage deformation, and is excellent in fluidity (melt fluidity).
• Polybutylene terephthalate resin is a polymerization component comprising at least terephthalic acid (terephthalic acid or an ester-forming derivative thereof) and alkylene glycol having 4 carbon atoms (1,4-butanediol or an ester-forming derivative thereof). It is a thermoplastic resin.
• the (A) polybutylene terephthalate resin of the present invention is not limited to polybutylene terephthalate homopolymer, but also includes polybutylene terephthalate containing isophthalic acid-modified polybutylene terephthalate and isophthalic acid-modified polyester.
• An isophthalic acid-modified polybutylene terephthalate and a polybutylene terephthalate containing an isophthalic acid-modified polyester can be preferably used.
• Isophthalic acid-modified polybutylene terephthalate is an alkylene glycol component of 1,4-butanediol or an ester-forming derivative thereof, and isophthalic acid or an ester-forming derivative thereof together with terephthalic acid or an ester-forming derivative thereof (lower alcohol ester such as dimethyl ester) Etc.) as a comonomer unit.
• the isophthalic acid-modified polyester includes terephthalic acid or an ester-forming derivative thereof and alkylene glycol having 2 to 4 carbon atoms, particularly preferably ethylene glycol, trimethylene glycol, 1,4-butanediol or an ester-forming derivative thereof.
• This is a copolymer comprising, as a main component, a polyester obtained by polycondensation reaction, into which isophthalic acid or an ester-forming derivative thereof (such as a lower alcohol ester such as dimethyl ester) is introduced as a comonomer unit.
• the amount of isophthalic acid comonomer unit introduced in isophthalic acid-modified polybutylene terephthalate or isophthalic acid-modified polyester is preferably 5 to 30 mol%, more preferably 10 to 30 mol%, and particularly preferably 10 to 20 mol%. If the amount introduced is less than 5 mol%, the crystallinity is high, and the low warpage effect may be low. Further, when the introduction amount exceeds 30 mol%, the strength and thermal stability, which are the advantages of the original polybutylene terephthalate, are greatly reduced, and the crystallization is remarkably reduced and delayed, thereby reducing the molding cycle.
• the content of isophthalic acid with respect to the total dicarboxylic acid component is preferably 5 to 30 mol%.
• Polybutylene terephthalate as a base resin can be used as a copolymer copolymerized with a copolymerizable monomer (hereinafter sometimes referred to simply as a copolymerizable monomer) as long as the effects of the present invention are not impaired. it can.
• a copolymerizable monomer include dicarboxylic acid components excluding terephthalic acid and isophthalic acid, diols other than alkylene glycol having 2 to 4 carbon atoms, oxycarboxylic acid components, and lactone components.
• a copolymerizable monomer can be used 1 type or in combination of 2 or more types.
• Dicarboxylic acids include aliphatic dicarboxylic acids (for example, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, hexadecandioyl carboxylic acid, C 4 ⁇ 40 dicarboxylic acids such as dimer acid, preferably C 4 ⁇ 14 dicarboxylic acids), alicyclic dicarboxylic acid component (e.g., hexahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, hymic C 8 ⁇ 12 dicarboxylic acids, such as acid), an aromatic dicarboxylic acid component other than terephthalic acid (e.g., naphthalene dicarboxylic acids such as phthalic
• aliphatic dicarboxylic acids for example, succ
• polyvalent carboxylic acid such as trimellitic acid and pyromellitic acid, or its ester formation derivative (alcohol ester etc.) etc. as needed.
• a polyfunctional compound such as trimellitic acid and pyromellitic acid, or its ester formation derivative (alcohol ester etc.) etc.
• a branched polybutylene terephthalate resin can also be obtained.
• Diols include, for example, aliphatic alkanediols excluding 1,4-butanediol [for example, alkanediols (for example, ethylene glycol, trimethylene glycol, propylene glycol, neopentyl glycol, hexanediol ( 1,6-hexanediol), octanediol (1,3-octanediol, 1,8-octanediol, etc.), lower alkane diols, such as decanediol, preferably a straight chain or branched chain C 2 ⁇ 12 alkane Diols, more preferably linear or branched C 2-10 alkane diols); (poly) oxyalkylene glycols (eg glycols having a plurality of oxy C 2-4 alkylene units, eg diethylene glycol, diprop
• a polyol such as glycerin, trimethylolpropane, trimethylolethane, pentaerythritol, or an ester-forming derivative thereof may be used in combination.
• a polyfunctional compound such as glycerin, trimethylolpropane, trimethylolethane, pentaerythritol, or an ester-forming derivative thereof may be used in combination.
• a branched polybutylene terephthalate resin can also be obtained.
• the proportion of the copolymerizable monomer can be selected from the range of, for example, about 0.01 to 30 mol%, and is usually 1 to 30 mol%, preferably 3 to 25 mol%, more preferably 5 to 5 mol%. It is about 20 mol% (for example, 5 to 15 mol%).
• the proportion of the homopolyester and the copolyester is such that the proportion of the copolymerizable monomer is relative to the total monomers.
• the range is about 0.1 to 30 mol% (preferably 1 to 25 mol%, more preferably 5 to 25 mol%).
• the former / the latter 99/1 to 1/99 (weight ratio), preferably It can be selected from the range of 95/5 to 5/95 (weight ratio), more preferably about 90/10 to 10/90 (weight ratio).
• the intrinsic viscosity (IV) of the (A) polybutylene terephthalate resin is preferably 1.0 dL / g or less, and more preferably 0.9 dL / g or less.
• polybutylene terephthalate resins or modified polyesters with different intrinsic viscosities for example by blending polybutylene terephthalate resins with intrinsic viscosities of 1.2 dL / g and 0.8 dL / g, an intrinsic viscosity of 1.0 dL / g or less is achieved. It may be realized.
• the intrinsic viscosity (IV) can be measured, for example, in O-chlorophenol at a temperature of 35 ° C.
• the glass fiber having a flat cross-sectional shape used in the present invention is a long diameter (longest linear distance in the cross section) and a short diameter (longest straight distance in the direction perpendicular to the long diameter).
• the glass fiber has a ratio of 1.3 to 10, preferably 1.5 to 8, particularly preferably 2 to 5.
• Specific shapes include a substantially oval shape, a substantially oval shape, a substantially eyebrow shape, and the like.
• (B) Glass fiber having a flat cross-sectional shape is excellent in mechanical strength and impact strength, suppresses warpage deformation, and is excellent in moldability.
• the glass fiber having a flat cross-sectional shape preferably has an average cross-sectional area of 100 to 300 micro square meters. If it is smaller than 100 micro square meters, the mechanical strength and impact strength are insufficient, and if it exceeds 300 micro square meters, problems such as gate clogging at the time of injection molding and wear of molds and molding machines occur.
• the amount of (B) glass fiber having a flat cross-sectional shape used in the present invention is 40 to 140 parts by weight, preferably 50 to 120 parts by weight, per 100 parts by weight of (A) polybutylene terephthalate resin.
• the blending amount is less than 40 parts by weight, the mechanical strength and impact strength are low, and when it exceeds 140 parts by weight, the fluidity is remarkably deteriorated.
• Such glass fiber (B) can be used regardless of the glass fiber form at the time of blending A glass, E glass, an alkali-resistant glass composition containing a zirconia component, chopped strands, roving glass, or the like.
• the glass fiber having a flat cross-sectional shape used in the present invention uses a nozzle having an appropriate hole shape such as an oval, an ellipse, a rectangle, or a slit as a bushing used for discharging molten glass.
• a nozzle having an appropriate hole shape such as an oval, an ellipse, a rectangle, or a slit as a bushing used for discharging molten glass.
• Prepared by spinning Also prepared by spinning molten glass from a plurality of adjacent nozzles having various cross-sectional shapes (including circular cross-sections), and joining the spun molten glass into a single filament it can.
• the (C) glycerin fatty acid ester used in the present invention is a fatty acid ester composed of glycerin and / or a dehydration condensate thereof and a fatty acid having 12 or more carbon atoms and having a hydroxyl value measured by the method described later of 200 or more.
• a fluidity improver or the like is added to a polybutylene terephthalate resin, even if the fluidity can be improved, a decrease in properties such as mechanical strength and toughness of the polybutylene terephthalate resin itself cannot be avoided.
• the fluidity of the polybutylene terephthalate resin composition can be efficiently improved while maintaining the above characteristics at a high level.
• Glycerin fatty acid ester can be produced by a method known per se, and a commercially available product may be used, and the esterification is adjusted so that the hydroxyl value measured by the method described below is 200 or more. Preferably, it has a hydroxyl value of 250 or more. When the hydroxyl value is less than 200, the effect of improving the fluidity is small, which is not preferable.
• Examples of the fatty acid having 12 or more carbon atoms constituting the ester of glycerin fatty acid ester include lauric acid, oleic acid, palmitic acid, stearic acid, behenic acid, montanic acid and the like, preferably a fatty acid having 12 to 32 carbon atoms, particularly Preferably, fatty acids having 12 to 22 carbon atoms are used, and lauric acid, stearic acid or behenic acid is particularly preferred. Those having less than 12 carbon atoms are not preferable because the heat resistance may be lowered, and those having more than 32 carbon atoms are not preferable because the effect of improving fluidity is small.
• glycerin fatty acid esters examples include glycerin monostearate, glycerin monobehenate, diglycerin monostearate, triglycerin monostearate, tetraglycerin stearic acid partial ester, decaglycerin lauric acid partial ester, and the like.
• the blending amount of (C) glycerin fatty acid ester is 0.05 to 5 parts by weight, preferably 0.5 to 3 parts by weight with respect to 100 parts by weight of (A) polybutylene terephthalate resin. (C) If the blending amount of glycerin fatty acid ester is less than 0.05 parts by weight, the effect of improving the fluidity may not be sufficiently obtained, and if it exceeds 5 parts by weight, the amount of gas generation increases with molding, There is a risk of damage to the appearance and mold contamination.
• the resin composition of the present invention may contain other resins as needed within a range not impairing the effects of the present invention.
• Other resins include polyester resins other than polybutylene terephthalate resins (polyethylene terephthalate, polytrimethylene terephthalate, etc.), polyolefin resins, polystyrene resins, polyamide resins, polyacetals, polyarylene oxides, polyarylene sulfides, fluorine resins, etc. Is exemplified.
• copolymers such as acrylonitrile-styrene resin, acrylonitrile-butadiene-styrene resin, and ethylene-ethyl acrylate resin are also exemplified. These other resins may be used alone or in combination of two or more.
• additives may be added to the resin composition of the present invention.
• additives include various stabilizers (antioxidants, ultraviolet absorbers, heat stabilizers, etc.), nucleating agents (crystallization nucleating agents), flame retardants, lubricants, mold release agents, antistatic agents, dyes / pigments, etc. Colorants, dispersants, and the like.
• a phosphorus stabilizer when polybutylene terephthalate and a modified polyester having a different alkylene glycol component are used in combination, it is preferable to add a phosphorus stabilizer to suppress transesterification.
• the phosphorus stabilizer used include organic phosphite compounds, phosphonite compounds, and metal phosphates.
• Specific examples include bis (2,4-di-t-4methylphenyl) pentaerythritol diphosphite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, tetrakis (2,4 Examples of the -di-t-butylphenyl) -4,4'-biphenylene phosphonite and the metal phosphate include monocalcium phosphate and monohydrate of monobasic sodium phosphate.
• reinforcing fillers can be added to the resin composition of the present invention as needed within a range not impairing the effects of the present invention.
• Other reinforcing fillers include glass fibers other than those specified in the present invention, milled glass fibers, glass beads, glass flakes, silica, alumina fibers, zirconia fibers, potassium titanate fibers, carbon fibers, graphite, calcium silicate, Silicates such as aluminum silicate, kaolin, talc and clay, metal oxides such as iron oxide, titanium oxide, zinc oxide, antimony oxide and alumina, carbonates and sulfates of metals such as calcium, magnesium and zinc, and carbonization
• the organic filler include silicon polyester, silicon nitride, boron nitride and the like, and examples of the organic filler include high melting point aromatic polyester fiber, liquid crystalline polyester fiber, aromatic polyamide fiber, fluororesin fiber, and polyimide fiber.
• the composition of the present invention is easily prepared by equipment and methods generally used as conventional resin composition preparation methods. For example, after mixing each component, kneading and extruding with a single-screw or twin-screw extruder to prepare pellets, then forming the pellets, once preparing pellets with different compositions, mixing the pellets in a predetermined amount Any method can be used, such as a method of obtaining a molded product having a desired composition after molding and a method of directly charging one or more of each component into a molding machine. Further, mixing a part of the resin component as a fine powder with other components and adding it is a preferable method for uniformly blending these components.
• the fluidity of the resin composition of the present invention can reflect the melt viscosity under a condition under a constant piston flow shear rate as an index.
• the melt viscosity of the resin composition of the present invention is 200 Pa ⁇ s or less, preferably 170 Pa ⁇ s or less, more preferably 150 Pa ⁇ s or less (for example, at a shear rate of 1000 sec ⁇ 1 at 260 ° C. in accordance with ISO 11443 (for example, 50 to 150 Pa ⁇ s).
• the measurement results are obtained in units of Pa ⁇ s as described above. The lower the numerical value, the better the fluidity during melting and the better fluidity during molding.
• melt index measured under conditions of ASTM D-1238 at 235 ° C and a load of 2160g is used as an index of fluidity, but the melt index is measured under a constant load.
• the shear rate is different.
• the melt viscosity measurement index under a constant piston flow is considered to be an index closer to the actual flow characteristics considering that actual injection molding is performed with a constant piston flow.
• the melt viscosity under such a constant shear rate condition is used as an index of fluidity.
• the resin composition of the present invention is excellent in melt fluidity as described above, it has good moldability and is useful for producing a molded article or molded article having high mechanical strength and heat resistance. .
• a molded product having a thin portion is suitable for manufacturing a molded product having a thin portion.
• it can be molded at an injection speed of 67 mm / sec with an injection molding machine having a clamping force of 100 t and a screw diameter of ⁇ 30 mm.
• the flow length at a thickness of 1 mm may be required to be 120 mm or more, and the flow length of 120 mm or more is possible with the resin composition of the present invention.
• Thin parts with a thickness of 1 mm or less in a part of the molded product include switches, capacitors, connectors, integrated circuits (ICs), relays, resistors, light emitting diodes (LEDs), coil bobbins, electronic devices, and portable terminals. , ECUs, various sensors, power modules, gear parts and their peripheral devices or their housings or chassis.
• Injection molding extrusion molding, compression molding, blow molding, vacuum molding, rotational molding, gas injection molding, etc. can be applied as a molding method for filling the resin into the mold, but injection molding is common. .
• Example 1 Injection molding, extrusion molding, compression molding, blow molding, vacuum molding, rotational molding, gas injection molding, etc. can be applied as a molding method for filling the resin into the mold, but injection molding is common. .
• Example 7 0.15 weight part of monocalcium phosphate is further added to the composition in a table

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• 2007
  • 2007-12-25 JP JP2007331722A patent/JP2009155367A/ja active Pending
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