WO2006095901A1 - Resine de polyester copolymerisee, methode de production et composition de resine contenant la resine de polyester copolymerisee - Google Patents

Resine de polyester copolymerisee, methode de production et composition de resine contenant la resine de polyester copolymerisee Download PDF

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Publication number
WO2006095901A1
WO2006095901A1 PCT/JP2006/304857 JP2006304857W WO2006095901A1 WO 2006095901 A1 WO2006095901 A1 WO 2006095901A1 JP 2006304857 W JP2006304857 W JP 2006304857W WO 2006095901 A1 WO2006095901 A1 WO 2006095901A1
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Prior art keywords
acid
polyester resin
compound
group
mol
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PCT/JP2006/304857
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English (en)
Japanese (ja)
Inventor
Hideki Tanaka
Yasunari Hotta
Kazunori Komatsu
Hiroshi Tachika
Naoki Watanabe
Takahiro Nakajima
Original Assignee
Toyo Boseki Kabushiki Kaisha
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Priority claimed from JP2005107617A external-priority patent/JP2006282937A/ja
Priority claimed from JP2005107619A external-priority patent/JP2006282938A/ja
Priority claimed from JP2005108849A external-priority patent/JP2006290907A/ja
Priority claimed from JP2005176530A external-priority patent/JP2006348182A/ja
Priority claimed from JP2005266789A external-priority patent/JP2007077267A/ja
Priority claimed from JP2005266790A external-priority patent/JP2007077268A/ja
Priority claimed from JP2005316448A external-priority patent/JP2006285195A/ja
Application filed by Toyo Boseki Kabushiki Kaisha filed Critical Toyo Boseki Kabushiki Kaisha
Publication of WO2006095901A1 publication Critical patent/WO2006095901A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/84—Boron, aluminium, gallium, indium, thallium, rare-earth metals, or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/06—Polyurethanes from polyesters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
    • C09J167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/087—Binders for toner particles
    • G03G9/08742—Binders for toner particles comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • G03G9/08755—Polyesters

Definitions

  • Copolyester resin and method for producing the same and resin composition containing copolyester resin
  • the present invention relates to a copolymerized polyester resin manufactured in the presence of a catalyst containing at least an aluminum compound, a resin composition containing a copolymerized polyester resin, and a coating material using the resin composition , Toner, non-resin resin, painted metal plate, hot melt adhesive, extrusion coating agent. Further, the present invention relates to a method for producing a copolymerized polyester resin.
  • the present invention relates to a copolymerized polyester resin produced with little coloring and without using a heavy metal catalyst, and a coating material thereof. Furthermore, the present invention relates to a method for producing such a copolymer polyester resin.
  • the present invention does not use a metal polymerization catalyst such as a tin compound, an antimony compound, a germanium compound, and a titanium compound, and mainly uses a polymerization catalyst mainly composed of an aluminum compound for the pre-coating of a metal plate.
  • the present invention relates to a polymerized polyester resin, a resin composition containing the same, and a metal plate coated with the resin composition.
  • the present invention provides a copolymer polyester resin and copolymer polyester using a polymerization catalyst mainly composed of an aluminum compound without using a metal polymerization catalyst such as tin compounds, antimony compounds, germanium compounds, and titanium compounds.
  • the present invention relates to a method for producing a resin, a resin composition for coating, and a coated metal sheet coated with the same.
  • the present invention also relates to an electrostatic charge developing toner comprising, as a binder component, a copolymerized polyester resin for electrostatic charge image using a polymerization catalyst mainly having an aluminum compound power.
  • the present invention relates to a recording apparatus with thermal fixing, mainly an electrophotographic printer such as a copying machine, a laser printer, and an LED printer, a printing apparatus, or an electrostatic recording system such as ion flow, ion injection, and discharge recording.
  • the present invention relates to a toner for developing an electrostatic image used for developing a latent image due to an electrostatic charge in a printer using the above, a printer using an electrostatic latent image formed by spontaneous polarization of a ferroelectric, and a printing device. More specifically, since a polymerization catalyst mainly composed of an aluminum compound is used, it is possible to provide a toner resin for electrostatic charge development that is inexpensive, does not contain heavy metals, and has excellent color image recording quality. I can do it.
  • the present invention also relates to a can outer surface coating resin composition
  • a can outer surface coating resin composition comprising a copolymer polyester resin obtained using a polymerization catalyst containing an aluminum compound as an active ingredient, and a can outer surface coated metal sheet coated with the same.
  • the present invention also relates to a paint resin composition for a can inner surface containing a copolymer polyester resin obtained using a polymerization catalyst containing an aluminum compound as an active ingredient, and a coated metal plate for a can inner surface coated with the same.
  • the present invention comprises a copolymerized polyester resin obtained by using a polymerization catalyst mainly composed of an aluminum compound without using a metal polymerization catalyst such as tin compounds, antimony compounds, germanium compounds and titanium compounds.
  • a polymerization catalyst mainly composed of an aluminum compound without using a metal polymerization catalyst such as tin compounds, antimony compounds, germanium compounds and titanium compounds.
  • the present invention relates to crystalline polyester resin and film, fabric and metal hot melt adhesives and extrusion coating agents using the same.
  • Polyester rosin is used in many fields, including physical properties, environmental suitability, adhesive properties, and price.
  • low molecular weight polyesters having a number average molecular weight of less than 7000 are used in powder paints, adhesives, various coating agents, binders and the like.
  • a carboxyl group-containing compound is used in polymerizing this low molecular weight polyester resin.
  • a catalyst for promoting esterification or transesterification is usually used.
  • antimony, titanium, germanium, and tin compounds are often used. These catalyst compounds are selected from the viewpoint of catalytic activity.
  • the color of rosin is darkened when antimony is used, and yellow when titanium is used.
  • germanium the color of rosin is good. It is very expensive and difficult to use.
  • the catalyst activity decreases due to the water generated during the force polymerization, which is a problem common to germanium and titanium, and the polymerization time becomes longer or the catalyst needs to be supplemented.
  • a polymerization catalyst such as a tin compound or an antimony compound contains a heavy metal, and a polyester not containing these is desired.
  • a polymerization formulation of a tin compound is disclosed in, for example, Patent Document 1!
  • Patent Document 1 Japanese Patent Application Laid-Open No. 6-220359
  • the first requirement for a coated metal sheet is excellent workability such as press working.
  • Conventionally used coating resins include alkyd resin, vinyl resin, and silicone resin, and are used as solvent-based, water-dispersed, and powder coatings.
  • the precoat resin composition requires a high degree of workability and hardness, and the performance of the conventional solvent system for refrigerator side top plates that require alkali resistance, gasket resistance, and contamination resistance is required.
  • Powder paint is used because it is inadequate, but it has excellent stain resistance but is not workable, and has a slower line speed and higher cost than solvent-based ones.
  • resin having excellent processability has insufficient weather resistance, and post-coating is mostly used for outdoor home appliances.
  • Patent Document 2 titan polymerization catalyst
  • Patent Document 3 tin polymerization catalyst
  • Patent Document 4 antimony system Proposal of polymerization catalyst
  • Patent Document 2 Japanese Patent Laid-Open No. 7-113057
  • Patent Document 3 Japanese Patent Application Laid-Open No. 2004-43722
  • Patent Document 4 JP-A-7-26200
  • Polymerization catalysts such as tin compounds and antimony compounds contain heavy metals, and V and polyesters containing these are desired.
  • the copolymerized polyester resin is colored, and when adipic acid is used as the copolymerization component, aliphatic dicarboxylic acid such as sebacic acid is used as the copolymer component. Inferior to the white paint, which is highly colored, the original white color cannot be obtained.
  • the germanium compound can be used effectively as the polymerization catalyst, but the price is extremely high.
  • polyester resin has excellent processability. It is not necessarily sufficient in moisture resistance and corrosion resistance, and as a primer resin resin used in combination, moisture resistance and corrosion resistance have been problems.
  • epoxy resin has excellent defects in moisture resistance and corrosion resistance, but lacks flexibility, and therefore has a drawback in that it cannot be applied to high-level processing. As a result of these circumstances, copolymerized polyester resin obtained by copolymerizing bisphenol A skeleton is currently the mainstream as a resin for primer coatings.
  • a resin for a primer coating a raw material containing an alkylene oxide adduct of bisphenol A and Z or bisphenol F as a glycol component is used, and a copolyester resin is produced in the presence of a polymerization catalyst.
  • a polymerization catalyst for example, those using a tin compound such as hydroxyptyl tin oxide as a polymerization catalyst (Patent Document 5), those using a titanium compound such as tetrabutyl titanate as a polymerization catalyst (Patent Documents 6 and 7) and An antimony compound such as antimony trioxide is known as a polymerization catalyst (Patent Document 8).
  • Patent Document 5 Japanese Patent Laid-Open No. 2001-81160
  • Patent Document 6 Japanese Patent No. 3317400
  • Patent Document 7 Japanese Patent Laid-Open No. 2001-278966
  • Patent Document 8 Japanese Patent Publication No. 62-5467
  • a powder that develops an electrostatic latent image in an electrophotographic system, an electrostatic recording system, and the like and is finally transferred to a recording paper or a substrate such as a film to form an image is referred to as toner.
  • a toner for developing an electrostatic image a kneader added with a colorant, a charge control agent, etc. after kneading, pulverizing and further classifying, externally adding a fluidity modifier or the like as necessary. Particles produced by a so-called pulverization method are used.
  • polyester resin As binder resin, styrene-acrylic copolymer resin has been mainly used, but in recent years, polyester resin having excellent low-temperature fixability, image surface gloss, and toughness has been accompanied by higher speed and colorization. It tends to be used.
  • the polyester resin used mainly is an unsaturated polyester resin obtained by condensation polymerization of aliphatic unsaturated carboxylic acids such as fumaric acid and maleic acid and diols having a bisphenol structure.
  • the A proposal regarding a toner using such an unsaturated polyester resin can be found in, for example, Patent Document 9.
  • aromatic polycarboxylic acids such as terephthalic acid and isophthalic acid
  • aliphatic diols such as ethylene glycol
  • alicyclic diols such as cyclohexane dimethanol
  • a number of patent proposals have been made on saturated polyester resin, which also includes the above-mentioned aromatic diol having a bisphenol structure.
  • Poly Ester resin has excellent gloss on the surface of the image after fixing, realizing a wide color reproduction range with good color development.
  • the polyester resin used as the main component of the toner is polymerized and manufactured in the presence of a polymerization catalyst.
  • a polymerization catalyst for example, those using tin compounds such as dibutyltinoxide and dibutyltin as polymerization catalysts (Patent Documents 12 to 14), and those using titanium compounds such as tetrabutyl titanate as polymerization catalysts (Patent Document 15) Also known are those using an antimony compound such as antimony trioxide and antimony as a polymerization catalyst (Patent Document 16).
  • Germanium compounds are powerful rare substances that can be used effectively as the above-mentioned polymerization catalysts, and have limited earth resources.
  • germanium compounds have a problem that they cannot provide toners that are extremely expensive in price.
  • Tiny compounds and antimony compounds also have a problem of coloring the copolyester resin. Furthermore, both are classified as heavy metals, and it is desirable to polymerize them without using them.
  • toner obtained by developing an electrostatic latent image on a recording sheet in a dry electrophotographic system or an electrostatic recording system is heated and fixed.
  • a heating method a heat roll is generally used.
  • silicone rubber, fluorine rubber, etc. having high releasability and elasticity are used.
  • the elastic rubber roll since the elastic rubber roll has a large heat capacity, it requires preheating, and it cannot be used for a while after the device is turned on. For the same reason, it is necessary to constantly pass current to keep the heater warm, so there is a big problem in terms of power saving.
  • a method of heating with a thermal head through a heat-resistant film has been proposed and put into practical use in some models.
  • the toner particles When heated, the toner particles melt and are fixed on the recording paper.
  • the melted toner resin partially adheres not only to the recording paper but also to the heat source side and contaminates the surface of the heat source.
  • This phenomenon is called an offset phenomenon, and if the fixing process is further continued with a contaminated heat source, the contamination is transferred to the subsequent recording paper and the quality of the recorded image is significantly reduced.
  • the powerful offset phenomenon is particularly noticeable in the fixing method in which the heat-resistant film and the thermal head described above are combined.
  • the toner binder resin has been improved! It is known that the offset phenomenon is reduced by broadening the molecular weight distribution of the binder resin and partially crosslinking or gelling.
  • a toner is produced by kneading and dispersing a colorant, a charge control agent, and in some cases magnetic powder, etc. in a binder resin, and adding a fluidizing agent after pulverization and classification with a jet mill or the like.
  • Patent Documents 17 and 18 propose that an amide wax, a ketone wax, a specific alkyl ketene dimer, or the like is blended as an offset preventing agent.
  • Patent Documents 19 to 29, etc. have proposed that the fixing properties can be improved by introducing alkyl or alkenyl-substituted succinic acid into the copolymer component of polyester resin as well.
  • Patent Documents 28 and 29 are proposed mainly for improving fixing characteristics in a fixing method in which a heat-resistant film and a thermal head are combined. Although the fixing characteristics are somewhat improved by such means, it is not possible to copolymerize much as the glass transition temperature is lowered as in the case of dimer acid copolymerization.
  • Patent Documents 30 and 31 include cyclohexene dicarboxylic acid anhydride (cyclohexane dicarboxylic acid) anhydride or cyclohexane dicarboxylic acid anhydride as a polyvalent carboxylic acid component, and a polyvalent carboxylic acid component having a bisphenol structure.
  • toner compositions for electrophotography using polyester resin obtained from alcohol by atmospheric pressure polymerization Such a proposal is Glass transition temperature of unsaturated polyester resin obtained by polycondensation of aliphatic unsaturated carboxylic acids such as fumaric acid and maleic acid and diols having bisphenol structure, which are mainly used as polyester resin for general use The main purpose is to improve the storage stability of the toner.
  • Patent Document 9 Japanese Patent Application Laid-Open No. 47-12334
  • Patent Document 10 Japanese Patent Laid-Open No. 4 12367
  • Patent Document 11 JP-A-5-165252
  • Patent Document 12 Japanese Patent Publication No. 8-30027
  • Patent Document 13 Japanese Patent Laid-Open No. 8-183841
  • Patent Document 14 JP 7-128907 A
  • Patent Document 15 Japanese Patent Application Laid-Open No. 8-129269
  • Patent Document 16 Japanese Patent Laid-Open No. 9 104741
  • Patent Document 17 JP 59-164560 A
  • Patent Document 18 Japanese Patent Application Laid-Open No. 59-228661
  • Patent Document 19 JP-A-59-164560
  • Patent Document 21 JP 59-29257 A
  • Patent Document 22 JP 59-29258 A
  • Patent Document 23 JP-A-59-198469
  • Patent Document 24 JP-A-59-223456
  • Patent Document 25 Japanese Patent Application Laid-Open No. 60-4947
  • Patent Document 26 Japanese Patent Laid-Open No. 61-176948
  • Patent Document 27 JP-A-61-240248
  • Patent Document 28 Japanese Patent Application Laid-Open No. 3-155563
  • Patent Document 29 Japanese Patent Application Laid-Open No. 3-122664
  • Patent Document 30 JP-A-56-1952
  • Patent Document 31 JP-A-58-17452
  • Metal cans are widely used as beverages, foods, and other packaging containers.
  • the outer surfaces of these cans are printed and painted for the purpose of metal anticorrosion, aesthetics, and content labeling.
  • a primer called size coating is applied to a surface-treated metal plate, followed by an intermediate coating called white coating (usually white), and several colors are added with oil-based ink. Printing is done.
  • white coating usually white
  • finish varnish is applied to protect the surface and improve the finished appearance. Size and white coating are often omitted from time to time. Finishing varnishes have often been used in recent years because the method of applying wet ink without drying the oil-based ink is omitted because the drying process is omitted.
  • finishing varnish The main characteristics of finishing varnish are as follows: (1) There is no suspicion of toxicity and environmental pollution of heavy metals (catalysts, etc.), environmental hormones, etc. (2) Wet ink properties: Finish varnish with wet-on-wet When the coating is applied, the ink layer will not bleed or aggregate, and the finish varnish layer will not be dented or repelled. (3) Blocking resistance: Sufficient workability to withstand complex molding and processing. Good adhesion to the substrate, no sticking force even when the coating plates are stacked, (4) Retort resistance: for heat sterilization (130 ° C x 30 min) treatment for sterilization of the inner surface of food cans And endurance.
  • the glass transition temperature (Tg) of the coating film is high, and the blocking resistance is good, but the workability is inferior. Is low and the workability is good. It has not reached.
  • the baking temperature of epoxy phenolic resin is high.
  • the generation of environmental hormones caused by bisphenol type resin becomes a problem.
  • polymerization catalysts for polyethylene terephthalate such as antimony, titanium, germanium, tin, and aluminum
  • Patent Document 35 an aluminum-based polymer has been proposed as a polymerization catalyst for copolymerized polyester resin.
  • Patent Document 35 there are no examples of specific polymerization catalysts disclosed at present.
  • Patent Document 32 Japanese Patent Laid-Open No. 50-32230
  • Patent Document 33 Japanese Patent Laid-Open No. 55-5936
  • Patent Document 34 Japanese Unexamined Patent Application Publication No. 2004-256633
  • Patent Document 35 Japanese Patent Application Laid-Open No. 2004-126544
  • tin-based, antimony-based, titanium-based, germanium-based, and the like are known as polymerization catalysts for copolymer polyesters.
  • polymerization catalysts for copolymer polyesters are known as polymerization catalysts for copolymer polyesters.
  • the following problems remain in these polymerization catalyst species.
  • Polymerization catalysts such as tin compounds and antimony compounds contain heavy metals, and polyesters that do not contain these are desired.
  • the antimony compound When the obtained copolymer polyester resin is dissolved in a solvent to form a varnish, the antimony compound has an agglomerate containing reduced antimony or antimony and has a defect as a paint. A dullness can be seen in the produced rosin.
  • the copolyester resin is colored, and when an aliphatic dicarboxylic acid such as adipic acid or sebacic acid is used as a copolymerization component, Inferior in color, the white color of the resin that is markedly colored by the resin cannot produce the original white color.
  • Germanium compounds have a remarkably high power price that can be used effectively as the polymerization catalyst.
  • the paint for the inner surface of cans is supplied on the assumption that the flavor and flavor of the contents of the cans will not be impaired and used in a wide variety of cans.
  • Catalyst, etc. no concern about toxicity and environmental pollution of environmental hormones, (2) resistance to heat sterilization (retort) treatment, (3) excellent adhesion and workability, (4) Excellent blister resistance and whitening resistance (content resistance) when heat-sterilized salt and acid content, (5) No deterioration of workability due to excessive baking during canning Degradation).
  • salt and vinyl resin and epoxy phenolic resin are often used as the resin for can inner surface paints.
  • the salt-based monomer remaining in the resin is a substance with serious sanitary problems such as galling.
  • the epoxicy phenolic rosin has a high baking temperature, and the generation of environmental hormones becomes a problem.
  • a proposal has been made to use a copolymerized polyester resin with a titanium-based polymerization catalyst without using a salt vinyl resin or a bisphenol type epoxy resin (patented) Reference 36 and Patent reference 37).
  • Patent Document 34 aluminum compounds and phosphorus compounds have been proposed (Patent Document 34), but the use of copolymerized polyester resins is still unknown.
  • Patent Document 36 Japanese Patent Laid-Open No. 2001-106969
  • Patent Document 37 Japanese Patent No. 2526631
  • Antimony, titanium, germanium, tin, and the like are known as polymerization catalysts for the copolyester. While coercive, such a metal plate copolymer for the inner surface of the can Regarding the production of polyester resin, these polymerization catalyst species had the following problems.
  • Polymerization catalysts such as tin compounds and antimony compounds contain heavy metals, and V and polyesters containing these are desired.
  • the copolymerized polyester resin is colored, and when adipic acid is used as the copolymerization component, aliphatic dicarboxylic acid such as sebacic acid is used as the copolymer component. Inferior to the white paint, which is highly colored, the original white color cannot be obtained.
  • the germanium compound can be used effectively as the polymerization catalyst, but the price is extremely high.
  • Hot melt adhesives and extrusion coating agents have features such as labor saving, short-time adhesion, and excellent productivity, and are used in a wide range of fields.
  • the thermoplastic resin used in this hot melt adhesive must be (1) easily melted by heating and exhibit excellent wettability to the adherend. (2) Do not cause deterioration such as oxidation, decomposition, or alteration during heating and melting. (3) Excellent adhesion. (4) Performance such as excellent heat resistance, hydrolysis resistance, cold resistance, weather resistance, solvent resistance, and flexibility is required.
  • hot melt adhesives with such basic performance are used in the form of films and powders when used, but also in the form of non-woven fabrics, etc., but may be molded into such shapes. It is further required that the adhesives do not block when used in. mainly Copolymerized polyester hot melt adhesives using titanium-based polymerization catalysts (Patent Documents 38 to 40) have good adhesiveness, heat resistance, weather resistance, and solvent resistance among these required performances. It is widely used in fields that make use of these features.
  • Patent Document 38 Japanese Patent Laid-Open No. 55-152772
  • Patent Document 39 JP-A-7-70535
  • Patent Document 40 JP-A-8-48961
  • antimony-based, titanium-based, germanium-based, tin-based and the like are known as conventional copolymerization polyester polymerization catalysts.
  • the following problems remained in these polymerization catalyst species.
  • Polymerization catalysts such as tin compounds and antimony compounds contain heavy metals, and V and polyesters containing these are desired.
  • the antimony compound should have a dullness in the copolymer polyester resin obtained.
  • the copolymerized polyester resin is colored, and when adipic acid is used as the copolymerization component, aliphatic dicarboxylic acid such as sebacic acid is used as the copolymer component.
  • aliphatic dicarboxylic acid such as sebacic acid is used as the copolymer component.
  • the white paint which is highly colored, the original white color cannot be obtained.
  • the color of the resin used as the adhesive layer may be a problem.
  • the germanium compound can be used effectively as the polymerization catalyst, but the price is extremely high.
  • the object of the present invention is to obtain a copolymer polyester resin without using a conventional catalyst such as an antimony compound, and to obtain a resin composition containing this copolymer polyester, And a paint, a toner, a binder resin, a coated metal plate, a hot melt adhesive, and an extrusion coating agent using the resin composition.
  • a conventional catalyst such as an antimony compound
  • the object of the present invention is to achieve efficient polymerization without using a problematic conventional catalyst such as an antimony compound, particularly when polymerizing a low molecular weight copolymer polyester, and has an excellent hue. Furthermore, it is an object of the present invention to produce a copolyester resin resin in which the problem of foreign matters derived from aluminum is solved, and to provide a coating material having excellent coating properties using this. Another object of the present invention is to provide a method for producing such a copolymer polyester resin.
  • An object of the present invention is to use a polymerization catalyst having an aluminum compound power that is less than that of a conventional catalyst such as an antimony compound or a tin compound.
  • a copolyester resin resin in which the problem of foreign matters derived from it has been solved, a coating composition for pre-coating using the same, and a coated metal sheet having the workability, hardness, impact resistance, and blocking resistance applied thereto. That is.
  • An object of the present invention is to provide a copolymer polyester containing bisphenol A and Z or bisphenol F component, which is one of the essential components of a copolymer polyester resin for a primer of a metal plate, mainly using an aluminum compound as a polymerization catalyst.
  • a resin that has a polymerization activity, suppresses coloring due to thermal stability, and contains few foreign substances derived from aluminum is a need for a resin that has a polymerization activity, suppresses coloring due to thermal stability, and contains few foreign substances derived from aluminum.
  • copolymer polyester resin containing bisphenol A and Z or bisphenol F component which is one of the essential components of the copolyester resin resin for primer.
  • the present invention provides a copolymerized polyester resin that can realize favorable fixing characteristics, storage stability, environmental stability, and is excellent in color image reproducibility, and can be suitably used as a toner for electrostatic images. It is an object to provide a toner for developing an electrostatic charge using [Coating resin composition for can outer surface and metal plate coated with the same]
  • the present invention considers environmental problems, is excellent in polymerization activity, suppressed coloring of rosin, and reduced foreign matter derived from aluminum. It is an object of the present invention to provide an object and a coated metal sheet coated with the same and having workability and resistance to deterioration over time.
  • the present invention considers environmental problems, has excellent polymerization activity, suppresses the coloring of rosin, and reduces the foreign matter derived from aluminum. It is an object of the present invention to provide an object and a coated metal sheet coated with the same and having workability and resistance to deterioration over time.
  • the object of the present invention is to use mainly an aluminum compound as a polymerization catalyst, have sufficient polymerization activity, suppress coloring due to poor thermal stability of the obtained copolymer polyester resin, and further prevent foreign matters derived from aluminum. It is to provide a copolymer polyester resin for a hot melt adhesive with a low content, and to solve the following problems.
  • polyester hot melt adhesives have excellent performance that almost satisfies the above-mentioned problems.
  • the initial adhesive strength is excellent, there is a drawback that it is difficult to achieve both hydrolysis resistance and blocking resistance at the time of winding the resin molding.
  • an aromatic polycarboxylic acid that is difficult to be hydrolyzed in the polyvalent carboxylic acid.
  • the melting point becomes high, and satisfactory peel adhesion strength at low temperature or room temperature cannot be obtained, or the adhesive must be bonded if it is not higher than the heat resistant temperature of the adherend during bonding.
  • an aromatic dicarboxylic acid is 20 More than mol%
  • the polyhydric alcohol component constituting the copolymer polyester resin is ethylene glycol, diethylene glycol, 1,3 prononediol, 1,4 butanediol, 2-methyl-1,3 propanediol, carbon number 5 to: LO alkylene glycol, 1, 4 cyclohexanedimethanol, polyhydric alcohol represented by formula 1, polyhydric alcohol represented by formula 2, and polyhydric alcohol represented by formula 3 Copolymer polyester resin characterized by the above.
  • R 2 is hydrogen or a methyl group
  • R 3 is either an ethylene group or a 1,2-propylene group
  • m and n are each 1 or more and 2 ⁇ m + n ⁇ 8.
  • R 4 and R 5 are alkyl groups having 1 to 6 carbon atoms.
  • p 0 or 1
  • R 6 is hydrogen, a methyl group or an ethyl group
  • R 7 is hydrogen, or an alkyl group having 1 or more carbon atoms
  • R 8 is hydrogen or an alkyl group having 1 or more carbon atoms Wherein at least one of R 6 , R 7 and R 8 is an alkyl group.
  • the copolymer polyester resin (i) mainly for powder coating is as follows.
  • polyvalent carboxylic acid components constituting the copolymer polyester 20 to 20 of isophthalic acid is present in the copolymer polyester resin polymerized in the presence of a polymerization catalyst containing at least an aluminum compound. 100 mole 0/0, polyhydric of the alcohol component, 2-methyl-1, 3-propanediol and Z or 1, copolyester ⁇ of 3-propanediol is 20 to 80 mole 0/0.
  • a paint comprising the copolymerized polyester resin (A) according to any one of (2) to (9) and a curing agent (B) capable of reacting with the (A).
  • the following [0048] (14) in the presence of at least one force becomes polymerization catalyst selected group force consisting of an aluminum compound Te method Nio ⁇ for producing a copolymerized polyester ⁇ , 100 polycarboxylic acid component mole 0/0 and the when, polyhydric alcohol component 90-150 mole 0/0 use a Te copolyester ⁇ method for producing the polymerization is carried out.
  • polymerization catalyst selected group force consisting of an aluminum compound Te method Nio ⁇ for producing a copolymerized polyester ⁇ , 100 polycarboxylic acid component mole 0/0 and the when, polyhydric alcohol component 90-150 mole 0/0 use a Te copolyester ⁇ method for producing the polymerization is carried out.
  • the polymerization reaction is performed using a part of the polyvalent carboxylic acid component, and then the remaining polyvalent carboxylic acid component is added to further perform the polymerization reaction (14) to (16) Copolymerization Method for producing polyester resin.
  • the copolymer polyester resin (iii) used in precoat paints that emphasizes blocking resistance is as follows. (30) is produced in the presence of a polymerization catalyst containing an aluminum compound, 10 to 70 moles of terephthalic acid (al) as a polycarboxylic acid component (a) 0/0, other aromatic and the terephthalic acid (al) Containing 80 mol% or more of the aromatic dicarboxylic acid (a2) and 25 mol of 2-methyl-1,3-propanediol and Z or 1,3-propanediol (gl) as the polyhydric alcohol component (g) % Of alkylene glycol having 5 to 10 carbon atoms and Z or alicyclic glycol ( g 2) of 75 mol% or less, and among the polyhydric alcohol component (g), the (gl) dallicol and (g2) glycol Is a copolymer polyester resin satisfying a total of 50 mol% or more, a glass transition temperature of 10
  • (31) is produced in the presence of a polymerization catalyst containing an aluminum compound, 10 to 70 moles of terephthalic acid (al) as a polycarboxylic acid component (a) 0/0, other aromatic and the terephthalic acid (al) Containing 80 mol% or more of the aromatic dicarboxylic acid (a2) and 25 mol of 2-methyl-1,3-propanediol and Z or 1,3-propanediol (gl) as the polyhydric alcohol component (g) % Of alkylene glycol having 5 to 10 carbon atoms and Z or alicyclic glycol ( g 2) of 75 mol% or less, and among the polyhydric alcohol component (g), the (gl) dallicol and (g2) glycol Is a copolymer polyester resin satisfying a total of 50 mol% or more, a glass transition temperature of 10 to 80 ° C, a reduced viscosity of 0.2 dlZg or more, and a specific gravity
  • polymerization catalyst containing an aluminum compound comprises at least one selected from the group consisting of aluminum compounds and at least one selected from the group consisting of phosphorus compounds.
  • the polymerization catalyst containing an aluminum compound is characterized by comprising at least one selected from the group consisting of aluminum compounds and at least one selected from the group forces consisting of alkali metals or alkaline earth metals ( 31) Pre-coated resin composition according to 31)
  • Alkali metal or alkaline earth metal power Li, Na or Mg or a compound power thereof is at least one kind selected from the group power of any of (31), (33) and (34) 2.
  • Alkali metal and alkaline earth metal are selected from Li, Na, Mg or their compound power
  • a coated metal sheet characterized by being coated and baked with the resin composition for coating according to (48).
  • the copolymerized polyester resin (V) used in the toner is as follows.
  • polyvalent carboxylic acid component 50 to 100 mol of aromatic dicarboxylic acid. / 0, other dicarboxylic acids force ⁇ to 50 mole 0/0, trifunctional or higher polycarboxylic acid force ⁇ ⁇ a 15 mole 0/0, the polyhydric alcohol component, bisphenol A and represented by the above formula 1 / or Bisufu phenol F mosquitoes with alkylene oxide ⁇ 5-100 mole 0/0, other glycols is located at 0-95 mole 0/0, trifunctional or more polyhydric alcohols force ⁇ to 15 mole 0/0 And a copolymerized polyester resin produced in the presence of a catalyst containing at least an aluminum compound.
  • Polyvalent alcohol component, bisphenol A and / or Bisufu phenol F alkylene oxide with mosquito ⁇ 5-100 mole 0/0, other glycols is 0 to 95 mole 0/0, 3 shown in the formula 1 or higher functional polyhydric alcohols force ⁇ ⁇ a 15 mole 0/0, at least aluminum - ⁇ beam compound containing to become electrostatic development copolyesters ⁇ prepared in the presence of a catalyst containing as Vine da one Toner.
  • the polyester resin has a glass transition temperature of 45 to 75 ° C, an acid value of 0.2 to 30 mgK OHZg, and a weight average molecular weight of 5000 to 50000 (51) to ( 5 3) The electrostatic charge developing toner described in the above.
  • the toner for electrostatic charge development according to any one of (52) to (55), which is an aromatic phosphonic acid or a derivative thereof.
  • Wax power The static endothermic peak described in (58) has a maximum endothermic peak at 60 to 130 ° C with respect to the endothermic peak of the DSC curve measured by a differential scanning calorimeter (DSC). toner.
  • DSC differential scanning calorimeter
  • the crystalline polyester resin has a maximum endothermic peak at 60 to 85 ° C with respect to the endothermic peak of the DSC curve measured by a differential scanning calorimeter (DSC) (58) or (59) The electrostatic charge developing toner according to (59).
  • DSC differential scanning calorimeter
  • (61) The electrostatic charge developing toner according to any one of (51) to (60), wherein the weight average particle diameter is 5 to 10 ⁇ m.
  • the copolymerized polyester resin (vi) used for the can outer coating is as follows.
  • polystyrene resin (65) Polymerized in the presence of a polymerization catalyst containing an aluminum compound.
  • a polymerization catalyst containing an aluminum compound Of the polyhydric carboxylic acid components, isophthalic acid is 20 to 80 mol%, and among the polyhydric alcohol components, one or more side-chain alkyl group containing Darikoru represented is 70 to: L00 mole 0/0, copolyester ⁇ (J) and the crosslinking agent is other glycol 0 to 30 mol%
  • the polymerization catalyst containing an aluminum compound is composed of at least one selected from the group consisting of aluminum compounds and at least one selected from group strengths including phosphorus compound strengths (65)
  • the coating resin composition for can outer surfaces as described.
  • the polymerization catalyst containing an aluminum compound is composed of at least one selected from the group consisting of aluminum compounds and at least one selected from the group consisting of alkali metals, alkaline earth metals and their compounds. (65) or (66), a can-resin composition for outer surfaces of cans.
  • the phosphorus compound is an aromatic phosphonic acid or a derivative thereof
  • the alkali metal is Li, Na and the alkaline earth metal is Mg
  • Copolymer polyester resin The filtration time of aluminum foreign matter insoluble in copolymer polyester resin in ⁇ is 5 hours or less, (65) to (71) A can-resin composition for can outer surface according to claim 1.
  • a coated metal sheet for can outer surfaces which is obtained by applying the coating resin composition for can outer surfaces according to any one of (65) to (72) to a metal sheet.
  • polymerization catalyst containing an aluminum compound and among divalent carboxylic acid components, aromatic dicarboxylic acid is 75-: LOO mol%, aliphatic and Z or alicyclic dicarboxylic acid.
  • the polyhydric alcohol component includes at least one polyalcohol having a side chain represented by the above formula 3 and Z or 1,4-cyclohexanedimethanol in a range from 30 to 100 mol 0. / 0, other polyalcohols force ⁇ to 70 mole 0/0 der Ru copolyester ⁇ .
  • aromatic dicarboxylic acid is 75-: LOO mol%, aliphatic and Z or alicyclic dicarboxylic acid.
  • the polyhydric alcohol component includes at least one polyalcohol having a side chain represented by the above formula 3 and Z or 1,4-cyclohexanedimethanol in a range from 30 to 100 mol 0. / 0, other polyalcohols force ⁇ to 70 mole 0/0 der Ru copolyester ⁇ (L) and cross-linking agent (M) Kakara made it can inner coating resin composition characterized.
  • the polymerization catalyst containing an aluminum compound is composed of at least one selected from the group consisting of aluminum compounds and at least one selected from group strengths including phosphorus compound strengths (75) Or the coating resin composition for can inner surfaces in any one of (76).
  • the polymerization catalyst containing an aluminum compound is composed of at least one selected from the group consisting of aluminum compounds and at least one selected from the group consisting of alkali metals, alkaline earth metals and their compounds. (75) to (77) characterized in that the paint resin composition for an inner surface of a can according to any one of the above.
  • the paint resin composition for can inner surfaces according to any one of (75) to (78), wherein the aluminum compound is a carboxylic acid-containing compound.
  • the alkali metal is Li, Na, and the alkaline earth metal is Mg ( 78)
  • a coated metal plate for a can inner surface wherein the paint resin composition for a can inner surface according to any one of (75) to (83) is applied to a metal plate.
  • the copolymerized polyester resin (viii) used in the hot melt adhesive and the extrusion coating agent is as follows.
  • terephthalic acid, 2, 6 Naphthalene dihydric power The total of at least one aromatic dicarboxylic acid for which rubonic acid power is also selected is 20 to: L00 mol%, and the polyhydric alcohol constituting the copolymer polyester resin
  • the total of at least one polyhydric alcohol selected from ethylene glycol, diethylene glycol and 1,4 butanediol is 50 to 100 mol.
  • a crystalline polyester resin characterized by having a 0 / force and a melting point.
  • the alkali metal or alkaline earth metal is at least one selected from Li, Na, Mg or a compound thereof, described in any of (89) to (91) Crystalline polyester resin.
  • a low molecular weight copolymer polyester resin can be efficiently polymerized, has excellent hue, does not contain heavy metals such as tin compounds and antimony compounds, and is a foreign substance derived from aluminum. It is possible to obtain a copolymerized polyester resin and a paint using the same.
  • the resin composition for precoat of the present invention According to the resin composition for precoat of the present invention, the resin composition for precoat with excellent polymerization activity, suppressed coloring of resin, and reduced foreign matters derived from aluminum, and the processability of applying this composition. It is possible to obtain a coated metal plate having excellent hardness, impact resistance and blocking resistance.
  • a copolymer containing bisphenol A and Z or bisphenol F which is one of the essential components of copolymer polyester resin for primer of a metal plate, is used.
  • a polymerized polyester resin By producing a polymerized polyester resin, it is possible to produce a copolymerized polyester resin in which polymerization activity, coloration of the resin are suppressed, and furthermore, the problem of reducing foreign matters derived from aluminum is solved.
  • the obtained copolymer polyester resin, the resin composition for coating, and the coated metal sheet coated with this resin have reduced polymerization activity and coloring of the resin, and further reduced foreign matters derived from aluminum.
  • a copolymerized polyester resin containing bisphenol A and Z or a bisphenol F component, which is one of the components of copolymer polyester resin is produced using a polymerization catalyst having an aluminum compound power.
  • the resin composition for a can outer surface paint and the coated metal plate for the outer surface of the can of the present invention the can excellent in polymerization activity, suppressed coloring of the resin, and further solved the problem of foreign matters derived from aluminum.
  • a resin composition for an outer surface coating and a coated metal plate for an inner surface of a can excellent in processability and resistance to deterioration with time can be obtained.
  • the resin composition for a can inner surface paint and the coated metal plate for a can inner surface of the present invention the can excellent in polymerization activity, suppressed coloring of the resin, and further solved the problem of foreign matters derived from aluminum.
  • a resin composition for an inner surface of a can and a coated metal plate for an inner surface of a can excellent in processability and resistance to deterioration over time can be obtained.
  • the polyester resin composition of the present invention exhibits excellent adhesion as compared with conventional polyester hot melt adhesives, and is excellent in hydrolysis resistance and blocking resistance. It is useful as a hot melt adhesive for bonding various plastic films and wooden boards or cloths, and bonding metals.
  • the crystalline polyester resin of the present invention has excellent transparency and is low in color, so that it is suitable for use in a film.
  • the present invention is a copolymer polyester resin manufactured in the presence of a catalyst containing at least an aluminum compound, and among the polycarboxylic acid components constituting the copolymer polyester resin, an aromatic dicarboxylic acid is used.
  • the acid is 20 mol% or more
  • the polyhydric alcohol component constituting the copolymer polyester resin is ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4 butanediol, 2-methyl-1,3-propanediol.
  • the copolymerized polyester resin of the present invention a copolymerized polyester resin polymerized in the presence of a catalyst containing at least an aluminum compound is used.
  • a catalyst containing at least an aluminum compound is used as the aluminum compound.
  • the aluminum compound a known aluminum compound can be used without limitation as much as metallic aluminum.
  • aluminum compounds include aluminum formate, aluminum acetate, basic aluminum acetate, aluminum propionate, aluminum oxalate, aluminum acrylate, aluminum laurate, aluminum stearate, aluminum benzoate, aluminum Carboxylates such as aluminum lichloroacetate, aluminum lactate, aluminum citrate, aluminum salicylate, inorganic salts such as aluminum chloride, aluminum hydroxide, aluminum hydroxide chloride, aluminum carbonate, aluminum phosphate, aluminum phosphonate, aluminum Methoxide, aluminum ethoxide, aluminum n-propoxide, aluminum iso-propoxide, aluminum n-butoxide, aluminum t-oxide Aluminum alkoxide, aluminum acetyl cetate, aluminum Aluminum chelate compounds such as mucetyl acetate, aluminum ethyl acetate, aluminum ethyl acetate acetate iso-propoxide, organoaluminum compounds such as trimethylaluminum, triethylaluminum and their partial
  • carboxylic acid salts are mentioned. Of these, carboxylic acid salts, inorganic acid salts and chelate compounds are preferred.
  • Aluminum acetate, basic aluminum acetate, aluminum chloride, aluminum hydroxide, aluminum hydroxide chloride, and aluminum acetyl chloride are also preferred. Nate is particularly preferred.
  • the amount of aluminum compound in the present invention with respect to the moles of all the structural units of the carboxylic acid component such as deer carboxylic acid or polycarboxylic acid of the polyester obtained TO 001 to:.
  • L0 Monore 0/0 power preferably, more preferably 0.005 to 0.5 Monore 0/0.
  • the addition amount of the aluminum component is required to be in a wide range because the catalytic activity largely varies depending on the type and combination of polyvalent carboxylic acid and diol used, and the polymerization method. This shows the same tendency with other polymerization catalysts.
  • the amount of polymerization catalyst needs to be greatly increased. Since the polymerization catalyst in the present invention exhibits sufficient catalytic activity, as a result, the resulting polyester has excellent thermal stability, thermal oxidation stability, and hydrolysis resistance, and the generation and coloring of foreign matters due to aluminum are suppressed. .
  • Examples of preparation of an aqueous solution of basic aluminum acetate are as follows. That is, water is added to basic aluminum acetate and sufficiently diffused at room temperature, and then dissolved at room temperature to 100 ° C. to obtain an aqueous solution. In this case, a lower temperature is preferable and a shorter heating time is preferable.
  • the concentration of the aqueous solution is preferably 10 to 30 g / l, particularly preferably 15 to 20 g / l.
  • the basic aluminum acetate aqueous solution is the same ethylene glycol solution. That is, ethylene glycol is added to the above aqueous solution.
  • the added amount of ethylene glycol is preferably 0.5 to 5.0 times the volume of the aqueous solution. More preferably, the amount is 0.8 to 2.0 times.
  • the water is distilled off by heating and stirring at 80 to 120 ° C. More preferably, heating is performed under reduced pressure and / or an inert gas atmosphere such as nitrogen or argon, and water is distilled off to prepare a catalyst solution.
  • the ethylene glycol is an example, and other alkylene glycols are used. Can be used in the same way.
  • the basic aluminum acetate described above is soluble in a solvent such as water glycol, and particularly used in water and Z or ethylene glycol to obtain catalytic activity and a copolymer obtained. It is also preferable from the viewpoint of reducing foreign matters of polyester.
  • the phosphoric acid compound constituting the polymerization catalyst in the present invention is not particularly limited, but phosphoric acid and phosphoric acid esters such as trimethyl phosphoric acid, triethyl phosphoric acid, furuluric acid, and trifururic acid, Phosphorous acid and trimethyl phosphite, triethyl phosphite, triphenyl phosphite, tris (2,4-di-tert-butylphenol) phosphite, tetrakis (2, 4-di-tert-butylphenol) 4 , 4 Phosphite such as bi-diene phosphite.
  • phosphoric acid and phosphoric acid esters such as trimethyl phosphoric acid, triethyl phosphoric acid, furuluric acid, and trifururic acid, Phosphorous acid and trimethyl phosphite, triethyl phosphite, triphenyl phosphite, tri
  • the phosphorus compound is a phosphonic acid compound, a phosphinic acid compound, a phosphine oxide compound, a phosphonous acid compound, a phosphinic acid compound, or a phosphine compound. It is at least one phosphorus compound selected from the group that also has compound power.
  • phosphorus compounds an effect of improving the catalytic activity is seen, and an effect of improving physical properties such as the thermal stability of the polyester is seen.
  • the use of phosphonic acid compounds is preferable because of their great effects of improving physical properties and catalytic activity.
  • the use of a compound having an aromatic ring structure is highly preferred because of its physical properties improving effect and catalyst activity improving effect.
  • the phosphonic acid compound, phosphinic acid compound, phosphine oxide compound, phosphonous acid compound, phosphinic acid compound, and phosphine compound are respectively represented by the following formulas This refers to a compound having the structure represented by 9).
  • Examples of the phosphonic acid compound in the present invention include dimethyl methylphosphonate, diphenyl methylphosphonate, dimethyl phenylrephosphonate, dimethyl phenylphosphonate, diphenol phenylphosphonate, dimethyl phosphophosphonate, and benzylphosphonic acid. Examples include jetil.
  • Examples include diphenylphosphinic acid, methyl diphenylphosphinate, diphenylphosphinic acid phenyl, phenylphosphinic acid, phenylphenylphosphinic acid methyl, and phenylphosphinic acid phenyl.
  • Examples of the phosphine oxide compound of the present invention include diphenylphosphine oxide, methyldiphenylphosphine oxide, and triphenylphosphine oxide.
  • the phosphorus compound in the present invention is represented by the following formula (Chemical Formula 10) to The compound represented by (Chemical Formula 15) is preferred.
  • R ° and R 6 each independently represent hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon group having 1 to 50 carbon atoms including a hydroxyl group, a halogen group, an alkoxyl group, or an amino group.
  • R 2 and R 3 each independently represent hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, including a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group.
  • the hydrocarbon group may be an alicyclic structure such as cyclohexyl, or an aromatic group such as phenyl naphthyl. An aromatic ring structure may be included.
  • the phosphorus compound includes, for example, dimethyl methylphosphonate, diphenyl methylphosphonate, dimethyl phenylphosphonate, jetyl phenylphosphonate, diphenylphenolphosphonate, benzylphosphonic acid.
  • a phosphorus metal salt compound is particularly preferable as the phosphorus compound.
  • the phosphorus metal salt compound is not particularly limited as long as it is a phosphorus compound metal salt.
  • a metal salt of a phosphonic acid compound is used, the polyester which is the subject of the present invention is used.
  • the effect of improving the physical properties and improving the catalytic activity are greatly preferred.
  • metal salts of phosphorus compounds include monometal salts, dimetal salts, and trimetal salts.
  • the metal portion of the metal salt is Li, Na, K, Be, Mg,
  • a material selected from Sr, Ba, Mn, Ni, Cu, and Zn is preferable because the effect of improving the catalytic activity is great.
  • Li, Na, and Mg are particularly preferable.
  • the phosphorus metal salt compound at least one selected from the compounds represented by the following general formula (Chemical Formula 19) is used, the effect of improving the physical properties and the effect of improving the catalytic activity are large. preferable.
  • R 1 represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group, or a halogen group. Alternatively, it represents a C 1-50 hydrocarbon group containing an alkoxyl group or amino group.
  • R 2 represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group.
  • R 3 represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group, an alkoxyl group, or a hydrocarbon group having 1 to 50 carbon atoms including carbonyl.
  • R 1 represents an integer of 1 or more
  • m represents 0 or an integer of 1 or more
  • l + m is 4 or less
  • M represents a (l + m) -valent metal cation
  • n represents an integer of 1 or more.
  • the hydrocarbon group may include an alicyclic structure such as cyclohexyl, a branched structure, or an aromatic ring structure such as phenyl naphthyl! [0108]
  • R 1 include phenyl, 1-naphthyl, 2-naphthyl, 9-anthryl, 4-biphenyl, 2-biphenyl, and the like.
  • R 2 examples include hydrogen, methyl group, ethyl group, propyl group, isopropyl group, n butyl group, sec butyl group, tert butyl group, long chain aliphatic group, fur group, naphthyl group.
  • Examples include hydroxide ions, alcoholate ions, acetate ions and cetylacetone ions.
  • R 1 represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon group having 1 to 50 carbon atoms including a hydroxyl group, a halogen group, an alkoxyl group, or an amino group.
  • R 3 represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group, an alkoxyl group or a hydrocarbon group containing 1 to 50 carbon atoms, 1 is an integer of 1 or more, m is 0 Or an integer of 1 or more, l + m is 4 or less, M represents a (l + m) -valent metal cation, and the hydrocarbon group is an alicyclic structure such as cyclohexyl, a branched structure, or phenyl naphthyl.
  • R 1 examples include phenyl, 1-naphthyl, 2-naphthyl, 9-anthryl, 4-biphenyl, 2-biphenyl, and the like.
  • R 30 examples include hydroxide ions, alcohol ions, acetate ions, acetylacetone ions, and the like.
  • the phosphorus metal salt compound includes lithium [(1 naphthyl) methylphosphonate], sodium [(1-naphthyl) methylphosphonate], magnesium bis [(1 naphthyl) methylphosphone.
  • Ethyl potassium [(2-naphthyl) methylphosphonate], magnesium bis [(2-naphthyl) methylphosphonate], lithium [benzylphosphonate], sodium [benzylphosphonate], magnesium bis [benzylphosphone] Acid ethyl], beryllium bis [benzyl phosphonate], strontium bis [benzyl phosphonate], manganese bis [benzyl phosphonate], sodium benzyl phosphonate, magnesium bis [benzyl phosphonate], sodium [(9-anthryl ) Ethyl phosphonate] Gnesium bis [(9-anthryl) methyl phosphonate], sodium [4-hydroxybenzyl phosphonate], magnesium bis [4-hydroxybenzyl phosphonate], sodium [4-chlorobenzyl phosphonate] , Magnesium bis [4 cyclopentyl phosphonate ethyl], sodium [methyl 4-amino benzyl]
  • lithium [(1 naphthyl) methylphosphonate], sodium [(1 naphthyl) methylphosphonate], magnesium bis [(1 naphthyl) methylphosphonate], lithium [benzylphosphonate], sodium [Benzylphosphonate], magnesium bis [benzylphosphonate], sodium benzylphosphonate, magnesium bis [ Benzylphosphonic acid] is particularly preferred!
  • a phosphorus compound having at least one P—OH bond is particularly preferred as the phosphorus compound.
  • the effect of improving the physical properties of the polyester is particularly enhanced, and these polyester compounds can be used together with the aluminum compound of the present invention during the polymerization of the polyester.
  • the effect of improving the catalytic activity is significant.
  • the phosphorus compound having at least one P—OH bond is not particularly limited as long as it is a phosphorus compound having at least one P—OH in the molecule.
  • the use of a phosphonic acid compound having at least one POH bond facilitates complex formation with an aluminum compound, thereby improving the physical properties of the polyester and improving the catalytic activity. Largely preferred.
  • a physical property improving effect catalyst can be obtained by using at least one compound selected from the compound power represented by the following general formula (Chemical Formula 21).
  • the effect of improving activity is large and preferable.
  • R 1 represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon group having 1 to 50 carbon atoms including a hydroxyl group, a halogen group, an alkoxyl group, or an amino group.
  • R 2 represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group, and a hydrocarbon group having 1 to 50 carbon atoms, n represents an integer of 1 or more, (It may also contain alicyclic structures such as hexyl, branched structures, and aromatic ring structures such as phenyl naphthyl.)
  • R 1 examples include phenyl, 1-naphthyl, 2-naphthyl, 9-anthryl, 4-biphenyl, 2-biphenyl, and the like.
  • R 2 examples include hydrogen and meso Tyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, long-chain aliphatic group, fur group, naphthyl group, substituted fur group, naphthyl group And groups represented by CH 2 CH 2 OH, and the like.
  • the phosphorus compound having at least one P—OH bond includes (1 naphthinole) methinorephosphonic acid ethinore, (1 naphthinore) methinorephosphonic acid, (2-naphthinore) methylphosphonic acid ethyl, benzylphosphone.
  • (1-naphthyl) methylphosphonate and benzylphosphonate are particularly preferred.
  • Examples of preferred phosphorus compounds in the present invention include phosphorus compounds represented by the chemical formula (Chemical Formula 22).
  • R 1 represents a hydrocarbon group having 1 to 49 carbon atoms, or a hydrocarbon group having 1 to 49 carbon atoms including a hydroxyl group, a halogen group, an alkoxyl group, or an amino group.
  • R 2 and R 3 each independently represent hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon group having 1 to 50 carbon atoms including a hydroxyl group or an alkoxyl group, which is an alicyclic structure or branched structure. And may contain an aromatic ring structure.
  • the phosphorus compound having a large molecular weight is more preferred because it is less likely to be distilled off during polymerization!
  • the phosphorus compound is preferably a phosphorus compound having a phenol moiety in the same molecule. Incorporation of a phosphorus compound having a phenol moiety in the same molecule increases the effect of improving the physical properties of the polyester, and a polyester compound having a phenol moiety in the same molecule is used during polymerization of the polyester. Therefore, the effect of increasing the catalytic activity is greater, and therefore the productivity of polyester is excellent.
  • the phosphorus compound having a phenol moiety in the same molecule is not particularly limited as long as it is a phosphorus compound having a phenol structure, but a phosphonic acid compound or phosphinic acid compound having a phenol moiety in the same molecule.
  • Compound, phosphine oxide-based compound, phosphonous acid-based compound, phosphinic acid-based compound, phosphine-based compound power Use of one or more compounds selected from the group consisting of polyester improves physical properties and improves catalytic activity Is preferable. Of these, the use of phosphonic acid compounds having one or more phenolic moieties in the same molecule is particularly preferred for improving the physical properties and improving the catalytic activity of polyester.
  • the phosphorus compound having a phenol moiety in the same molecule is preferably a compound represented by the following general formulas (Chemical Formula 29) to (Chemical Formula 31).
  • R 1 is a substituent having a phenol moiety, such as a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group, a halogen group, an alkoxyl group, or an amino group.
  • R 4 , R 5 and R 6 each independently represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group, a halogen group or an alkoxyl group, Represents a hydrocarbon group having 1 to 50 carbon atoms including a substituent such as an amino group.
  • R 2 and R 3 each independently represent hydrogen, a hydrocarbon group having 1 to 50 carbon atoms including a substituent such as a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group.
  • the hydrocarbon group may contain an alicyclic structure such as a branched structure such as cyclohexyl or an aromatic ring structure such as phenyl or naphthyl.
  • the ends of R 2 and R 4 may be bonded to each other.
  • phosphorus compounds having a phenol moiety in the same molecule include, for example, p-hydroxyphenylphosphonic acid, p-hydroxyphenylphosphonic acid dimethyl, p-hydroxyphenylphosphonic acid jetyl, p —Hydroxyphenol phosphonic acid diphenyl, bis (p-hydroxyphenyl) phosphinic acid, bis (p-hydroxyphenol) methyl phosphinate, bis (p-hydroxyphenol) phosphinic acid P-hydroxyphenol phosphinic acid, p-hydroxyphenol phosphinic acid methyl, p-hydroxyphenol phosphinic acid phenol, p-hydroxyphenol phosphinic acid, p —Methyl hydroxyphenylphosphinate, p-hydroxyphenylphosphinate, bis (p-hydroxyphenol) phosphine oxa Id, tris (p-hydroxyphenyl) phosphine oxide, bis (p-hydroxyphenol)
  • SANKO-220 manufactured by Sanko Co., Ltd.
  • R 3 represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group.
  • R 4 is hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, hydroxyl group, an alkoxyl group, or an carbo - to display the hydrocarbon group having 1 to 50 carbon atoms including Le.
  • Examples of R 40 — include hydroxide ions, alcohol ions, acetate ions, acetylacetone ions, and the like.
  • n an integer of 1 or more.
  • the hydrocarbon group may contain an alicyclic structure such as cyclohexyl, a branched structure, or an aromatic ring structure such as phenyl naphthyl. )
  • At least one selected from the compound power represented by the following general formula (Formula 37) is preferable.
  • ⁇ ⁇ ⁇ ⁇ represents an n-valent metal cation.
  • N represents 1, 2, 3 or 4.
  • M is selected from Li, Na, K, Be, Mg, Sr, Ba, Mn, Ni, Cu, and Zn, the effect of improving the catalytic activity is greatly preferred. Of these, Li, Na, and Mg are particularly preferable.
  • Specific phosphorus metal salt compounds of the present invention include lithium [3,5 tert-butyl 4-
  • lithium [3,5-ditert-butyl-4-hydroxybenzylphosphonate] sodium [3,5-ditert-butyl 4-hydroxybenzylphosphonate]
  • magnesium bis [3,5 —Di-tert-butyl 4-hydroxybenzylphosphonate] is particularly preferred!
  • a specific phosphorus compound power having at least one P-OH bond represented by the following general formula (Chemical Formula 38) is also selected. At least one kind is particularly preferred.
  • R 3 represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group.
  • n represents an integer of 1 or more.
  • the hydrocarbon group may contain an alicyclic structure such as cyclohexyl, a branched structure, or an aromatic ring structure such as phenyl naphthyl.
  • At least one selected from compound power represented by the following general formula (Chemical Formula 39) is preferable.
  • R 3 represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group, or alkoxy. Represents a hydrocarbon group having 1 to 50 carbon atoms including a sulfur group. Hydrocarbon groups may include alicyclic structures such as cyclohexyl, branched structures, and aromatic ring structures such as phenyl naphthyl!
  • R 3 examples include hydrogen, methyl group, ethyl group, propyl group, isopropyl group, n butyl group, sec butyl group, tert butyl group, long chain aliphatic group, phenol group, Naphthyl group, substituted phenyl group, naphthyl group, group represented by CH 2 CH OH, etc.
  • the specific phosphorus compound having at least one P—OH bond includes ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 3,5-di-tert-butyl.
  • 4-hydroxybenzylphosphonate methyl 3,5-di-tert-butyl 4-hydroxybenzylphosphonate isopropyl, 3,5-ditert-butyl 4-hydroxybenzyl phosphonate phenol, 3,5-di-tert-butyl Examples include octadecyl 4-hydroxybenzylphosphonate, 3,5-di-tert-butyl 4-hydroxybenzylphosphonic acid, and the like. Of these, 3,5-ditertbutyl-4-hydroxybenzylphosphonate and 3,5-ditert-butyl-4-hydroxybenzylphosphonate methyl are particularly preferred.
  • At least one type of phosphorus compound selected from the specific phosphorus compounds represented by the following general formula (Chemical Formula 40) is: preferable.
  • R 2 each independently represents hydrogen or a hydrocarbon group having 1 to 30 carbon atoms.
  • R 4 each independently represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon group having 1 to 50 carbon atoms including a hydroxyl group or an alkoxyl group.
  • n represents an integer of 1 or more.
  • the hydrocarbon group may contain an alicyclic structure such as cyclohexyl, a branched structure, or an aromatic ring structure such as phenyl naphthyl.
  • R 4 each independently represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon group having 1 to 50 carbon atoms including a hydroxyl group or an alkoxyl group.
  • the hydrocarbon group may contain an alicyclic structure such as cyclohexyl, a branched structure, or an aromatic ring structure such as phenyl naphthyl.
  • R 3 and R 4 include a short-chain aliphatic group such as hydrogen, a methyl group, and a butyl group, a long-chain aliphatic group such as octadecyl, a phenyl group, a naphthyl group, and a substituted group.
  • a short-chain aliphatic group such as hydrogen, a methyl group, and a butyl group
  • a long-chain aliphatic group such as octadecyl
  • a phenyl group a naphthyl group
  • a substituted group examples include an aromatic group such as a naphthyl group and a group represented by CH 2 CH 3 OH.
  • specific phosphorus compounds include 3,5-di-tert-butyl-4-hydroxybenzylphosphonate diisopropyl, 3,5-ditert-butyl 4-hydroxybenzyl diphosphonate, 3,5 -Ditert-butyl 4-hydroxybenzylphosphonate dioctadecyl, 3,5-ditert-butyl 4-hydroxybenzylphosphonate diphenyl, and the like.
  • dioctadecyl 3,5-di-tert-butyl-4-hydroxybenzyl phosphonate and di-phenyl 3,5-di-tert-butyl 4-hydroxybenzyl phosphonate are particularly preferred! /.
  • the compound compounds represented by the chemical formulas (Chemical Formula 42) and (Chemical Formula 43) are also selected as particularly desirable compounds in the present invention. At least one kind of Linyi compound.
  • Irganoxl222 manufactured by Ciba 'Specialty' Chemicals
  • Irganoxl425 manufactured by Chinoku 'Specialty' Chemicals
  • phosphorus compounds preferably used in the present invention include phosphonic acid compounds having a linking group (X) represented by (Chemical 44) or (Chemical 45) shown below or (Chemical formula 46). And a phosphonic acid compound having no linking group (X) represented by:
  • R 1 represents an aromatic ring structure having 6 to 50 carbon atoms or a heterocyclic structure having 4 to 50 carbon atoms, and the aromatic ring structure or the heterocyclic structure has a substituent.
  • X is a linking group and contains an aliphatic hydrocarbon having 1 to 10 carbon atoms (which may not be a linear, branched or alicyclic structure), or a substituent.
  • C1-C10 aliphatic hydrocarbon (does not matter even if it is linear, branched or alicyclic) o one, -OCH one, one SO-, one CO-, -COCH one,- CH OCO, 1 NHCO—,
  • the R 2 and R 3 each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms including a hydroxyl group or an alkoxyl group.
  • the hydrocarbon group may have an alicyclic structure, a branched structure or an aromatic ring structure.
  • the substituent of the aromatic ring structure and the heterocyclic structure of the phosphorus compound represented by the formula (Chemical Formula 44) is a hydrocarbon group having 1 to 50 carbon atoms (even if it is a straight chain, an alicyclic structure, a branched structure) Or an aromatic ring structure, which may be halogen-substituted), a hydroxyl group or a halogen group, an alkoxyl group having 1 to 10 carbon atoms or an amino group (alkyl having 1 to 10 carbon atoms or Or tro group or carboxy group is an aliphatic carboxylic acid ester group having 1 to 10 carbon atoms!
  • Examples of the phosphorus compound represented by the formula (Formula 44) include the following. Specifically, benzylphosphonic acid, benzylphosphonic acid monoethyl ester, 1-naphthylmethylphosphonic acid, 1 naphthylmethylphosphonic acid monoethyl ester, 2-naphthylmethylphosphonic acid, 2 naphthylmethylphosphonic acid monoethyl ester 4-phenyl, benzylphosphonic acid, 4-phenyl, benzylphosphonic acid monoethyl ester, 2-phenyl, benzylphosphonic acid, 2-phenyl, benzylphosphonic acid monoethyl ester, 4-chloro, benzene Dilphosphonic acid, 4-chloro, benzylphosphonic acid monoethyl ester, 4-chloro, benzylphosphonic acid jetyl ester, 4-methoxy, benzylphosphonic acid, 4-methoxy, benzylphosphonic acid, 4-
  • R ° is a hydroxyl group, a C1-C10 alkyl group, a COOH group or —C OOR 4 (R 4 represents a C1-C4 alkyl group), an alkylene glycol group Alternatively, it represents a monoalkoxyalkylene glycol group (monoalkoxy represents C1-C4, and alkylene glycol represents C1-C4 glycol).
  • R 1 represents an aromatic ring structure such as benzene, naphthalene, biphenyl, diphenyl ether, diphenyl thioether, diphenyl sulfone, diphenyl methane, diphenyl dimethyl methane, diphenyl ketone, anthracene, phenanthrene, and pyrene.
  • R 2 and R 3 are each independently a hydrogen atom, C1-C It represents a C1-C4 hydrocarbon group having 4 hydrocarbon groups, a hydroxyl group or an alkoxyl group.
  • m represents an integer of 1 to 5, and when R ° is plural, the same substituent or a combination of different substituents may be used.
  • n represents 0 or an integer of 1 to 5.
  • examples of the phosphorus compounds in which the aromatic ring structure having a substituent is benzene are as follows. .
  • Examples include benzylphosphonic acids in which a hydroxyl group is introduced into the benzene ring, such as loxybenzylphosphonic acid, 6-hydroxybenzylphosphonic acid jetyl ester, 6-hydroxybenzylphosphonic acid monoethyl ester, and 6-hydroxybenzylphosphonic acid. It is not limited.
  • 2 n-butylbenzylphosphonic acid jetyl ester 2 n-butylbenzylphosphonic acid monomethyl ester, 2 n-butylbenzylphosphonic acid, 3 n-butylbenzylphosphonic acid jetyl ester, 3-n-butylbenzyl Phosphonic acid monoethyl ester, 3-n-butylbenzylphosphonic acid, 4 n-butylbenzylphosphonic acid jetyl ester, 4 n-butylbenzylphosphonic acid monoethyl ester, 4 n-butylbenzylphosphonic acid, 2, 5 n-dibutylbenzyl Phosphonic acid jetyl ester, 2,5 n-dibutylbenzylphosphonic acid monoethyl ester, 2,5 n-dibutylbenzylphosphonic acid, 3,5-n-dibutylbenzylphosphonic acid jetyl ester, 3,5-n-dibutylbenz
  • 2 carboxybenzylphosphonic acid jetyl ester 2 carboxybenzylphosphonic acid monoethyl ester, 2 carboxybenzylphosphonic acid, 3 carboxybenzylphosphonic acid jetyl ester, 3-carboxybenzylphosphonic acid monoethyl ester, 3 —Carboxybenzylphosphonic acid, 4 Carboxybenzylphosphonic acid jetyl ester, 4 Carboxybenzylphosphonic acid monoethyl ester, 4 Carboxybenzylphosphonic acid, 2,5-dicarboxybenzylphosphonic acid jetyl ester, 2,5-dicarboxybenzylphosphonic acid monoethyl ester, 2,5-dicarboxybenzylphosphonic acid, 3,5-dicarboxybenzylphosphonic acid Acid ethyl ester, 3,5-dicarboxybenzylphosphonic acid monoethyl ester, 3,5-dicarboxybenzylphosphonic acid, 2-methoxycarbonylbenz
  • the phosphorus compound in which the aromatic ring structure having a substituent is benzene is not limited to the above-mentioned single substituent species.
  • a hybrid of a substituted group, a hydroxyl group, an alkyl group, a carboxyl group, a carboxyester group, a 2-hydroxyethoxy group, and a 2-methoxyethoxy group can also be used.
  • examples of the phosphorus compounds having a substituted aromatic ring structure of naphthalene include the following. .
  • the phosphorus compound having an aromatic ring structure having a substituent is naphthalene is not limited to the above-mentioned single substituent species.
  • a mixture of a group, a hydroxyl group, an alkyl group, a carboxyl group, a carboxyester group, a 2-hydroxyethoxy group, and a 2-methoxyethoxy group can also be used.
  • examples of the phosphorus compounds in which the aromatic ring structure having a substituent is biphenyl include the following. . That is, 4- (4-hydroxyphenyl) benzylphosphonic acid jetyl ester, 4- (4-hydroxyphenyl) benzylphosphonic acid monoethyl ester, 4- (4-hydroxyphenyl) benzylphosphonic acid, 4- (4-n-butylphenyl) benzylphosphonic acid jetyl ester, 4- (4-n-butylphenyl) benzylphosphonic acid monoethyl ester, 4- (4 n-butylphenyl) benzylphosphonic acid, 4 — (4-Carboxyphenyl) benzylphosphonic acid jetyl ester, 4- (4-carboxyphenyl) benzylphosphonic acid monoethyl ester, 4- (4-carboxyphenyl) benzyl
  • the phosphorus compound in which the aromatic ring structure having a substituent is biphenyl is not limited to the above-mentioned single substituent species.
  • a mixture of the above-mentioned substituent, hydroxyl group, alkyl group, carboxyl group, carboxyester group, 2-hydroxyethoxy group, and 2-methoxyethoxy group can also be used.
  • examples of the phosphorus compounds in which the aromatic ring structure having a substituent is diphenyl ether include the following. Can be mentioned. In other words, 4- (4-hydroxyphenyl) benzylphosphonic acid jetyl ester, 4- ( 4-Hydroxyphenyl) benzylphosphonic acid monoethyl ester, 4- (4-hydroxyphenyl) benzylphosphonic acid, 4- (4 n-butylphenyl) benzylphosphonic acid monoethyl ester, 4- (4 n-butylphenyl) benzylphosphonic acid monoethyl ester, 4- (4-butylphenyl) benzylphosphonic acid, 4- (4-butylphenyl) benzylphosphonic acid, 4- (4-carboxyphenyl) benzylphosphonic acid monoethyl ester, 4- (4-carboxyl Phenoxy) benzylphosphonic acid monoethyl ester, 4-one (four
  • the phosphorus compound having a substituent aromatic ring structure is diphenyl ether is limited to the above-mentioned single substituent species.
  • a mixture of the above-mentioned substituents, hydroxyl group, alkyl group, carboxyl group, carboxyester group, 2-hydroxyethoxy group, and 2-methoxyethoxy group can also be used.
  • examples of the phosphorus compounds in which the aromatic ring structure having a substituent is diphenyl ether are as follows.
  • the phosphorus compound in which the aromatic ring structure having a substituent is a diphenyl ether is not limited to the above-mentioned single substituent species. And a hybrid of a substituted group, a hydroxyl group, an alkyl group, a carboxyl group, a carboxyester group, a 2-hydroxyethoxy group, and a 2-methoxyethoxy group can be used.
  • examples of the phosphorus compound having a substituent aromatic ring structure of diphenylsulfone include the following. . 4- (4-hydroxyphenylsulfuryl) benzylphosphonic acid jetyl ester, 4- (4-hydroxyphenylsulfol) benzylphosphonic acid monoethyl ester, 4- (4-hydroxyphenylsulfuryl) benzyl Phosphonic acid, 4- (4-n-butylphenylsulfuryl) benzylphosphonic acid monoethyl ester, 4- (4-n-butylphenylsulfuryl) benzylphosphonic acid monoethyl ester, 4- (4- Butylphenylsulfol) benzilphosphonic acid, 4- (4-carboxyphenylsulfol) benzylphosphonic acid monoethyl ester, 4- (4-carbox
  • the phosphorus compound whose aromatic ring structure having a substituent is diphenylsulfone is not limited to the above-mentioned single substituent species.
  • a mixture of the above-described substituent, hydroxyl group, alkyl group, carboxyl group, carboxyester group, 2-hydroxyethoxy group, and 2-methoxyethoxy group can also be used.
  • examples of the phosphorus compounds in which the aromatic ring structure having a substituent is diphenylmethane are as follows.
  • Phosphonic acids into which a carboxyl group, a carboxylic acid ester group, an alkylene glycol group, a monomethoxyalkylene glycol group and the like have been introduced are not limited thereto.
  • the phosphorus compounds represented by the formula (Chemical Formula 45) are limited to the above-mentioned single substituent species.
  • a mixture of the above-mentioned substituents, hydroxyl group, alkyl group, carboxyl group, carboxyester group, 2-hydroxyethoxy group, and 2-methoxyethoxy group can also be used.
  • examples of the phosphorus compounds represented by the formula (Chemical Formula 45) include the following. Can be mentioned.
  • the phosphorus compounds represented by the formula (Chemical Formula 45) are limited to the above-mentioned single substituent species.
  • a compound in which the above-mentioned substituent, hydroxyl group, alkyl group, carboxyl group, carboxyester group, 2-hydroxyethoxy group, and 2-methoxyethoxy group are mixed can also be used.
  • examples of the phosphorus compounds in which the aromatic ring structure having a substituent is diphenyl ketone are as follows. That is, 4- (4-hydroxybenzoyl) benzylphosphonic acid jetyl ester, 4- (4-hydroxybenzoyl) benzylphosphonic acid monoethyl ester, 4- (4-hydroxybenzoyl) benzylphosphonic acid, (4 n-butylbenzoyl) benzylphosphonic acid monoethyl ester, 4- (4 n-butylbenzoyl) benzylphosphonic acid monoethyl ester, 4- (4-butylbenzoyl) benzylphosphonic acid, 4- (4-butylbenzoyl) benzylphosphonic acid, 4- (4-carboxybenzoyl) benzylphosphonic acid monoester 4- (4-Carboxybenzoyl) benzylphosphonic acid monoethyl ester, 4- (4-Carboxybenz
  • the phosphorus compound whose aromatic ring structure having a substituent is diphenylketone is not limited to the above-mentioned single substituent species.
  • a mixture of a substituent, a hydroxyl group, an alkyl group, a carboxyl group, a carboxyester group, a 2-hydroxyethoxy group, and a 2-methoxyethoxy group can also be used.
  • examples of the phosphorus compounds having an anthracene aromatic ring structure having a substituent are as follows. . 9- (10-hydroxy) anthrylmethylphosphonic acid jetyl ester, 9- (10-hydroxy) anthrylmethylphosphonic acid monoethyl ester, 9- (10-hydroxy) anthrylmethylphosphonic acid, 9- (10- n -Butyl) anthrylmethylphosphonic acid jetyl ester, 9- (10-n-butyl) anthrylmethylphosphonic acid monoethyl ester, 9 (10-n-butyl) anthrylylphosphonic acid, 9- (10-carboxy) anthrylmethylphosphonic acid 9- (10-carboxy) anthrylmethylphosphonic acid 9- (10-carboxy) 9- (2-hydroxyethoxy) anthrylmethylphosphone 9- (10-carboxy) anthrylmethylphosphonic acid 9- (10-carboxy) anthrylmethylphosphonic acid 9- (10-carboxy) anthrylmethylphosphonic acid 9- (10-
  • the phosphorus compound having an aromatic ring structure having an anthracene is not limited to the above-mentioned single substituent species.
  • a hybrid of the above-described substituent, hydroxyl group, alkyl group, carboxyl group, carboxyester group, 2-hydroxyethoxy group, and 2-methoxyethoxy group can also be used.
  • examples of the phosphorus compounds having a substituent aromatic ring structure is phenanthrene are as follows. .
  • the phosphorus compound having an aromatic ring structure having a substituent is phenanthrene is not limited to the above-mentioned single substituent species.
  • a hybrid of the above-described substituent, hydroxyl group, alkyl group, carboxyl group, carboxyester group, 2-hydroxyethoxy group, and 2-methoxyethoxy group can also be used.
  • examples of the phosphorus compounds in which the aromatic ring structure having a substituent is pyrene include the following. . That is, 1- (5-H Droxy) pyrenylmethylphosphonic acid jetyl ester, 1- (5-hydroxy) pyrenylmethylphosphonic acid monoethyl ester, 1- (5-hydroxy) pyrenylmethylphosphonic acid, 1- (5-n-butyl) pyrylmethylphosphone 1- (5-n-butyl) pyrylmethylphosphonic acid monoethyl ester, 1- (5-n-butyl) pyrylmethylphosphonic acid, 1- (5-carboxy) pyrenylmethylphosphone 1- (5-carboxy) pyrylmethylphosphonic acid monoethyl ester, 1- (5-carboxy) pyrylmethylphosphonic acid, 1- (5-hydroxyethoxy) pyrylmethylphosphonic acid Tilester, 1- (5-
  • the phosphorus compound in which the aromatic ring structure having a substituent is pyrene is not limited to the above-mentioned single substituent species. And a mixture of a substituted group, a hydroxyl group, an alkyl group, a carboxyl group, a carboxyester group, a 2-hydroxyethoxy group, and a 2-methoxyethoxy group can be used.
  • Substituents such as hydroxyl group, alkyl group, carboxyl group, force oxyester group, 2-hydroxyethoxy group and 2-methoxyethoxy group introduced into the above-mentioned series of aromatic rings are aluminum at the time of polymerization of polyester. It is presumed to be deeply involved in complex formation with atoms. In addition, some of them are similar to carboxyl groups or hydroxyl groups that are functional groups at the time of polyester formation, and are easily dissolved or incorporated in the polyester matrix. .
  • R Q an aromatic ring structure (R 1) is compared to the unsubstituted groups are hydrogen atom, Cl ⁇ of the present invention CIO alkyl group, —COOH group or —COOR 4 (R 4 represents a C1 to C4 alkyl group), alkylene glycol group or monoalkoxyalkylene glycol group (monoalkoxy is C1 to C4, alkylene glycol is C1
  • the phosphorus compound substituted with ⁇ C4 glycol) is preferable in terms of the foreign matter reducing effect that is achieved only by improving the catalytic activity.
  • Examples of the substituent bonded to the aromatic ring structure include C1 to C10 alkyl groups, carboxyl and carboxy ester groups, alkylene glycols and monoalkoxyalkylene glycols. More preferred in terms of the effect of reducing foreign matter are carboxyl and carboxyl ester groups, alkylene glycols and monoalkoxyalkylene glycols. The reason for this is unknown, but it is presumed to be due to improved compatibility with the polyester and the catalyst medium, alkylendalycol.
  • the phosphorus compound (Chemical Formula 46) having no linking group (X) preferably used in the present invention is as follows.
  • R 1 represents a heterocyclic structure aromatic ring structure or 4-50 carbon atoms having 6 to 50 carbon atoms
  • the aromatic ring structure or a heterocyclic structure be substituted! / ⁇ R 2 and R 3 each independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms including a hydroxyl group or an alkoxyl group.
  • a ring structure or a branched structure may have an aromatic ring structure.
  • the substituent of the aromatic ring structure and heterocyclic structure of the phosphorus compound represented by the formula (Chemical Formula 46) is a hydrocarbon group having 1 to 50 carbon atoms (an alicyclic structure, a branched structure, an aromatic ring even if it is linear) These may be structures which may be halogen-substituted), hydroxyl groups, halogen groups, C1-C10 alkoxyl groups or amino groups (C1-C10 alkyl or alkyl groups). ) Or -tro group or carboxy group is an aliphatic carboxylic acid ester group having 1 to 10 carbon atoms!
  • Is a formyl group or an acyl group ⁇ is a sulfonic acid group , Sulphonic acid amide groups (Alkyl groups with 1 to 10 carbon atoms or alkyl groups are not affected), phosphoryl-containing groups, nitrile groups
  • one or more cyanoalkyl groups are also selected.
  • the aromatic ring structure of the above is selected from benzene, naphthalene, biphenyl, diphenyl ether, diphenyl thioether, diphenyl sulfone, diphenyl methane, diphenyl dimethyl methane, anthracene, phenanthrene, and pyrene power.
  • the heterocyclic structure is selected from furan, benzofuran, isobenzofuran, dibenzofuran, naphthalane and phthalide.
  • Examples of the phosphorus compound represented by the formula (Formula 46) that can be used in the present invention include the following phosphorus compounds. That is, (3--toro, 5-methyl) -phenolphosphonic acid jetyl ester, (3--toro, 5-methyl) -phenylphosphonic acid monoethyl ester, (3--toro, 5-methyl) -Phenolphosphonic acid, (3-Tro, 5-methoxy) -Phenolphosphonic acid ethyl ester, (3-Tro, 5-methoxy) -Phenolphosphonic acid monoethyl ester, (3-Nitro, 5 —Methoxy) -phenylphosphonic acid, (4 chloro) -phenylphosphonic acid jetyl ester, (4 chloro,)-phenylphosphonic acid monoethyl ester, (4 chloro) -phenylphosphonic acid, (5-chloro) ,)-Phenolphosphonic acid jetyl
  • the above-described Linyi compound having no linking group may have a slightly lower polymerization activity than the above-mentioned Linyi compound having a linking group.
  • copolymerization polyester polymerization is performed. It can be used as a catalyst.
  • Phosphorus compound is a force known as a heat stabilizer for polyesters. Even if these compounds are used in combination with conventional metal-containing polyester polymerization catalysts, it is possible to greatly promote melt polymerization. It was an unknown force. In fact, the phosphorus compound in the present invention is added when the polyester is melt-polymerized using an antimony compound, a titanium compound, a tin compound or a germanium compound, which is a typical catalyst for polyester polymerization, as a polymerization catalyst. However, it has not been observed that polymerization is accelerated to a substantially useful level.
  • the amount of the phosphorus compound in the present invention preferably from 0.001 to 2.0 mole 0/0 with respect to the number of moles of all the structural units of the polycarboxylic acid component of the copolyester obtained, 0. 005-1. it is more preferably 0 mol 0/0. If the addition amount of the phosphorus compound is less than 0.001 mol%, the effect of addition may not be achieved. If the addition amount exceeds 2.0 mol%, the catalytic activity as a copolymerized polyester polymerization catalyst is reduced. The tendency of the decline varies depending on the amount of aluminum used.
  • At least one selected from an alkali metal, an alkaline earth metal, and a compound power thereof is preferably present as a second metal-containing component. It is an aspect. The coexistence of these second metal-containing components is preferred because the mixing into the glycol component distilled off during the polymerization is further suppressed compared to the case where the above-mentioned phosphorus compound is present.
  • coexistence of the above-mentioned second metal-containing component, particularly a lithium compound, in the catalyst system can be achieved by increasing the amount of addition when the polymerization temperature needs to be kept low, for example, 240 to 260 ° C. This is a preferred embodiment because it can have polymerization activity.
  • alkali metal when adding alkaline earth metals and their compounds, its amount M (mol 0/0), to the number of moles of all the polycarboxylic acids units constituting the polyester, 1 X 10- 6 or 1.0 mole% less preferably 5 X 10- 6 ⁇ 0 than the preferred tool be.
  • 5 model was le%, more preferably 1 X 10- 5 ⁇ 0. 3 mol%, especially preferred are 1 X 10- 5 ⁇ 0. 1 mol%. Since the amount of alkali metal and alkaline earth metal added is small, it is possible to increase the reaction rate without causing problems such as reduced thermal stability, generation of foreign matter, coloring, and degradation of hydrolysis resistance. It is.
  • the present invention it is preferable to use it in addition to aluminum or a compound thereof.
  • the second ano-rekari earth metal Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Of these, at least one selected from Ba force is preferred, and at least one selected from Li, Na, Mg or a compound thereof is more preferable.
  • Li is the most preferable element for the composition of the present invention.
  • the alkali metal or alkaline earth metal compound include saturated aliphatic carbonates such as formic acid, acetic acid, propionic acid, butyric acid, and succinic acid, and unsaturated aliphatic carboxylic acids such as acrylic acid and methacrylic acid.
  • aromatic carboxylates such as benzoic acid, halogen-containing carboxylates such as trichlorodiacetic acid, hydroxycarboxylates such as lactic acid, thearic acid, salicylic acid, carbonic acid, sulfuric acid, nitric acid, phosphoric acid, phosphonic acid, carbonic acid
  • Inorganic acid salts such as hydrogen, hydrogen phosphate, hydrogen sulfide, sulfurous acid, thiosulfuric acid, hydrochloric acid, hydrobromic acid, chloric acid, bromic acid, 1-propanesulfonic acid, 1-pentanesulfonic acid, naphtho Organic sulfonates such as tarene sulfonic acid, organic sulfates such as lauryl sulfate, methoxy
  • alkali metals alkaline earth metals or their compounds
  • a strongly alkaline one such as a hydroxide
  • these are dissolved in a diol such as ethylene glycol or an organic solvent such as an alcohol.
  • a strong substance such as a hydroxide
  • the polyester is liable to undergo side reactions such as hydrolysis during polymerization, and the polymerized polyester tends to be easily colored. Tend to decrease.
  • the alkali metal of the present invention or a compound thereof or the alkaline earth metal or a compound thereof is preferably a saturated aliphatic carboxylate, an unsaturated aliphatic carboxylate, an aroma of an alkali metal or an alkaline earth metal.
  • Group Carboxyl salt halogen-containing carboxylate, hydroxy carboxylate, sulfuric acid, nitric acid, phosphoric acid, phosphonic acid, hydrogen phosphate, hydrogen sulfide, sulfurous acid, thiosulfuric acid, hydrochloric acid, hydrobromic acid, chloroacid, bromic acid
  • the polymerization catalyst according to the present invention is another polymer catalyst such as an antimony compound, a germanium compound, a titanium compound, or a tin compound, and the addition of these components is a polyester as described above. It is effective to improve the productivity by shortening the polymerization time to use it in the range of the addition amount without causing a problem in the characteristics of the resin.
  • a catalyst that exhibits a sufficient catalytic effect can be obtained even when the addition amount of aluminum as a polyester polymerization catalyst is small.
  • Specific examples of the method for preparing the same solution when basic aluminum acetate is used as the aluminum compound are shown below. In the following, ethylene glycol is taken as an example, but the solvent can be changed as appropriate, and the following is read depending on the solvent used.
  • Basic aluminum acetate (hydroxyaluminum diacetate; manufactured by Aldrich) was dispersed in distilled water at a concentration of 2 OgZl and dissolved by heating at 95 ° C. for 2 hours with stirring.
  • An equal amount (volume ratio) of ethylene glycol was charged into the flask together with the aqueous solution, and the system power was distilled off while stirring at 70-90 ° C for several hours under reduced pressure (133 Pa).
  • An ethylene glycol solution of a -um compound was prepared.
  • Irganox 1222 (manufactured by Chinoku 'Specialty' Chemicals) as a phosphorus compound was charged into a flask together with ethylene glycol, heated at 160 ° C for 12 hours with stirring under nitrogen purge, and 30gZl of phosphorus compound ethylene A glycol solution was prepared.
  • the respective ethylene glycol solutions obtained in the preparation examples of the aluminum compound and the preparation example of the phosphorus compound are charged into a flask and mixed at room temperature so that the aluminum and phosphorus atoms are in a molar ratio of 1: 2.
  • the catalyst solution was prepared by stirring for 5 hours.
  • Lithium acetate 2H 2 O and sodium acetate as alkali metal compounds (Nacalai Co., Ltd.)
  • the reagent was manufactured in a flask together with ethylene glycol, and a force without stirring under nitrogen substitution prepared an ethylene glycol solution of an alkali metal compound at 30 g / l at room temperature.
  • an ethylene glycol solution of the above-described aluminum compound Z an ethylene glycol solution of a phosphorus compound and an alkali metal compound ethyl ether.
  • a glycol glycol solution it is also possible to use a glycol glycol solution in combination.
  • composition ratio of the polyvalent carboxylic acid component and the polyhydric alcohol component constituting the copolymerized polyester resin of the present invention varies depending on the intended use. The following is a description for each application.
  • the amount of isophthalic acid in the acid component in the polyester resin of the present invention is 18 mol% or more, preferably 20 mol% or more, and if it is less, the softening point of the polyester resin tends to be high. For example, when used as a powder coating, the appearance of the coating film may be deteriorated. In addition, when used in solvent-soluble paints and water-dispersed paints, there is a possibility that the solubility in solvents and water dispersibility will decrease, making it difficult to produce paints.
  • the upper limit of isophthalic acid may be 100 mol%.
  • dicarboxylic acid component in addition to isophthalic acid, aromatic dicarboxylic acids such as terephthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, phthalic anhydride, succinic acid, glutaric acid, adipic acid, sebacic acid, Aliphatic dicarboxylic acids such as azelaic acid, dodecanedioic acid and dimanoic acid, unsaturated dicarboxylic acids such as fumaric acid, maleic anhydride, terpene maleic acid adducts, 1,4-cyclohexanedicarboxylic acid, tetrahydric acid
  • aromatic dicarboxylic acids such as terephthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, phthalic anhydride, succinic acid, glutaric acid, adipic acid, sebacic acid
  • Aliphatic dicarboxylic acids such as azelaic acid, dodecan
  • 2-Methyl-1,3propanediol and Z or 1,3-propanediol, which are glycol components, are inferior in mechanical properties of the coating film when less than 20 mol%, and exceed 80 mol%.
  • the temperature of the soft transition point and the glass transition temperature are low, and powder coatings prepared from this may cause blocking during storage.
  • the darlicol component that can be used in the present invention, 2-methyl-1,3 propanediol and Z or 1,3 propanediol are suitable. Otherwise, ethylene glycol, propylene glycol, 1,4 butanediol, 1,2 Butanediol, neopentyl glycol, 1,5 pentanediol, 3-methyl-1,5 pentanediol, 2 ethyl-2-butyl-1,3 propanediol, 2,4 jetyl 1,5 Pentanediol, 1-methyl-1,8 octanediol, 3-methyl-1.6 hexanediol, 4-methyl-1,7 heptanediol, 4-methyl-1,8 octanediol, 4 propyl1.8 octanediol, 1,9-nonanediol, Aliphatic glycols such as diethylene glycol, triethylene glycol, polyethylene glycol, polyethylene
  • the polyester resin of the present invention may be copolymerized with 1 to 16 mol% of a tri- or tetrafunctional monomer component as a branched component in either or both of an acid component and a glycol component.
  • a tri- or tetrafunctional monomer component as a branched component in either or both of an acid component and a glycol component.
  • branching components if it exceeds 16 mol% of the total monomer, depending on the type of branching agent, it may become an unsuitable resin that is partially gelled, and the hydroxyl value of the obtained resin exceeds 70 mgKOHZg. As a result, the hardness of the resulting coating film may become high and the flexibility may be poor.
  • Examples of the tri- or tetra-functional component that can be used as a branching agent in the present invention include trimellitic anhydride, pyromellitic anhydride, methylcyclohexanetricarboxylic acid, trimethylolpropane, trimethylolethane, glycerin, pentaerythritol, and the like. Can be mentioned. From these, one or more can be selected and used.
  • the copolymerized polyester resin of the present invention has a number average molecular weight measured by gel permeation chromatography (GPC) of 2000 to 7000, more preferably 2500 to 6500. . If the number average molecular weight is lower than 2000, the mechanical properties of the coating film may be insufficient, and if it exceeds 7000, the smoothness of the coating film may be inferior. When used for water-dispersed type or solvent-soluble type, the number average is 3 ⁇ 4 3 ⁇ 4.
  • the copolymerized polyester resin of the present invention preferably has a hydroxyl value measured by a method of acetylation using pyridine as a solvent and refluxing at its boiling point, when used as a powder coating, preferably 20 to 70 mg KOHZg, More preferably, it is 25-65 mgKOHZg. If the hydroxyl value is lower than 20 mg KOHZg, sufficient mechanical properties tend to be difficult to obtain. If it exceeds the range of 70 mg KOH / g, adding a suitable amount of curing agent (blocked isocyanate) will increase the cost, and it will not be possible to improve the strength and film performance. The hardness may be high and the flexibility may be inferior.
  • the blending amount of the block silicate curing agent is less than the amount commensurate with the hydroxyl value, sufficient mechanical properties of the coating film can be obtained.
  • those with a hydroxyl value of less than 2 OmgKOHZg are also used.
  • the copolymer polyester resin of the present invention has a soft spot measured by the ring and ball method CFIS K2207) of 105 to 140 ° C when used as a powder coating, more preferably 110 to 135 ° C. It is. When used for water-dispersed or solvent-soluble types, those with a soft spot of 140-220 ° C are also used.
  • the copolymer polyester resin of the present invention has a glass transition temperature measured by a differential scanning calorimetry (DSC) of 40 to 75 ° C when used as a powder coating, more preferably 40 to 70 °. C.
  • the softening point and glass transition temperature when the soft transition point is lower than 105 ° C and the glass transition temperature is lower than 40 ° C, it is easy to cause blocking during storage when used as a powder coating.
  • the glass transition temperature higher than the softening point S140 ° C or higher is higher than 75 ° C, the finished appearance of the coating film, especially the smoothness, may be deteriorated.
  • glass transition point temperature force less than 0 ° C or more than 75 ° C is also used.
  • the reaction can be promoted by pressurizing or depressurizing operation or by using an inert gas, which may be different from the transesterification method or the direct esterification method.
  • the acid component may be a polybasic acid containing a strong lpoxyl group, or a compound obtained by esterifying a carboxyl group with methanol. In the former case, the polymerization proceeds by an esterification reaction by dehydration, and in the latter case, the polymerization proceeds by an ester exchange reaction by demethanol.
  • all the raw materials may be added to the reaction vessel at once and allowed to react.
  • the raw materials may be added sequentially.
  • only a part of the acid component and the daricol component The catalyst component to be described is first charged into the reaction vessel and the esterification reaction or transesterification reaction proceeds. Then, the remaining acid component is charged and the esterification reaction or transesterification reaction proceeds again. I like it.
  • the acid component is often in a powder form, while the glycol component is often in a liquid state. Therefore, if all the raw materials are added to the reaction vessel at once, there are too many powder components and it takes a heavy load to stir, so there is a possibility that the reaction rate may slow down.
  • the acid component to be added first is the total acid component
  • the polymerization reaction is allowed to proceed while introducing nitrogen into the reaction system.
  • nitrogen By introducing nitrogen, the generated water and methanol vapor can be efficiently discharged out of the system, so that the polymerization reaction can proceed efficiently.
  • Nitrogen can be simply flowed into the gas phase of the reaction system, but it is better to publish directly into the reaction mixture.
  • the polymerization reaction of the polyester resin in the present invention is preferably performed in the range of 150 to 300 ° C. It is desirable to raise the temperature mildly in order to suppress sublimation and bumping of the raw material. Completion of the reaction is based on the method in which the theoretical amount of water or alcohol is discharged, the method of measuring the carboxyl group or hydroxyl group at the molecular end by titration, the method of measuring the melt viscosity or soft spot of the reactant, etc. Can be determined.
  • a step of reducing the pressure at 6500 to 90000 Pa may be introduced for the purpose of removing excess glycol component, remaining water and alcohol. good. If it is less than 6500 Pa, the glycol component may be higher than the target molecular weight due to excessive removal of the glycol component, and if it exceeds 90000 Pa, the darlicol, water or alcohol is efficiently removed. There is a risk that it cannot be done. When used for water-dispersed type or solvent-soluble type, it has a step to further advance the polycondensation reaction in a high vacuum state of lOOOPa or less!
  • a depolymerization reaction or a modification reaction may be performed after completion of the polymerization reaction.
  • a polycarboxylic acid and Z or a polyhydric alcohol to the molten polyester resin to react.
  • the polyvalent power capable of constituting the above-described polyester resin Rubonic acid and polyhydric alcohol can be used.
  • terephthalic acid, isophthalic acid, trimellitic acid, pyromellitic acid, ethylene glycol, neopentyl glycol, trimethylolpropan, pentaerythritol are used for reasons such as controlling reaction and increasing reactive end groups. Glycerin and the like are preferably used.
  • the reaction is preferably carried out in the range of 150 to 290 ° C for 1 to 300 minutes.
  • Examples of the modification reaction include a ring-opening addition reaction of a latathone monomer to a polyester resin. This makes it possible to produce a block type polyester resin in which a poly-strength prolatatone is bonded to the end of the polyester resin.
  • ⁇ single-strength plutathon is preferable.
  • the reaction is preferably carried out in the range of 150 to 290 ° C for 1 to 300 minutes.
  • the polyester resin (A) produced as described above can be blended with a curing agent (B) capable of reacting with (A) to form a coating material.
  • the curing agent capable of reacting with the polyester resin (A) include alkyl etherified aminoformaldehyde resins, epoxy compounds and isocyanate compounds, alkyl etherified phenol resins, and silane coupling agents.
  • alkyl etheraminoformaldehyde resins are preferred in terms of reactivity and hardness.
  • Epoxy compounds are preferred in terms of weather resistance and acid resistance.
  • Block isocyanate is preferable from the viewpoint of solution stability and toughness.
  • Alkyl etherified aminoformaldehyde resin is, for example, formaldehyde or paraformaldehyde alkylated with an alcohol having 1 to 4 carbon atoms such as methanol, ethanol, n-propanol, isopropanol, n-butanol.
  • Examples thereof include benzoguanamine, methoxylated methylol melamine, butoxylated methylol melamine, methoxy Z-butoxy mixed methylol melamine, and butoxylated methylol benzoguanamine.
  • diglycidyl ether of bisphenol A and its oligo Diglycidyl ether of hydrogenated bisphenol A and oligomers thereof orthophthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, terephthalic acid diglycidyl ester, p-oxybenzoic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester Hexahydrophthalic acid diglycidyl ester, succinic acid diglycidyl ester, adipic acid diglycidyl ester, sebacic acid diglycidyl ester, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1, 4 butanediol diglycidyl ether, 1, 6 hexanediol diglycidyl ether and polyalkylene glycol diglycidyl ethers, trimellitic acid triglycidino
  • the isocyanate compounds include aromatic and aliphatic diisocyanates and polyisocyanates having a valence of 3 or more, and any of low molecular compounds and high molecular compounds may be used.
  • the isocyanate compound may be a blocked isocyanate.
  • Isocyanate blocking agents include, for example, phenols such as phenol, thiophenol, methylthiophenol, ethinoretioenole, crezo monole, xylenenole, resonoresinole, nitrophenol, kuroenofenol, acetooxime, methyl Ethyl ketoxime, Siku Oximes such as oral hexanone oxime, alcohols such as methanol, ethanol, propanol and butanol, halogen-substituted alcohols such as ethylene chlorohydrin, 1,3-dichloro-2-propanol, t-butanol, t-pentanol, Tertiary alcohols such as ⁇ -force prolatatam, ⁇ -valerolatatam, y- buti-oratalata, e-prote pyrrolatatam, etc
  • silane coupling agents include j8— (3,4 epoxycyclohexenole) ethinotritrimethoxysilane, j8— (3,4 epoxycyclohexyl) ethyltrimethylsilane, ⁇ -glycidoxypropyl lipoline.
  • Examples include methyl ethoxysilane and ⁇ -glycidoxypropyl methyl jetoxy silane.
  • the curing agent ( ⁇ ) component is handled when used as a powder coating.
  • the mixing ratio of the curing agent ( ⁇ ) is preferably such that the ratio of the reactive functional group equivalent to the hydroxyl equivalent of the polyester resin is in the range of 0.8 to 1.2.
  • the coating composition of the present invention has a constitution such as pigments such as titanium oxide, carbon black, organic color pigments, inorganic color pigments, dyes, aluminum flakes, silica, talc, and sodium sulfate depending on the purpose and application.
  • Additives such as pigment, glass fiber, colloidal silica, and wax can be added.
  • the inorganic pigments used in the present invention include inorganic pigments, colored pigments, luster materials, extender pigments, antifouling pigments, and the like.
  • inorganic pigments such as titanium dioxide, iron oxide, chromium oxide, chromate, carbon black, acid silicate, zinc phosphate, iron phosphate, aluminum phosphate, zinc phosphite, aluminum tripolyphosphate, etc.
  • Phosphoric acid-based anti-pigment pigments calcium molybdate, aluminum molybdate, barium molybdate, etc., molybdate-type anti-fog pigments, vanadium-type anti-fog pigments such as vanadium oxide, chromate pigments such as strontium chromate and zinc chromate , Silicate pigments such as calcium silicate, water-dispersed silica, Fine silica such as fumed silica can be used.
  • bright materials such as aluminum flakes, copper bronze flakes, mica-like iron oxide, mica flakes, mica-like iron oxide coated with metal oxides, and mica flakes coated with metal oxides can also be mentioned.
  • organic pigments such as phthalocyanine blue, phthalocyanine green, carbazole dioxazine violet, anthrapyrimidine yellow, isoindolinone yellow, indanthrene bunore, quinatalidone red may be used in combination.
  • the effect when used as a powder coating material, the effect is exhibited to the maximum, and it is preferable. However, it is of course possible to use it as a solvent-soluble or water-dispersed coating material.
  • the powder coating is usually blended with a pigment or other filler, a flow regulator such as an acrylate polymer, a curing catalyst, a pinhole inhibitor such as benzoin, and the like, kneaded using a known melt kneader, Then, it is pulverized and classified to form a powder coating material.
  • the powder coating thus obtained is applied and baked on a metal steel plate or the like by a known electrostatic coating method or fluidized dip coating method.
  • the polyester resin of the present invention can be widely used for adhesives, coating agents, binders for toners, raw materials for synthesis of polyurethane resins, plasticizers, etc., only for paint applications.
  • the production method of the copolymerized polyester resin (i) mainly for powder coating is as follows.
  • the present invention relates to a method for producing a copolymerized polyester in the presence of a polymerization catalyst containing at least an aluminum compound.
  • the acid component is 100 mol%
  • the glycol component is 90 to 150 mol%. Particularly effective when used for polymerization.
  • the glycol component is used in an amount exceeding 150 mol%, it may be difficult to obtain a copolymerized polyester resin having a target molecular weight due to the remaining excess glycol component.
  • the glycol component is less than 90 mol%, the esterification reaction or transesterification reaction does not proceed efficiently, and it may be difficult to obtain a copolymerized polyester resin having the targeted molecular weight.
  • Glycol component preferably be used 95 to 120 mol% instrument 95 to:! L 10 mole 0/0 is most preferred to use /,.
  • a polybasic acid containing a carboxyl group is used as the acid component.
  • a compound obtained by esterifying a good carboxyl group with methanol or the like may be used.
  • the polymerization proceeds by an esterification reaction by dehydration, and in the latter case, the polymerization proceeds by an ester exchange reaction by demethanol.
  • the number average molecular weight of the polyester resin produced by the production method of the present invention is preferably 2000 to 7 000. If it is less than 2000, the resin is brittle and, for example, the coating strength tends to be low even when used as a coating agent. Even trying to produce more than 7000 polyester resin, the polymerization time tends to be very long.
  • all the raw materials may be added to the reaction vessel at once and allowed to react.
  • the raw materials may be added sequentially.
  • only a part of the acid component, the dallicol component, and the catalyst component described below are first charged into the reaction vessel, and the esterification reaction or transesterification reaction is allowed to proceed. Then, the remaining acid component is charged and the esterification reaction is performed again. Or, it is preferable to carry out the procedure in which the transesterification reaction proceeds.
  • the acid component is often in a powder form, while the glycol component is often in a liquid state.
  • the acid component to be added first is preferably 20 to 80% by weight of the total acid component! /.
  • the polymerization reaction is allowed to proceed while further introducing nitrogen into the reaction system.
  • nitrogen By introducing nitrogen, the generated water and methanol vapor can be efficiently discharged out of the system, so that the polymerization reaction can proceed efficiently.
  • Nitrogen can be simply flowed into the gas phase of the reaction system, but it is better to publish directly into the reaction mixture.
  • the polymerization reaction of the polyester resin in the present invention is preferably performed in the range of 150 to 300 ° C. It is desirable to raise the temperature mildly in order to suppress sublimation and bumping of the raw material. Completion of the reaction is based on the method in which the theoretical amount of water or alcohol is discharged, the method of measuring the carboxyl group or hydroxyl group at the molecular end by titration, the method of measuring the melt viscosity or soft spot of the reactant, etc. Can be determined.
  • a step of reducing the pressure at 6500 to 90000 Pa is introduced for the purpose of removing excess glycol component, remaining water and alcohol. You may enter. If it is less than 6500 Pa, the glycol component may be higher than the target molecular weight due to excessive removal of the glycol component, and if it exceeds 90000 Pa, the darlicol, water or alcohol is efficiently removed. There is a risk that it cannot be done.
  • copolymer polyester resin (ii) used in precoat paints with an emphasis on processability is as follows.
  • the acid component used in the copolymer polyester resin (C) to be produced is 30 to 80 mol% of terephthalic acid, preferably 30-60 mole 0/0 and the sum is 70 to 100 molar 0/0 of terephthalic acid and other aromatic dicarboxylic acids, preferably 90 to 100 mole 0/0 other dicarboxylic acids force ⁇ to 30 mole 0/0 It is. If the amount of terephthalic acid exceeds 80 mol%, good solvent solubility cannot be obtained, and if it is less than 30 mol%, a good balance between good cacheability and hardness cannot be obtained. If the total of aromatic dicarboxylic acids is less than 70 mol%, good alkali resistance, food contamination resistance, weather resistance and hardness cannot be obtained.
  • aromatic dicarboxylic acids other than terephthalic acid that are copolymerized with the copolymerized polyester resin (C) of the present invention include isophthalic acid, orthophthalic acid, and 2,6-naphthalenedicarboxylic acid. Of these, terephthalic acid and isophthalic acid are particularly preferably used as the aromatic dicarboxylic acid from the viewpoint of processability and hardness.
  • Examples of other dicarboxylic acids copolymerized with the copolymerized polyester resin (C) of the present invention include succinic acid, glutaric acid, adipic acid, sebacic acid, dodecanedioic acid, azelaic acid, and dimer acid.
  • Examples of the alicyclic dicarboxylic acid copolymerized with the copolymerized polyester resin (C) of the present invention include 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid.
  • alicyclic dicarboxylic acids such as acids.
  • unsaturated polycarboxylic acids such as trimellitic anhydride and pyromellitic anhydride, unsaturated acids such as fumaric acid, itaconic acid, dimer acid, dodecelucono and succinic acid 2
  • a dicarboxylic acid having a heavy bond may be used in combination.
  • the glycol component copolymerized with the copolymerized polyester resin (C) of the present invention includes 2-methyl-1,3-propanediol and / or 1,3-propanediol.
  • Le 0/0 preferably from 10 to 25 mole 0/0
  • alkylene glycol having 5 to 10 carbon atoms is 75 to 99 molar 0/0, preferably from 75 to 90 mole 0/0. If 2-methyl-1,3 propanediol and Z or 1,3 propanediol exceeds 25 mol%, good cacheability cannot be obtained, and alkali resistance also decreases. If it is less than 1 mol%, good hardness cannot be obtained.
  • the alkylene glycol having 5 to 10 carbon atoms used in the present invention specifically includes 1,5-pentanediol, 1,6 hexanediol, 3-methyl-1,5-pentanediol, 2-methyl-1 , 5 Pentanediol, 1,7 octanediol, 1,9-nonanediol, alkylene glycols such as 1,10-decanediol, 1,2-cyclohexanedimethanol, 1,3 cyclohexanedimethanol, 1 , 4-cyclohexanedimethanol.
  • a polyhydric polyol such as trimethylolethane, trimethylolpropane, glycerin or pentaerythritol may be used in combination as long as the content of the present invention is not impaired.
  • dicarboxylic acid glycol containing a sulfonic acid metal base may be used in an amount of 5 mol% or less.
  • dicarboxylic acid containing a sulfonic acid metal base include metal salts such as 5-sulfoisophthalic acid, 4 sulfonaphthalene-2,7-dicarboxylic acid, and 5- (4-sulfophenoxy) isophthalic acid. .
  • Examples of the darlicol containing a sulfonic acid metal base include metal salts such as 2-sulfo-1,4-butanediol and 2,5-dimethyl-3-sulfo-2,5-hexanediol.
  • metal salts include salts of Li, Na, K, Mg, Ca, Cu, Fe and the like.
  • the copolymerized polyester resin (C) of the present invention after the polyester resin is polymerized, trimellitic anhydride, phthalic anhydride, pyromellitic anhydride, succinic anhydride, anhydrous 1, 8 Naphthalic acid, 1,2-cyclohexanedicarboxylic anhydride, etc. may be added afterwards to give the acid value.
  • trimellitic anhydride phthalic anhydride, pyromellitic anhydride, succinic anhydride, anhydrous 1, 8 Naphthalic acid, 1,2-cyclohexanedicarboxylic anhydride, etc.
  • the preferred acid value is 20-300 equivalents Zl0 6 g. More preferably from 50 to 150 eq Z1 0 6 g. If the acid value exceeds 300 equivalents / 10 6 g, good cacheability will not be obtained.
  • the specific gravity of the copolymerized polyester resin (C) of the present invention is 1.21 to L30. Specific gravity is 1.
  • the glass transition temperature of the copolymerized polyester resin (C) of the present invention is 45 ° C or lower, preferably 10 to 30 ° C. When the glass transition temperature exceeds 45 ° C, it becomes hard and good strength cannot be obtained.
  • the reduced viscosity of the copolymerized polyester resin (C) of the present invention is not less than 0.2 dlZg, preferably not less than 0.4 dlZg. If it is less than 2 dlZg, good cacheability cannot be obtained.
  • Known methods such as transesterification, in which dimethyl ester and glycol are transesterified before polymerization, a method in which a small amount of xylene is added and a dehydration reaction is carried out at normal pressure, and a reaction vessel not equipped with a decompression device
  • JP-A-6-220359 disclosed in Example 1 of JP-A-6-220359
  • a method of polymerizing by raising the temperature after removing condensed water at a temperature not exceeding 100 ° C under normal pressure, etc. Is synthesized.
  • the polymerization catalyst of the present invention can use an aluminum compound, a phosphorus compound, an alkali metal and / or an alkaline earth metal
  • the resin composition for coatings of the present invention can be used by blending a curing agent (D) capable of reacting with the copolymerized polyester resin (C).
  • a curing agent capable of reacting with the copolymerized polyester resin (C).
  • solvent resistance can be imparted, and various coating film properties such as processability, hardness, stain resistance, chemical resistance, and corrosion resistance can be improved.
  • the copolymerized polyester resin (C) of the present invention and the curing agent (D) capable of reacting with these include isocyanate compounds, alkyl etherified aminoformaldehyde resins, epoxy compounds, and phenol resins. Etc. Of these, alkyl etherified aminoformaldehyde resin and resol type phenol resin are preferable from the viewpoint of processability. Furthermore, it is preferable to block the isocyanate stable toy compound, which is particularly preferred for the isocyanate compound from the viewpoint of acid resistance.
  • the isocyanate compound includes aromatic and aliphatic diisocyanates and triisocyanate or higher polyisocyanates, and may be either a low molecular compound or a high molecular compound.
  • aromatic and aliphatic diisocyanates and triisocyanate or higher polyisocyanates may be either a low molecular compound or a high molecular compound.
  • Isocyanate blocking agents include, for example, phenols such as phenol, thiophenol, ethylthiophenol, cresonole, xylenore, resonoresinole, nitrophenol, and black mouth phenol, acetoxime, methyl ketyl ketoxime, Oximes such as cyclohexanone oxime, alcohols such as methanol, ethanol, propanol and butanol, halogen-substituted alcohols such as ethylene chlorohydrin and 1,3-dichloro1-2propanol, and tertiary compounds such as t-butanol and t-pentanol Grade alcohols, epsilon prolactams, ⁇ -noratolatatam, y-butyroratam, ⁇ -propirolatam, and other ratatams.
  • phenols such as phenol, thiophenol, ethylthiophenol, cre
  • Blocky Isocyanate can be obtained by addition reaction of the above-mentioned isocyanate compound, isocyanate blocking agent, and a conventionally known appropriate method.
  • Alkyl etherified aminoformaldehyde resin is, for example, formaldehyde or paraalkyl etherified with an alcohol having 1 to 4 carbon atoms such as methanol, ethanol, n-propanol, isopropanol, or n-butanol. It is a condensation product of formaldehyde, etc.
  • Metokishii spoon melamine, Ri Ah at butoxy methylol melamine or methoxylated / Butokishii spoon mixed melamine may be used alone, or in combination.
  • the epoxy compounds include diglycidyl ether of bisphenol ⁇ and its oligomer, diglycidyl ether of hydrogenated bisphenol A and its oligomer, diglycidyl orthophthalate, diglycidyl isophthalate, diglycidyl terephthalate Esters, p-oxybenzoic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, succinic acid diglycidinoresestenole, adipic acid diglycidinoresestenole, cenosinic acid diglycidinole Ester, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4 butanediol diglycidyl ether, 1,6 hexanediol diglycidyl ether, and poly Alkylene glycol diglycidyl ethers, trimellitic acid t
  • aldehyde is added to phenol in the presence of an alkali catalyst.
  • alkali catalyst examples thereof include a resol type resin reacted and a novolak type obtained by reacting phenols with an aldehyde in the presence of an acidic catalyst, which means a suitable crosslinking agent, and a resol type resin is particularly preferable.
  • the phenols used in these phenolic fats are: phenol, 0 cresol monole, p cresol, m-cresol, m-methoxy phenol, 2, 3 xy lenenole, 2, 5 xy lenol, p- tert butyl phenol, p ethyl phenol, Bisphenol A, bisphenol F, etc., and these mono-trimethylol compounds and their condensates, or their alkyl ethers, or various modifications such as epoxy modification, oil modification, melamine modification, and amide modification. Can be used.
  • Preferable phenols that can be used as a raw material include phenol, m-cresol, bisphenol A, and bisphenol F that are tri- or higher functional as a phenol.
  • curing agents are preferably used in combination with a known curing agent or accelerator selected according to the type.
  • the baking temperature of the modified copolymerized polyester resin of the present invention can be arbitrarily selected depending on the size and thickness of the metal plate, the capability of the baking furnace, the curability of the paint, and the like.
  • a mixer such as a roll kneader, a ball mill, a sand mill or a blender is used.
  • paint coating, electrostatic coating, etc. are selected as appropriate.
  • the coating composition of the present invention can contain pigments such as titanium oxide, additives such as glass fiber, silica, and wax according to the purpose and application.
  • the resin composition for coatings of the present invention is usually used in a form dissolved in an organic solvent.
  • an ionic group such as a sulfonic acid metal base
  • an aqueous dispersion is used.
  • the organic solvent include toluene, xylene, Solvesso 100 and 150, ethyl acetate, butyl acetate, methyl solvate, cetyl sorb, butyl sorb, ethyl carbitol, butyl carbitol, methyl ceryl acetate, It is appropriately selected from ethyl acetate sorb acetate, methyl carbitol acetate, butyl carbitol acetate, methyl ethyl ketone, cyclohexanone, isophorone, N-methylpyrrolidone, dibasic acid ester, etc.
  • the coating composition of the present invention itself exhibits sufficient characteristics even when applied to a metal plate and baked, but when it is required to further improve the corrosion resistance or the like, the primer coat is used.
  • Epoxy resin, polyester resin, and urethane resin may be used as the agent.
  • copolymerized polyester resin (iii) used in the precoat paint that places particular emphasis on blocking resistance is as follows.
  • the carboxylic acid component ( a ) produced in the presence of the polymerization catalyst containing the aluminum compound used in the present invention and constituting the copolymer polyester resin is 10 to 70 mol% of terephthalic acid (al).
  • the total amount of acid (al) and other aromatic dicarboxylic acid (a2) is 80 mol% or more
  • the glycol component (g) is 2-methyl-1,3-propanediol and Z or 1,3-propanediol ( gl) 25 mol% or more of alkylene glycol of 5 to 10 carbon atoms and Z or alicyclic glycol (g2) 75 mol% or less of the glycol component (g) and (gl) glycol and (g2) glycol
  • carboxylic acid component constituting the copolyester ⁇ (E) of the present invention is terephthalic acid 1 0-70 mole 0/0, preferably 20 to 60 mole 0/0, and terephthalic acid and other aromatic total di- carboxylic acid is 80 to: LOO mol 0/0, preferably 90 to: L00 mole 0 /. , And the other dicarboxylic acid force ⁇ ⁇ 20 mol 0/0.
  • the carboxylic acid component terephthalic acid exceeds 70 mole 0/0 not good solvent solubility can be obtained, not obtained good processability and hardness Roh "lance is less than 10 mol%. Also, if the total of aromatic dicarboxylic acids is less than 80 mol%, good hardness, stain resistance, blocking resistance, pressure mark resistance, alkali resistance, and weather resistance cannot be obtained.
  • aromatic dicarboxylic acids other than terephthalic acid that are copolymerized in the copolymerized polyester resin ( ⁇ ) constituting the present invention include isophthalic acid, orthophthalic acid, and 2,6-naphthalene dicarboxylic acid. .
  • terephthalic acid and isophthalic acid in combination is particularly preferred in view of the balance between drawability, workability, impact resistance and hardness.
  • carboxylic acids other than the above include aliphatic dicarboxylic acids such as succinic acid, daltaric acid, adipic acid, sebacic acid, dodecanedicarboxylic acid, azelaic acid, 1,2-cyclohexanedicarboxylic acid, 1, 3 —Cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid and other alicyclic dicarboxylic acids can be mentioned, but alicyclic dicarboxylic acids are preferred.
  • a polyvalent carboxylic acid such as trimellitic anhydride or pyromellitic anhydride may be used in combination as long as the content of the invention is not impaired.
  • the glycol component (g) copolymerized with the copolymer polyester resin (E) constituting the present invention is 2-methyl-1,3-propanediol and Z or 1,3-propanediol (gl) force ⁇ 25 ⁇ : LOO Monore 0/0, preferably ⁇ or 30-90 Monore 0/0, more preferably ⁇ or 50-90 Monore 0/0, alkylene glycol and ⁇ or alicyclic glycols having a carbon number of 5 to 10 (g2) 0-75 mole 0/0, preferably from 10 to 50 mol%, the sum of the Darikoru 50 mol% or more.
  • 1,3-propanediol as an alkylene glycol having 5 to 10 carbon atoms, for example, 3-methyl-1,5-pentanediol has a main chain having 5 or more carbon atoms and an alkyl group in the side chain. It is particularly preferable to use a combination of varnish and the surface strength of varnish stability and processability over time.
  • the copolymerized polyester resin (E) constituting the present invention it is preferable to copolymerize alkylene glycol having 5 to 10 carbon atoms and Z or alicyclic glycol. These are copolymerized to give flexibility and improve workability and impact resistance. Can do good.
  • polyester with a high glass transition temperature is required, the use of alicyclic glycol is preferred because of its workability and impact resistance.
  • the alkylene glycol having 5 to 10 carbon atoms used in the present invention specifically includes 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 2-methyl-1,5-pentane.
  • Examples include diol, 1,9-nonanediol, 1,10 decandiol, 1,4 cyclohexane dimethanol, 1,3 cyclohexane dimethanol, and 1,2 cyclohexane dimethanol.
  • Particularly preferred for the physical properties of the coating film are 1,6 hexanediol and 1,5 pentanediol.
  • alicyclic glycol used in the present invention examples include 1,4 cyclohexane dimethanol, 1,3 cyclohexane dimethanol, 1,2 cyclohexane dimethanol, hydrogenated bisphenol A, and the like. Can be mentioned. 1,4 cyclohexane dimethanol is also particularly preferred for the physical properties of the coating film.
  • a polyhydric polyol such as trimethylol ethane, trimethylol propane, glycerin or pentaerythritol may be used in combination as long as the content of the invention is not impaired.
  • metal salts such as 5-sulfoisophthalic acid, 4-sulfonaphthalene-1,7-dicarboxylic acid, 5 [4-sulfophenoxy] isophthalic acid or 2-sulfo-1,4-butanediol, 2,5 dimethyl-3 —
  • Dicarboxylic acids or glycols containing metal sulfonates such as metal salts such as sulfo-2,5 hexanediol may be used within the range of 5 mol% or less of the total acid or total glycol component! / ,.
  • the copolymerized polyester resin (E) used in the present invention has curability and surface properties of the coating film, preferably an acid value of 20 to 350 equivalents Zl0 6 g, more preferably 50 to 250 equivalents Zl0 6 g. It is desirable. By adding an acid value, the curability is improved and the strength, scratch resistance, stain resistance, etc. are further improved. When the acid value exceeds 350 equivalents of Zl0 6 g, the cacheability decreases, which is preferable.
  • the method of adding acid value to polyester resin is to polymerize polyester resin, under normal pressure, trimellitic anhydride, phthalic anhydride, pyromellitic anhydride, succinic anhydride, 1,8 naphthalic acid anhydride, 1, 2 It is preferable to add an acid value by post-installing cyclohexanedicarboxylic acid or the like.
  • the copolymerized polyester resin (E) used in the present invention has a glass transition temperature of 10 to 80 ° C, preferably 15 to 60 ° C. If the glass transition temperature is less than 10 ° C, good hardness, scratch resistance, stain resistance, and drawability cannot be obtained. Workability and impact resistance are reduced.
  • the copolymerized polyester resin (E) used in the present invention has a reduced viscosity of 0.2 dlZg or more, preferably 0.3 dlZg, more preferably 0.4 dlZg or more. If the reduced viscosity is less than 0.2 dlZg, good processability, drawability, hardness and impact resistance cannot be obtained.
  • the polyester resin (E) used in the present invention has a specific gravity of 1.21-1.30, preferably 1.22-1.28. If the specific gravity is less than 1.21, good balance of hardness, drawing workability and workability cannot be obtained, and the stain resistance is poor. If the specific gravity exceeds 1.30, good solvent solubility cannot be obtained.
  • the preferred number average molecular weight of the copolymerized polyester resin (E) used in the present invention is 300,000 or more, more preferably 8000 or more. If it is less than 3000, the workability, hardness, and impact resistance deteriorate.
  • the preferred hydroxyl value is 30 to 500 equivalents of Zl0 6 g, more preferably 30 to 250 equivalents / 10 6 g. As the hydroxyl value is higher than 500 equivalents / 10 6 g, the workability and impact resistance decrease. If the hydroxyl group is less than 30 equivalents of Zl0 6 g, the reactivity with the curing agent becomes poor, and the hardness and stain resistance are reduced.
  • the precoat resin composition of the present invention is used by blending a curing agent (F) capable of reacting with the copolymerized polyester resin (E).
  • ( ⁇ ) / (F) 90 ⁇ 10 to 70 ⁇ 30. If ( ⁇ ) exceeds 95 ⁇ 5, the coating film hardness, stain resistance, blocking resistance, and pressure mark resistance will decrease. On the other hand, when ( ⁇ ⁇ ) is less than 60 ⁇ 40, workability and impact resistance are deteriorated.
  • Examples of the curing agent (F) capable of reacting with the copolymerized polyester resin ( ⁇ ) constituting the present invention include alkyl etherified aminoformaldehyde resins, epoxy compounds, and isocyanine one-toy compounds. .
  • Alkyl etherified aminoformaldehyde resin is, for example, formaldehyde or paraformaldehyde alkylated with an alcohol having 1 to 4 carbon atoms such as methanol, ethanol, ⁇ -propanol, isopropanol, ⁇ -butanol and urea, ⁇ , ⁇ —Condensation products with ethylene urea, dicyandiamide, aminotriazine, etc., and methoxylated methylol— ⁇ , ⁇ —ethylene urea, methoxylated methylol dicyandiamide, methoxylated methylol benzoguanamine, butoxylated methylol benzoguanamine, methoxy Methylol melamine, butoxylated methyl Examples include roll melamine, methoxyl ⁇ ⁇ / butoxylated mixed methylolmelamine, butoxylated methylol benzoguanamine, etc., but due to processability
  • Epoxy compounds include diglycidyl ether of bisphenol A and oligomers thereof, diglycidyl ether of hydrogenated bisphenol A and oligomers thereof, orthophthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, and terephthalic acid diglycidyl ester.
  • Esters p-oxybenzoic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, succinic acid diglycidyl ester, adipic acid diglycidyl ester, sebacic acid diglycidyl ester, ethylene glycol diglycidyl ether , Propylene glycol diglycidyl ether, 1,4 butanediol diglycidyl ether, 1,6 hexanediol diglycidyl ether and polyalkylene glycol Cole diglycidyl ethers, trimellitic acid triglycidinole esterolate, triglycidyl isocyanurate, 1,4-diglycidinole aged xybenzene, diglycidyl propylene urea, glycerol triglycidyl ether, trimethylol noreethane triglycid
  • the isocyanate compound includes aromatic and aliphatic diisocyanates and polyisocyanates having a valence of 3 or more, and may be either a low molecular compound or a high molecular compound.
  • aromatic and aliphatic diisocyanates and polyisocyanates having a valence of 3 or more, and may be either a low molecular compound or a high molecular compound.
  • the isocyanate compound may be a blocked isocyanate.
  • Isocyanate blocking agents include, for example, phenols such as phenol, thiophenol, methylthiophenol, ethinoretioenole, crezo monole, xylenenole, resonoresinole, nitrophenol, kuroenofenol, acetooxime, methyl Ethyl ketoximes, hexanone oxime oximes, alcohols such as methanol, ethanol, propanol, butanol, halogen-substituted alcohols such as ethylene chlorohydrin, 1,3-dichloro-2-propanol, t-butanol , Tertiary alcohols such as t-pentanol, ⁇ —force prolatatam, ⁇ —valerolatatam, y —buty oral ratatam, e-prote pyrrolatatam etc., and other
  • crosslinking agents may be used in combination with a known curing agent or accelerator selected according to the type.
  • the coating composition of the present invention exhibits sufficient performance even when it is applied to a metal plate and baked, but when it is required to further improve the corrosion resistance, etc., a primer coat is used.
  • a primer coat is used as the agent.
  • epoxy resin, polyester resin, urethane resin, etc. may be used as the agent.
  • the baking temperature of the coating composition of the present invention depends on the size and thickness of the steel sheet and the capacity of the baking furnace.
  • a mixer such as a roll kneader, a ball mill or a blender is used.
  • a blender such as a roll kneader, a ball mill or a blender is used.
  • paint coating roller coating, roll coater, spray coating, electrostatic coating, etc. are selected as appropriate.
  • the coating composition of the present invention has a constitution such as titanium oxide, carbon black, pigments such as organic color pigments and inorganic color pigments, dyes, aluminum flakes, silica, talc, and sodium sulfate depending on the purpose and application.
  • Additives such as pigment, glass fiber, colloidal silica, and wax can be added.
  • the bisphenol A and Z or bisphenol F alkylene oxide-containing product used in the present invention is composed of all glycol components.
  • ⁇ : LOO Monore 0/0 are intended to be included preferably ⁇ or 15 to 80 Monore 0/0, further [this preferably ⁇ or 25 to 60 Monore%. If it is 5 mol% or less, the above-mentioned characteristics such as corrosion resistance and workability of the above-mentioned bisphenol ⁇ and ⁇ or bisphenol F alkylene oxide adduct may not be exhibited.
  • the acid component used in the copolymer polyester resin (G) to be produced is an aromatic dicarboxylic acid 50-: LOO mol% , the preferred properly 70 to: LOO mol 0/0, more preferably from 80 to 100 mol 0/0. If the aromatic dicarboxylic acid is less than 50 mol%, good acid resistance, chemical resistance and scratch resistance cannot be obtained! / ⁇ .
  • Examples of the aromatic dicarboxylic acid copolymerized with the copolymerized polyester resin (G) of the present invention include terephthalic acid, isophthalic acid, orthophthalic acid, and 2,6-naphthalenedicarboxylic acid.
  • the aromatic dicarboxylic acid it is particularly preferable to use terephthalic acid and isophthalic acid in combination in terms of physical properties and solubility of the coating film.
  • the content of aromatic dicarboxylic acids 50-100 Monore 0/0, more preferably from 80-100 Monore 0/0.
  • the other dicarboxylic acid copolymerized with the copolymerized polyester resin (G) of the present invention is 50 mol% or less, and preferably 30 mol% or less.
  • examples of other dicarboxylic acids include aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, dicarboxylic acids having an unsaturated double bond, and the like. These dicarboxylic acids are not essential, but, for example, aliphatic dicarboxylic acid and Z or alicyclic dicarboxylic acid can be provided with flexibility mainly by copolymerization, so that processability can be improved.
  • dicarboxylic acids having an unsaturated double bond reduce melt viscosity without lowering the glass transition temperature, impart curability with actinic rays such as UV and EB, and acrylic grafts.
  • actinic rays such as UV and EB
  • acrylic grafts can be used as a functional group for
  • Examples of the aliphatic dicarboxylic acid copolymerized with the copolymerized polyester resin (G) of the present invention include succinic acid, glutaric acid, adipic acid, sebacic acid, dodecanedioic acid, azelaic acid, dasleic acid, Imamic acid etc. are mentioned.
  • Examples of the alicyclic dicarboxylic acid copolymerized with the copolymerized polyester resin (G) of the present invention include 1,2 cyclohexanedicarboxylic acid, 1,3 cyclohexanedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid.
  • the acid resistance which is preferred from the viewpoint of processability, is preferably 30 mol% or less for adipic acid, sebacic acid, and 1,4-cyclohexanedicarboxylic acid.
  • the glycol component copolymerized with the copolymerized polyester resin (G) of the present invention includes the bisphenol A and / or bisphenol F ethylene oxide adduct and Z or propylene oxide addition represented by the above formula 1. Other glycols other than those are usually used in combination.
  • glycols include ethylene glycol, propylene glycol, neopentyl alcohol, 1,3 propanediol, 2-methyl-1,3 propanediol, 2-butyl-2-ethyl-propanediol, 1,4 butanediol, 1, 2 Butanediol, 1,3 Butanediol, 1,5 Pentanediol, 1,6 Hexanediol, 1,7 Octanediol, 1,9-Nonanediol, 3-Methyl-1,5 Pentanediol, 3-Methyl, 8— Alkylene glycols such as methyl-1,8 octanediol, alicyclic glycols such as 1,4 cyclohexane dimethanol, 1,2 cyclohexane dimethanol, TCD glycol, diethylene glycol, polyethylene glycol, polypropylene glycol Polyalkylene glycols such as It is done
  • glycols are selected as appropriate from the viewpoints of economics and physical properties of the coating, but ethylene glycol, diethylene glycol, 2-methyl-1,3 propanediol, neopentyl glycol, 1,4 cyclohexanedimethanol, 1,5-pentanediol, 1,6-hexanediol and the like are preferable.
  • polyvalent carboxylic acids such as trimellitic acid and pyromellitic acid or polyhydric polyols such as trimethylolethane, trimethylolpropane, glycerin, and pentaerythritol are generally used or 0.1 to When 3 mol% is used, the acid resistance can be further improved.
  • the copolymer polyester resin of the present invention is copolymerized with a dicarboxylic acid containing an unsaturated double bond having a double bond, preferably at 30 mol% or less, more preferably at 10 mol% or less.
  • Dicarboxylic acids containing unsaturated double bonds include a, ⁇ Fumaric acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid as unsaturated dicarboxylic acids, 2,5-norbornane dicarboxylic anhydride, tetrahydrophthalic anhydride, as alicyclic dicarboxylic acids containing unsaturated double bonds, A dimer acid etc. can be mentioned.
  • the melt viscosity can be lowered without lowering the glass transition temperature, and the softness point can be lowered. Both blocking properties can be achieved. Furthermore, there is a feature that the reactivity with the curing agent can be improved.
  • unsaturated dicarboxylic acids containing the above double bonds preferred are fumaric acid, maleic acid and 2,5-norbornene dicarboxylic acid (endobicyclo (2, 2, 1) —5 heptene-1,2,3 dicarboxylic acid). Acid) and particularly preferred is fumaric acid.
  • the copolymerized polyester resin of the present invention in which an unsaturated double bond is copolymerized can reduce the melt viscosity while maintaining a high glass transition temperature and a high molecular weight, and thus is suitable for heat seal coating.
  • both blocking resistance and film-forming property melting property at low temperature
  • it is also suitable for powder coatings, hot melt adhesives, electrostatic toner applications and the like.
  • radical polymerization inhibitor Mainly used for the prevention of gelation due to double bond cleavage when polymerizing copolyester resin (A) Even if it is added after polymerization to increase the storage stability of polyester resin Good.
  • the radical polymerization inhibitor include known ones such as phenolic acid antioxidants, phosphorus antioxidants, amine antioxidants, sulfur acid antioxidants, and inorganic compound acid antioxidants.
  • Phenolic antioxidants include 2,5-di-t-butylhydroquinone, 4,4-butyldenbis (3-methyl-6-t-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5) t-Butylphenyl) butane, 1, 3, 5 tris-methyl-2, 4, 6-tris (3,5-di-tert-butyl 4-hydroxybenzyl) benzene, tris (3,5-di-tert-butyl-4-hydroxyphenol ) Isocyanurate and the like or derivatives thereof.
  • Phosphorus antioxidants include tri (noelphenol) phosphite, triphenyl phosphate, diphenylisodecyl phosphite, trioctadecyl phosphite, tridecyl phosphatase. Ito, diphenyl-decyl phosphite, 4,4, -butylidene-bis (3-methyl-6-t-butylyl-ditridecyl phosphite), distearyl-pentaerythritol diphosphite, trilauryl trithiophosphite, etc. Or derivatives thereof.
  • Amine antioxidants include phenol-naphthanaphthylamine, phenothiazine, N, N, 1-diphenyl and 1-phenolamine, N, N, 1-dinaphthalyl and 1-phenylamine. N cyclohexyl N, 1-fluoro-p-dirangeamine, aldol alpha naphthylamine, 2,2,4 trimethyl-1,2 dihydrate quinoline polymer, or derivatives thereof.
  • Sulfuric acid inhibitors include thiobis (N-phenylrubber 1-naphthylamine, 2 mercaptobenzazole, 2-mercaptobenzoimidazole, tetramethylthiuram disulfide, nickel isopropyl xanthate, or derivatives thereof. Can be mentioned.
  • Nitro compound-based antioxidants include 1, 3, 5 tri-trobenzene, p-trosodiphenylamine, p-trosodimethylaline, 1-black mouth 3 -trobenzene, o dito mouth Examples thereof include benzene, m-dinitrobenzene, p-dinitrobenzene, ⁇ -trobenzoic acid, nitrobenzene, 2-tro 5 cyanothiophene, and the like.
  • Inorganic compound antioxidants include FeCl, Fe (CN), CuCl, CoCl, Co (CIO)
  • a phenol-based antioxidant and an amine-based oxidic inhibitor preferably have a melting point of 120 in terms of thermal stability.
  • a melting point of 170 ° C or higher is more preferable, and a melting point of 170 ° C or higher is more preferable.
  • Specific examples include phenothiazine, 4,4, -butylidenebis (3-methyl-6-t-butylphenol).
  • the addition amount of the radical polymerization inhibitor is preferably 0.001 to 0.5 parts by weight, more preferably 0.01 to 0.5 parts by weight with respect to 100 parts by weight of the copolymerized polyester resin (G). 0.1 part by weight. If less than 001 parts by weight, the thermal stability during polymerization of the polyester is low and there is a risk of gelation due to double bond cleavage, which may make it difficult to produce a high molecular weight polyester. Exceeding this may adversely affect the physical properties of the cured coating film.
  • a direct polymerization method in which dicarboxylic acid and glycol are directly esterified and polymerized under normal pressure or under pressure as exemplified in the Examples, dimethyl ester of dicarboxylic acid and glycol
  • a known method such as an ester exchange method in which an ester is exchanged and then polymerizing, a method in which a small amount of xylene is added and a dehydration reaction is performed at normal pressure, and a reaction kettle that is not equipped with a decompression device
  • 6-220359 it is synthesized by a method of polymerizing by raising the temperature after removing condensed water at a temperature not exceeding 100 ° C under normal pressure. Is done.
  • an aluminum compound, a phosphorus compound, an alkali metal and Z or an alkaline earth metal can be used.
  • the copolymerized polyester resin (G) of the present invention can change its properties depending on the application, but the glass transition temperature is preferably 0 to 80 ° C, more preferably 40 to 80 °. C. When the temperature is less than 0 ° C, the workability is good. Scratch resistance, chemical resistance, boiling water resistance, blocking resistance, and the like may be lowered. If it exceeds 80 ° C, the acid resistance is good, but the workability may decrease, which is not preferable.
  • the copolymer polyester resin (A) of the present invention preferably has a number average molecular weight of 2,000 or more, more preferably 5,000 to 35,000. If the number average molecular weight is less than 2,000, there is a risk that physical properties such as processability and impact resistance will deteriorate.
  • dicarboxylic acid glycol containing a sulfonic acid metal base may be used in an amount of 5 mol% or less.
  • dicarboxylic acid containing a sulfonic acid metal base include metal salts such as sulfoterephthalic acid, 5-sulfoisophthalic acid, 4 sulfonaphthalene-1,2 dicarboxylic acid, and 5 (4-sulfophenoxy) isophthalic acid.
  • Examples of darlicol containing a sulfonic acid metal base include metal salts such as 2-sulfo-1,4 butanediol and 2,5 dimethyl-3-sulfo-2,5 hexanediol.
  • metal salts include salts such as Li, Na, K, Mg, Ca, Cu, and Fe.
  • a trivalent or higher carboxylic acid such as trimellitic anhydride or pyromellitic anhydride at 5 mol% or less of the total acid component.
  • acid addition such as trimellitic anhydride, phthalic anhydride, and ethylene glycol bistrimellitate dianhydride is added to give an acid value.
  • trimellitic anhydride, phthalic anhydride, and ethylene glycol bistrimellitate dianhydride is added to give an acid value.
  • the reactivity with rosin, phenolic rosin, and epoxy rosin is improved, and further, metal adhesion is improved, and scratch property can be improved, which is preferable.
  • the modified copolymer polyester resin (H) of the present invention is produced by modifying the copolymer polyester resin (G) using various chemical reactions. That is, vinyl modification with a vinyl polymerizable monomer, epoxy resin modification with an epoxy compound, or urethane modification with an isocyanate compound may be performed. In the case of vinyl modification, dicarboxylic acids having unsaturated double bonds such as fumaric acid and oleic acid are copolymerized with polyester resin to introduce unsaturated double bonds into the polyester resin.
  • Epoxy resin modification is performed by adding an acid anhydride such as trimellitic anhydride or hydrous phthalic acid to the terminal hydroxy group of polyester resin, followed by terminal carboxyl modification, and then the carboxyl group and epoxy resin. It can be synthesized by a known method such as a method in which fat is epoxy-modified in the presence of a catalyst such as triphenylphosphine.
  • a carboxyl group may be introduced by using a carboxyl group-containing glycol such as dimethylol propionic acid as a chain extender.
  • urethane modification it is synthesized by a known method such as blending a low molecular weight polyester diol and a chain extender if necessary and reacting with a diisocyanate compound.
  • a carboxyl group-containing diol such as dimethylolpropionic acid may be used as the chain extender V, and the carboxyl group may be introduced into the side chain b.
  • the copolymer polyester resin (G) and Z of the present invention or a copolymer polyester resin (H) obtained by modifying these and a curing agent (I) capable of reacting with these are used for coatings.
  • solvent resistance can be imparted, and various coating film properties such as processability, hardness, stain resistance, chemical resistance, and corrosion resistance can be improved.
  • the copolymer polyester resin (G) of the present invention and cocoon or copolymer polyester resin ( ⁇ ) obtained by modifying these and the curing agent (I) capable of reacting with these are the isocyanate compounds.
  • alkyl ether amide formaldehyde resins, epoxy compounds and phenol resins are preferred from the viewpoint of processability.
  • alkyl etherified aminoform aldehyde resins and resol type phenol resins are preferred from the viewpoint of processability.
  • Isocyanate compounds include aromatic and aliphatic diisocyanates and trivalent or higher polyisocyanates, which may be either low molecular compounds or high molecular compounds.
  • Isocyanate blocking agents include, for example, phenols such as phenol, thiophenol, ethylthiophenol, cresonole, xylenore, lesonoresinore, nitrophenol, and black mouth phenol, acetoxime, methylethylketooxime, Oximes such as cyclohexanone oxime, alcohols such as methanol, ethanol, propanol and butanol, halogen-substituted alkyls such as ethylene chlorohydrin, 1,3-dichloro-1,2-propanol, etc.
  • Examples thereof include tertiary alcohols such as coles, t-butanol and t-pentanol, ratatas such as ⁇ -force prolactam, ⁇ -noratalata, y-butyroratam and ⁇ -propirolatam.
  • Other examples include active methylene compounds such as aromatic amines, imides, acetylethylacetone, acetyl acetate, and malonate, mercaptans, imines, ureas, diaryl compounds, and sodium bisulfite.
  • the blocked isocyanate is obtained by addition reaction of the above isocyanate compound, the isocyanate blocking agent, and an appropriate conventionally known method.
  • Alkyl etherified aminoformaldehyde resin is, for example, formaldehyde or paraalkyl etherified with an alcohol having 1 to 4 carbon atoms such as methanol, ethanol, ⁇ -propanol, isopropanol, or ⁇ -butanol.
  • Formaldehyde is a condensation product of urea, ⁇ , ⁇ '-ethyleneurea, dicyandiamide, aminotriazine, etc., and methoxylated methylol- ⁇ , N'-ethyleneurea, methoxylated methylol dicyandiamide, methoxylated methylol.
  • Nzoguanamine proxiated methylol benzoguanamine, methoxylated methylol melamine, butoxylated methylol melamine, methoxylated / butoxy ⁇ mixed methylol melamine, butoxylated methylol benzoguanamine, etc.
  • Epoxy compounds include bisphenol ⁇ diglycidyl ether and its oligomer, hydrogenated bisphenol A diglycidyl ether and its oligomer, orthophthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, and diglycidyl terephthalate.
  • Esters p-oxybenzoic acid diglycidyl ester, tetrahydride phthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, succinic acid diglycidyl ester, adipic acid diglycidyl ester, sebacic acid diglycidyl ester, ethylene glycol diglycidyl Ether, propylene glycol diglycidyl ether, 1,4 butanediol diglycidyl ether, 1,6 hexanediol diglycidyl ether, and polyalkylene glycol Lumpur diglycidyl ethers, trimellitic Santo Re glycidioxypropyl Honoré Este Honoré, triglycidyl Honoré iso Xia sulfonate, 1, 4 Jigurishijinore old Kishibenze , Diglycidyl propylene urea, glycerol triglycidyl ether
  • examples of the phenolic resin include a resol type resin made by reacting phenol with an aldehyde in the presence of an alkali catalyst, and a novolak type made by reacting phenols with an aldehyde in the presence of an acidic catalyst. It means a suitable crosslinking agent, and a resol type rosin is particularly preferable.
  • the phenols used in these phenolic fats are: phenol, 0 cresol monole, p cresol, m-cresol, m-methoxy phenol, 2, 3 xy lenenole, 2, 5 xy lenol, p- tert butyl phenol, p ethyl phenol, Bisphenol A, bisphenol F, etc., and these mono-trimethylol compounds and their condensates, or their alkyl ethers, or various modifications such as epoxy modification, oil modification, melamine modification, and amide modification. Can be used.
  • Preferable phenols that can be used as a raw material include phenols having three or more functional groups as phenol, m-cresol, bisphenol A, and bisphenol F.
  • curing agents are preferably used in combination with a known curing agent or accelerator selected according to the type.
  • the baking temperature of the modified copolymerized polyester resin of the present invention can be arbitrarily selected depending on the size and thickness of the metal plate, the capability of the baking furnace, the curability of the paint, and the like.
  • a mixer such as a roll kneader, a ball mill, a sand mill or a blender is used.
  • roller coating, roll coater, spray coating, electrostatic coating, etc. are appropriately selected.
  • the modified resin composition of the present invention is an extender pigment such as titanium oxide, talc, barium sulfate or clay, or a chromium-containing antifungal pigment such as zinc chromate, strontium chromate or calcium chromate, depending on the purpose and application.
  • an extender pigment such as titanium oxide, talc, barium sulfate or clay
  • a chromium-containing antifungal pigment such as zinc chromate, strontium chromate or calcium chromate, depending on the purpose and application.
  • Colloidal silica, tripolyphosphate such as aluminum tripolyphosphate, zinc phosphate, phosphite, phosphomolybdate, molybdate, cyanamide zinc calcium, borate, calcium silica
  • Non-chromium anti-fading materials such as known colorants, additives such as silica and wax, flame retardants, glass fiber, etc. Can be combined.
  • the resin composition for coatings of the present invention is usually used in a form dissolved in an organic solvent.
  • an ionic group such as a sulfonic acid metal base or a carboxyl group is introduced.
  • a carboxyl group it is used after neutralizing with various amine compounds.
  • the organic solvent include toluene, xylene, Solvesso 100 and 150, ethyl acetate, butyl acetate, methyl solvate, cetyl sorb, butynocellerosonoleb, ethyl carbitol, butyl carbitol, and methyl.
  • modified copolyester resin of the present invention is suitable for coating the back side of a painted metal plate because it exhibits sufficient characteristics even if it is applied and baked on itself.
  • a top coating known as a top coat can be applied.
  • the modified copolymerized polyester resin of the present invention can be used as an image recording medium by applying it to paper or plastic film. Compared with the conventional technology, excellent printability and anti-fingerprint properties can be obtained.
  • the copolymer polyester resin (V) used in the toner is as follows.
  • the composition of the polyester resin used for the noder resin of the electrostatic charge developing toner is such that the acid component is 50 to 100 mol% of an aromatic dicarboxylic acid, 0 to 50 mol% of other carboxylic acid, trifunctional
  • the polyvalent carboxylic acid is 0 to 15 mol%
  • the glycol component is an alkylene oxide adduct of bisphenol A and Z or bisphenol F represented by the formula 1 above, and other glycols 0 to 95 mol%, trifunctional or higher polyhydric alcohol 0 to 15 mol%.
  • 0 mol% indicates an optional component.
  • the above-mentioned formula 1 used as the darikol component of the copolymerized polyester resin in the present invention is preferably a bisphenol A and Z or bisphenol F alkylene oxide-enriched product, preferably for all glycol components. 5 ⁇ : LOO mole 0/0, preferably 15 to 95 model %, More preferably 25 to 95 mol%. If it is 5 mol% or less, it may not be possible to obtain a predetermined melt viscosity capable of exhibiting the low-temperature fixability possessed by the above bisphenol A and Z or bisphenol F alkylene oxide-containing product.
  • the alkylene oxide portion is preferably ethylene oxide or 1,2-propylene oxide.
  • the acid component used in the copolymer polyester resin is an aromatic dicarboxylic acid 50 to: LOO mol%, preferably 70 to: LOO mol%, more preferably. Is 80-: L00 mol%. If the aromatic dicarboxylic acid is less than 50 mol%, the glass transition temperature of the resin is lowered, and for example, blocking at a high temperature of 45 ° C may not be suppressed.
  • Examples of the aromatic dicarboxylic acid copolymerized with the polyester resin for electrostatic charge development of the present invention include terephthalic acid, isophthalic acid, orthophthalic acid, and 2,6-naphthalenedicarboxylic acid.
  • the aromatic dicarboxylic acid it is particularly preferable to use terephthalic acid and isophthalic acid in combination in terms of coating film properties and solubility.
  • the other dicarboxylic acid copolymerized with the polyester resin is 0 to 50 mol%, preferably 0 to 30 mol%.
  • examples of other dicarboxylic acids include aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, and dicarboxylic acids having an unsaturated double bond. These dicarboxylic acids are not essential, but, for example, an aliphatic dicarboxylic acid and Z or an alicyclic dicarboxylic acid can be copolymerized to achieve both anti-blocking properties and low-temperature fixing properties.
  • the saturated aliphatic dicarboxylic acid and unsaturated aliphatic dicarboxylic acid copolymerized with the polyester resin for electrostatic charge development of the present invention include succinic acid, fumaric acid, maleic anhydride, citraconic acid, itaconic acid, glutar Acid, adipic acid, sebacic acid, dodecanedioic acid, azelaic acid, dimer acid, alkyl or alkenyl-substituted succinic acid.
  • succinic acid fumaric acid, maleic anhydride, citraconic acid, itaconic acid, glutar Acid, adipic acid, sebacic acid, dodecanedioic acid, azelaic acid, dimer acid, alkyl or alkenyl-substituted succinic acid.
  • Examples include alicyclic dicarboxylic acids such as 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid.
  • alicyclic dicarboxylic acids such as 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid.
  • the glycol component to be copolymerized with the copolymerized polyester resin of the present invention includes those other than the bisphenol A and Z or bisphenol F ethylene oxide adduct and the Z or propylene oxide adduct represented by the above formula 1.
  • Other glycols are usually used in combination in the range of 0 to 95 mol%.
  • glycols include ethylene glycol, 1,2 propylene glycol, neopentyl glycol, 1,3 propanediol, 2-methyl-1,3 propanediol, 2 butyl-2-ethyl propanediol, 1, 4 Butanediol, 1,2-butanediol, 1,3 butanediol, 1,5 pentanediol, 1,6 hexanediol, 1,7 octanediol, 1,9-nonanediol, 3-methyl-1,5 pentanediol, Alkylene glycols such as 3-methyl, 8-methyl-1,8 octanediol, 1,4 cyclohexanedimethanol, 1,2 cyclohexanedimethanol, 3 (4), 8 (9) -tricyclo [5.
  • Alicyclic glycols such as decanedimethanol, diethylene glycol, polyethylene glycol, polypropylene glycol And polyalkylene glycols such as From the viewpoint of polyester polymerizability and toner properties, ethylene glycol, 1,2-propylene glycol, neopentyl glycol, 1,4 cyclohexane dimethanol, etc. are preferred!
  • the trifunctional or higher polyvalent carboxylic acids include pyromellitic acid, trimellitic acid, trimesic acid, 3, 4, 3, 4, 4-biphenyltetracarboxylic acid, 2, 5, 7 naphthalenetricarboxylic acid.
  • Acid 1 2, 4 naphthalene tricarboxylic acid, 1, 2, 4 butane tricarboxylic acid, 1, 2, 5 hexane tricarboxylic acid, 1, 3 dicarboxyl 2-methyl 2-methylenecarboxypropane, 1, 2, 4 cyclo Hexanetricarboxylic acid, tetra (methylenecarboxyl) methan, 1,2,7,8 octanetetracarboxylic acid, empor trimer acid and the like.
  • These acid anhydrides or lower alkyl ester compounds may also be used!
  • trifunctional or higher polyhydric alcohols include sorbitol, 1, 2, 3, 6 hexanthrone, 1, 4-sonolebitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1, 2, 4 butanetriol. 1, 2, 5 Pentanetriol, Glicello , 2-methylpropanetriol, 2-methyl-1,2,4butanetriol, trimethylolethane, trimethylolpropane, 1,3,5 trihydroxymethylbenzene, and the like.
  • the temperature dependence of the melt viscosity becomes mild, and the hot fixing roll is resistant to hot. There is an advantage that the offset property is excellent.
  • a monofunctional monomer may be introduced into the polyester for the purpose of blocking the polar group at the end of the polyester molecule and improving the environmental stability of the toner charging characteristics.
  • Monofunctional monomers include benzoic acid, black mouth benzoic acid, bromobenzoic acid, parahydroxybenzoic acid, sulfobenzoic acid monoammonium salt, sulfobenzoic acid monosodium salt, cyclohexylaminocarboxylic benzoic acid, n-dodecylamino benzoic acid, tert-butyl benzoic acid, naphthalene carboxylic acid, 4 methyl benzoic acid, 3 methyl benzoic acid, salicylic acid, thiosalicylic acid, phenol acetic acid, acetic acid, propionic acid, butyric acid, iso Monocarboxylic acids such as butyric acid, octanecarboxylic acid, lauric acid, stearyl acid, and lower al
  • a radical polymerization inhibitor Mainly used to prevent gelation due to double bond cleavage when polymerizing copolyester resin, it may be added after polymerization in order to increase the storage stability of polyester resin.
  • the radical polymerization inhibitor include known antioxidants such as phenolic antioxidants, phosphorus antioxidants, amine antioxidants, sulfur antioxidants, and inorganic compound antioxidants.
  • Phenolic antioxidants include 2,5-di-t-butylhydroquinone, 4,4-butyldenbis (3-methyl-6-t-butylphenol), 1,1,3 tris (2-methyl-4-hydroxy-5) t-Butylphenyl) butane, 1, 3, 5 tris-methyl-2, 4, 6-tris (3,5-di-tert-butyl 4-hydroxybenzyl) benzene, tris (3,5-di-tert-butyl-4-hydroxyphenol ) Isocyanurate, or derivatives thereof.
  • Phosphorous antioxidants include tri (noelphenol) phosphite, triphenyl phosphite, diphenyl isodecyl phosphite, trioctadecyl phosphite, tridecyl phosphite, diphenyl decyl phosphite. 4, 4, -butylidene-bis (3-methyl-6-t-butylphenyl-ditridecylphosphite), distearyl-pentaerythritol diphosphite, trilauryltrithiophosphite, or their derivatives. It is done.
  • Amine-based antioxidants include ferro- ⁇ naphthylamine, phenothiazine, ⁇ , ⁇ , 1 diphenyl ⁇ phenylenediamine, ⁇ , N 'di 1 j8 naphthyl 1 p phenylene diamine, N cyclohexane.
  • Examples include hexyl N, one-f-loop, p-direnamine, aldol a naphthylamine, 2,2,4 trimethyl-1,2,2 dihydrate quinoline polymer, and derivatives thereof.
  • Sulfuric acid and sodium hydroxide inhibitors include thiobis (N-phenol- ⁇ -naphthylamine, 2-mercaptobenzazole, 2-mercaptobenzoimidazole, tetramethylthiuram disulphide, nickel isopropyl xanthate, etc. Or a derivative thereof.
  • Nitro compound-based antioxidants include 1, 3, 5 tri-trobenzene, ⁇ -trosodiphenylamine, ⁇ -trosodimethylaline, 1-black mouth, 3-trobenzene, ⁇ dito mouth Examples thereof include benzene, m-dinitrobenzene, p-dinitrobenzene, ⁇ -trobenzoic acid, nitrobenzene, 2-tro 5 cyanothiophene, and the like.
  • Inorganic compound-based antioxidants include FeCl, Fe (CN), CuCl, CoCl, Co (CIO)
  • a phenol-based antioxidant and an amine-based oxidic inhibitor preferably have a melting point of 120 in terms of thermal stability.
  • a melting point of 170 ° C or higher is more preferable, and a melting point of 170 ° C or higher is more preferable.
  • Specific examples include phenothiazine, 4,4, -butyldenbis (3-methyl-6-t-butynole / noreno).
  • the addition amount of the radical polymerization inhibitor is preferably in the range of 0.001 to 0.5 parts by weight, more preferably 0.01 to 0.1 parts by weight per 100 parts by weight of the copolymer polyester resin. Part. If it is less than 001 parts by weight, the thermal stability during the polymerization of the polyester is low, resulting in double bond cleavage. There is a risk of Louis candy and it may be difficult to produce a high molecular weight polyester, and if it exceeds 0.5 parts by weight, the physical properties of the cured coating film may be adversely affected.
  • the copolyester is a direct polymerization method in which a divalent or higher polyvalent carboxylic acid and a divalent or higher glycol are directly esterified and polymerized at normal pressure or under pressure, and a dimethyl ester of dicarboxylic acid.
  • the glass transition temperature is preferably 45 to 75 ° C, more preferably 45 to 70 ° C in order to satisfy the blocking resistance. Below 45 ° C, the toner may block in an environment of 45 ° C. When the temperature exceeds 75 ° C, the anti-blocking property is good, but the melt viscosity of the toner becomes high and the low-temperature fixing property may be remarkably deteriorated.
  • the polyester resin has a weight average molecular weight of 5,000-50,000, preferably S, more preferably 6,000-35,000. If the molecular weight is too low, the toner becomes brittle and may cause toner damage or carrier contamination in the developer containing the carrier.
  • the acid value is preferably 0.2 to 30 mg KOHZg from the viewpoint of charge amount and environmental stability.
  • the binder of the toner for developing an electrostatic charge of the present invention may be one kind of polyester resin. Two or more kinds of blends may be used in order to satisfy blocking resistance, low temperature fixing characteristics and hot offset resistance. In particular, it is highly desirable to use crystalline polyester resin in combination with low-temperature fixing characteristics.
  • the addition amount of the above-mentioned crystalline polyester resin is preferably in the range of 0 to 10% by mass in the toner noder resin.
  • the melting point defined by the maximum endothermic peak temperature at the time of temperature rise measured by a differential scanning calorimeter (DSC) of the crystalline polyester resin is preferably 70 to 130 ° C. More preferably, the temperature is 80 to 125 ° C.
  • the melting point is less than 70 ° C, the viscosity of the toner decreases and toner adhesion to the photoconductor tends to occur.
  • the melting point exceeds 130 ° C, the low-temperature fixability is poor. It may become.
  • dicarboxylic acid glycol containing sulphonate metal base may be used in an amount of 5 mol% or less.
  • dicarboxylic acid containing a sulfonic acid metal base include metal salts such as sulfoterephthalic acid, 5-sulfoisophthalic acid, 4-sulfonaphthalene-1,7 dicarboxylic acid, and 5 (4-sulfophenoxy) isophthalic acid.
  • glycols containing a sulfonic acid metal base examples include metal salts such as 2 sulfo-1,4-butanediol and 2,5 dimethyl-3-sulfo-2,5-hexanediol.
  • metal salts include salts of Li, Na, K, Mg, Ca, Cu, Fe and the like.
  • Colorants, charge control agents, fluidity modifiers and the like blended in the toner for developing an electrostatic charge image of the present invention are not particularly limited, and known ones can be used as necessary.
  • a dye, a pigment, carbon black, or the like may be used. These dyes, pigments, carbon black, etc. may be used alone or in combination as required. In particular, it is preferable to use a dye from the viewpoint of spectral transmission characteristics.
  • pigments are used for coloring
  • benzidine-based, azo-based, and isocindolin-based pigments are used for yellow coloring
  • azo-rake-based, rhodamine-lake-based, quinacridone-based, naphthol-based, diketopyrrolopyrrole are used for magenta coloring.
  • Pigment strength Phthalocyanine pigments and indanthrene pigments are preferably used for cyan coloring.
  • black toner carbon black or the like can be used.
  • carbon black thermal black, acetylene black, channel black, furnace black, lamp black and the like can be used.
  • dyes When dyes are used for coloring, azo, nitro, quinoline, quinophthalone, and methine dyes are used for yellow coloring, and anthraquinone, azo, and xanthene dyes are used for cyan coloring for magenta coloring. Anthraquinone, phthalocyanine and indoor-phosphorus dyes are preferably used.
  • the above-described polyester resin can be used as it is for the toner nonder resin, but for the purpose of further improving the performance to prevent offset to the roller, a wax, in particular Polyolefin waxes such as polyethylene wax and polypropylene wax may be contained.
  • the amount of wax added above is the binder resin for toner.
  • the content is preferably in the range of 0 to 10% by mass.
  • the melting point of the wax defined by the maximum endothermic peak temperature at the time of temperature rise measured by a differential scanning calorimeter (DSC) is preferably 70 to 130 ° C. More preferably, it is 80-125 degreeC.
  • the melting point of these waxes is preferably 70 to 130 ° C.
  • Specific product names of those corresponding to the above polyolefin wax include Mitsui Chemicals' noisy wax 800P, 400P, 200P, 100P, 720P, 420P, 320P, 405MP, 320MP, 4051E, 2203A, 1140H, NL800, Force that can illustrate NP055, NP105, NP505, NP805, etc. It is not limited to this.
  • the binder resin for toner of the present invention may contain natural waxes such as ceramic wax, rice wax, sugar wax, urushi wax, beeswax, carnauba wax, candelilla wax, montan wax and the like.
  • the addition amount is preferably in the range of 0 to 10% by mass in the toner binder resin.
  • hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, microcrystalline wax, paraffin wax, etc., because of their low dispersion in toner and high releasability.
  • the power at which hydrocarbon waxes by the Fischer-Tropsch method are preferably used.
  • One or two or more kinds of waxes may be used in small amounts as required. Examples include the following:
  • Acids of aliphatic hydrocarbon waxes such as acid polyethylene wax or block copolymers thereof; main components are fatty acid esters such as carnauba wax, sazol wax, and montanic acid ester wax And fatty acid esters such as deoxidized carnauba wax which are partially or fully deoxidized.
  • saturated linear fatty acids such as palmitic acid, stearic acid, and montanic acid
  • unsaturated fatty acids such as pracidic acid, elestearic acid, and phosphoric acid
  • stearyl alcohol, aralkylenoreconole behe- Saturated alcohols such as Norano Reconore, Canolenovinoreno Recenore, Serino Reno Recenore, and mesyl alcohol
  • Long-chain alkyl alcohols Polyhydric alcohols such as sorbitol
  • Saturated fatty acid bisamides such as methylenebisstearic acid amide, ethylene bis-succinic acid amide, ethylene bislauric acid amide, hexamethylene bisstearic acid amide; ethylene bisoleic acid amide, hexane Unsaturated fatty acid amides such as methylenebisoleic acid amide, N, N'-dioleyl adipic acid amide, N, N-dioleyl sebacic acid amide; m-xylene bisstearic acid amide, N, N —Aromatic bisamides such as distearyl isophthalic acid amide; fatty acid metal salts such as calcium stearate, calcium laurate, zinc stearate, magnesium stearate (generally referred to as metal soap), and aliphatic hydrocarbons Using vinyl monomers such as styrene and acrylic acid in Waxes; partially esterified products of fatty acids such as behenic acid monogly
  • charge control agent a known charge control agent such as Niguguchishin, quaternary ammonia salt metal-containing azo dye can be appropriately selected and used.
  • the amount is 0.1 to 10 parts by mass, which is usually used with respect to 100 parts by mass of the toner nonder resin.
  • an inorganic or organic fine powder may be externally added to the toner particles in order to improve the fluidity of the toner.
  • external additives for toner include fine powders such as colloidal silica, alumina, titanium oxide, polytetrafluoroethylene, polyvinylidene lide, polymethyl methacrylate, ultrafine polystyrene particles, and silicone. Hydrophobized silica and titanium oxide are preferably used.
  • the hydrophobizing method is provided by chemically treating with an organosilicon compound that reacts or physically adsorbs with silica fine powder and Z or silicone oil.
  • Silica fine powder produced by vapor phase oxidation of a halogen compound is preferably treated with an organic compound.
  • the content of external additives is 0 with respect to 100 parts by weight of untreated toner.
  • 01 to 5 parts by weight is preferred 0.1 to 5 parts by weight is more preferred.
  • the production method of the toner for developing an electrostatic charge image in the present invention is not particularly limited, and a colorant, a charge control agent and the like are mixed with a binder resin, and are melted using a kneader such as a heating mixer or an etatruder. After kneading, cooling, pulverizing with a jet mill, etc., and classifying, the average particle A so-called pulverization method in which a fluidity modifier or the like is externally added to a powder having a diameter of 5 to 15 m can be used. Another method is to mix and disperse a colorant, charge control agent, etc. in a solution consisting of a solvent and a binder resin, then introduce the solution into an aqueous system and suspend it! / Tonerization method by wet process such as tanning, coarse emulsification and classification drying can be used.
  • a kneader such as a heating mixer or an etatruder.
  • the polyester resin exhibits water dispersibility (self-emulsifying property).
  • the polyester resin is emulsified and dispersed in an aqueous system, and the polyester resin fine particles contained in the obtained dispersion are used, and the aqueous dispersion of the pigment and the aqueous dispersion of the wax are slowly agglomerated in water.
  • a method of obtaining a toner whose shape is controlled by growing it to a size suitable for the heat treatment and heat-sealing can be exemplified.
  • the toner for electrostatic charge development of the present invention preferably has a weight average particle diameter in the range of 5 to 10 ⁇ m. If it is less than 5 m, the powder fluidity may deteriorate, and if it exceeds 10 m, the image quality may deteriorate.
  • the weight average particle diameter is measured using a COULTER COUNTER MODEL TA II type manufactured by Coulter.
  • copolyester resin (vi) used in the can outer coating it is as follows.
  • the dicarboxylic acid component force isophthalic acid 2 0-80 mole 0/0, preferably from 30 to 70 mol%.
  • aromatic dicarboxylic acids other than isophthalic acid include terephthalic acid, orthophthalic acid, and naphthalenedicarboxylic acid.
  • aliphatic dicarboxylic acid having 2 to 12 carbon atoms include succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, and dimer acid.
  • Examples of the alicyclic dicarboxylic acid include 1,4-cyclohexanedicarboxylic acid, tetrahydrophthalic acid, hexahydrophthalic anhydride, hexahydroisophthalic acid, and 1,2-cyclohexenedicarboxylic acid.
  • Examples of unsaturated dicarboxylic acids include fumaric acid, maleic acid, and terpene monomaleic acid addition resistance.
  • the isophthalic acid component is less than 20 mol% of the dicarboxylic acid component, the wet ink property is inferior and the processability is poor. I'm so inferior. Moreover, the stability of the varnish is reduced when it exceeds 80 mol 0/0 in the dicarboxylic acid component.
  • dicarboxylic acids other than isophthalic acid include terephthalic acid and orthophthalic acid as aromatic dicarboxylic acids, and hexahydric oral phthalic anhydride (hydrogenated orthophthalic acid) as alicyclic dicarboxylic acids. It is particularly preferable from the aspect of gloss.
  • the glycol component is the above formula one or more forces also branched alkyl group containing Darikoru 70 having a 2: LOO mol 0/0, the other glycol component It is preferably 0 to 30 mol%, but it is preferable to contain 1 to 60 mol% of a glycol compound in which at least one of Rl and R2 in formula 2 has 2 to 6 carbon atoms in the total glycol. .
  • the side chain alkyl group-containing daricol having 1 to 6 carbon atoms includes neopentyl dalycol, 2, 2 jetyl 1,3 propanediol, 2-n-butyl-2-ethyl 1,3 propanediol, 2,2 di n-butyl-1, Examples include 3 propanediol, 2-ethyl 2-n-hexyl, 1,3 propanediol, 2,2 di-n-hexyl, 1,3-propanediol, and the like.
  • glycol components include ethylene glycol, propylene glycol, 1,3 propanediol, 1,4 butanediol, 1,3 butanediol, 1,5 pentanediol, 1,6 hexanediol, diethylene glycol, triethylene glycol
  • Te is the total acid component! /, Relative to the total alcohol Ingredients, 0.1 to 5 mole 0/0, preferably 0. 5 3 mol 0/0 it is preferable to contain a trivalent or more polycarboxylic acids and Z or polyol component.
  • a trivalent or higher polycarboxylic acid and Z or polyol the reactivity with the curing agent can be improved, and the polymerization rate can be improved. If the polycarboxylic acid and the Z or polyol component exceeds 5 mol%, the processability becomes poor.
  • Trivalent or higher polycarboxylic acids include aromatic polycarboxylic acids such as trimellitic acid and pyromellitic acid, and aliphatic polycarboxylic acids such as butanetetracarboxylic acid. A carboxylic acid etc. can be mentioned.
  • Examples of the trivalent or higher polyol component include glycerin, polyglycerin, trimethylolethane, trimethylolpropane, and pentaerythritol.
  • the copolymerized polyester resin used in the present invention may be given an acid value by any method.
  • the purpose of giving the acid value include acceleration of curing of the cross-linking agent and improvement of adhesion with the metal material for cans.
  • the preferred acid value range is 40-200 eqZl0 6 g. If it exceeds 200 eqZl0 6 g, retort resistance may decrease.
  • a depolymerization method in which a polyvalent carboxylic acid anhydride is added in the latter stage of polymerization, a high acid value is added at the prepolymer (oligomer) stage, this is then polymerized, and an acid value is added.
  • the former depolymerization method is preferred because of its ease of operation and easy target acid value.
  • Polyhydric carboxylic acid anhydrides used for acid addition in such depolymerization methods are anhydrous phthalic acid, tetrahydrophthalic anhydride, succinic anhydride, trimellitic anhydride, pyromellitic anhydride, anhydrous anhydride Hexahydrophthalic acid, ethylene glycol bistrimellitate dianhydride, and the like. Preferred are trimellitic anhydride and ethylene glycol bistrimellitate dianhydride.
  • the copolymerized polyester resin of the present invention has a reduced viscosity of 0.2 to 0.8 dlZg, preferably 0.3 to 0.7 dlZg. If the reduced viscosity is less than 0.2 dlZg, the processability is lowered, and if it exceeds 0.8 dZg, the sharpness and wet ink properties are lowered, and the solubility and the compatibility with melamine resin are reduced.
  • Examples of the cross-linking agent used in the present invention include forces such as alkyl etheramine formaldehyde resin, resol type phenol resin, isocyanate compound, and the like. Compatibility with the polyester resin resin, reactivity, From the viewpoint of sharpness and wet ink properties, alkyl etherated aminoformaldehyde resin is preferred.
  • Alkyl etherified aminoformaldehyde resin is, for example, formaldehyde or paraformaldehyde that is alkyl etherified with an alkyl alcohol having 1 to 4 carbon atoms such as methanol, ethanol, n-propanol, isopropanol, and n-butanol.
  • methoxylated methylol urea methoxylated methylol-N, N, monoethylene urea, methoxylated methylol dicyandiamide, methoxylated methylol melamine, methoxylated methylol benzoguanamine, butoxylated methylol melamine, Forces that include butoxylated methylol dicyandiamide, butoxylated methylol benzoguanamine, etc.
  • processable surface strengths such as methoxylated methylol melamine, butoxylated methylol melamine, and benzoguanamine rosin, each used alone or in combination. can do.
  • the ratio of the copolyester and the alkyl etheraminoformaldehyde resin is preferably 95Z5 to 60Z40 (weight ratio), more preferably 92 to 8 to 70.
  • the proportion of the copolymerized polyester exceeds 95% by weight, the desired blocking resistance, retort resistance and coating film hardness are insufficient, which is not preferable.
  • it is less than 60% by weight the cacheability is lowered, which is preferable!
  • the coating composition of the present invention may contain ⁇ -toluenesulfonic acid, phosphoric acid monoalkyl ester, or amine salt of ⁇ -toluenesulfonic acid as a curing catalyst.
  • the amount of the catalyst used is 0 to 5% by weight based on the formaldehyde resin.
  • the coating composition of the present invention is generally used in a form dissolved in an organic solvent.
  • the organic solvent include toluene, xylene, Solvesso 150.
  • a poor solvent that does not damage the ink layer is used from the viewpoint of wettability, such as Solvesso 150, Susolzol 1500, Solvesso 100, and alcohols such as butanol and octanol.
  • a system solvent is preferably used as a main component.
  • a blender such as a roll kneader, a ball mill, or a blender is used.
  • roller coating, roll coater, curtain flow coater, spray coating, electrostatic coating, etc. are appropriately selected.
  • the baking temperature of the coating composition depends on the size and thickness of the steel plate, the capacity of the baking furnace, the curability of the coating, etc. Any selection may be made.
  • the resin composition for paints of the present invention is excellent in processability and can be used for so-called white coating. Further, depending on the purpose and application, pigments such as titanium oxide, iron oxide, carbon, calcium carbonate, talc, and aluminum and additives such as glass fiber, silica, and wax can be used as necessary.
  • the following is related to the copolymerized polyester resin (vii) used in the paint for the inner surface of cans.
  • aromatic dicarboxylic acids terephthalic acid, isophthalic acid orthophthalic acid, naphthoquinone data dicarboxylic acids and the like, among this preferably contains terephthalic acid in the total acid content of 25 mol 0/0 above.
  • the other dicarboxylic acid in the polycarboxylic acid component accounts for 0 to 25 mol%.
  • aliphatic and Z or alicyclic dicarboxylic acids include succinic acid, dartaric acid, adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, dimer acid, and other aliphatic dicarboxylic acids, 1,4-cyclohexane.
  • the copolymerized polyester resin (L) used in the present invention includes at least one polyalcohol having a side chain as represented by the above formula 3 among the polyalcohol components, and Z or 1 , 30 the Cyclohexanedicarboxylic methanol to 4 cycloalkyl: L 00 mole 0/0, preferably 40-90 mol%, other polyalcohol component Ca ⁇ to 70 mole 0/0, preferably from 10 to 60 mole 0/0 Is in range.
  • Examples of the polyalcohol of formula 3 include propylene glycol (1,2 propanediol), 1,2 butanediol, 1,3 butanediol, 2-methyl-1,3 propanediol, neopentyl glycol, 2 butyl-2 Ethyl 1,3 propane diol, 2,2 Jetyl 1,3 propane diol, 2,4 dimethyl 1,3 pentane diol, 2,2 dimethyl 1,3 pentane diol, 2,2 dimethyl 1,3 butane diol, etc. , One or more of these can be used in combination
  • Examples of other polyalcohol components include ethylene glycol, 1,3 propanediol, 1,3 butanediol, 1,4 butanediol, 1,5 pentanediol, 1,4 pentanediol, and 1,3 pentanediol.
  • 1,4-pentanediol 3-methyl-1,5-pentanediol, 1,6 hexanediol, 1-methyl-1,8-octanediol, 3 propyl 1,5 pentanediol, 3-methyl-1,6-hexanediol, Aliphatic glycols such as 4-methyl-1,7 heptanediol, 4-methyl-1,8 octanediol, 4 propyl 1,8 octanediol, 1,9-nonanediol, diethylene glycol, triethylene glycol, polyethylene glycol
  • Polyether glycols such as polypropylene glycol and polytetramethylene glycol, 1, 3 cyclohexane dimethanol, 1, 2 cyclohexane dimethanol, tricyclodecane glycols, water-added bisphenols, etc.
  • Polyalcohol can be listed, and one or more of these can be selected and used.
  • preferred for hygiene are ethylene glycol, 1,3 propanediol, 1,4 butanediol, 1,3 butanediol, diethylene glycol, and one or more of these can be selected. Can be used.
  • 1,4-cyclohexanedimethanol and Z or 1, 2 as glycol components Copolymerized polyester resin used in the present invention using an appropriate amount of propanediol is a copolymer polyester used in the present invention using an appropriate amount of 1,4-cyclohexanedimethanol and Z or 2-methyl-1,3-propanediol.
  • propanediol is a copolymer polyester used in the present invention using an appropriate amount of 1,4-cyclohexanedimethanol and Z or 2-methyl-1,3-propanediol.
  • 1,4-Cyclohexanedimethanol is preferably used in the range of 10 to 30 mol% of the polyalcohol component.
  • 1,4 butanediol is a preferred glycol because of its good compatibility with resole type phenolic resin.
  • the copolymerized polyester resin (L) used in the present invention uses a polycarboxylic acid component or polyalcohol component with a tri- or higher functional polycarboxylic acid or Z and a polyalcohol as long as the processability is not lowered. May be.
  • the trifunctional or higher polycarboxylic acid component include trimellitic acid, pyromellitic acid, and benzophenone tetracarboxylic acid.
  • Examples of the trifunctional or higher polyalcohol component include glycerin, trimethylolethane, trimethylol. Mechirorupu port pan, Man - Thor, sorbitol, pentaerythritol, and the like a methyl Darco Sid.
  • trimellitic acid trimethylolethane, trimethylol bread, glycerin and the like are preferable.
  • the number average molecular weight is preferably 5, 000 to 100,000 force ⁇ , more preferably ⁇ or 8,000 to 30, 000.
  • Preferred! /! Glass transition temperature (Tg) is 15-120 ° C, more preferably 30-100 ° C. If the number average molecular weight is less than 5,000, the coating film becomes brittle and the workability and hot water resistance are poor, and if it exceeds 100,000, the coating workability may be reduced. In addition, if the glass transition temperature is less than 15 ° C, the retort resistance is poor, and a Tg of 30 ° C or higher is desirable especially for contents that require flavor properties.
  • Tg exceeds 120 ° C, workability and painting workability may be deteriorated.
  • the number average molecular weight mentioned here is measured by gel permeation chromatography (GPC) using a standard polystyrene calibration curve, and the glass transition temperature (Tg) is measured by differential thermal analysis (DSC). It is.
  • the copolymerized polyester resin (L) used in the present invention may be given an acid value by any method. Good.
  • Examples of the purpose of giving an acid value include accelerating the curing of the crosslinking agent and improving the adhesion with the metal material for cans.
  • the preferred acid value range is 40-200 eq.Z 10 6 g. If it exceeds 200 eq./10 6 g, retort resistance may be reduced or acid addition components may elute into the contents.
  • a depolymerization method in which a polyvalent carboxylic acid anhydride is added in the latter stage of polymerization, a high acid value is added at the prepolymer (oligomer) stage, this is then polymerized, and a copolymer having an acid value is obtained.
  • the former depolymerization method is preferred because it is easy to operate and the target acid value can be easily obtained.
  • Polyhydric carboxylic acid anhydrides used for acid addition in such a depolymerization method are anhydrous phthalic acid, tetrahydrophthalic anhydride, succinic anhydride, trimellitic anhydride, pyromellitic anhydride, anhydrous anhydride Hexahydrophthalic acid, ethylene glycol bistrimellitate dianhydride, and the like.
  • Preferred are trimellitic anhydride and ethylene glycol bistrimellitate dianhydride.
  • Examples of the crosslinking agent (M) used in the paint resin composition for inner surfaces of cans of the present invention include amino resin, phenol resin, isocyanate compound, epoxy resin, and the like. From the standpoint, amino resin and phenol resin are preferable. In particular, amino resin is preferred for crosslinkability with polyester resin, processability, and resistance to contents.
  • amino-fats the reaction of melamine, urea, benzoguanamine, acetoguanamine, steroguanamine, spiroguanamine, dicindiamide and other aldehyde components with formaldehyde, paraformaldehyde, acetoaldehyde, benzaldehyde and other aldehyde components
  • the methylolated amino coconut resin obtained by this is mentioned.
  • the aminocolate also includes those obtained by etherifying the methylol group of this methylolaminoamino resin with an alcohol having 1 to 6 carbon atoms. Among these, it can be used alone or in combination. In terms of hygiene, amino-fats using melamine and benzoguanamine are preferred, and more preferred are amino-fats using benzoguanamine which are excellent in retort resistance and extractability.
  • Amino benzoic acid using benzoguanamine was methyl etherated benzoguanamine rosin, which was obtained by etherifying some or all of the methylol groups of methylolated benzoguanamine rosin with methyl alcohol, and butyl ether with butyl alcohol.
  • a butyl etherified benzoguanamine resin or a mixed ether benzoguanamine resin with methyl ether or butyl ether etherified with both methyl alcohol and butyl alcohol is preferred.
  • isobutyl alcohol and n -butyl alcohol are preferred.
  • the amino rosin using melamine includes methyl ether melamine obtained by etherifying a part or all of methylol group of methylol melamine rosin with methyl alcohol, and butyl ether melamine butyl ether with butyl alcohol.
  • Preferred is a resin or a mixed etherified melamine resin mixed with methyl ether or butyl ether etherified with both methyl alcohol and butyl alcohol.
  • the phenolic resin is not particularly limited, but a resol type resin made by reacting phenolic resin with an aldehyde in the presence of an alkali catalyst, and phenol reacted with an aldehyde in the presence of an acidic catalyst.
  • a novolak type is exemplified, and resol resin is particularly suitable as a crosslinking agent.
  • the phenols used in these phenolic resins are phenol, 0-cresol, p-cresol, m-cresol, m-methoxyphenol, 2,3-xylenol, 2,5-xylenol, p-tert-butyl.
  • Alkylphenols such as phenol and p-ethylphenol, bisphenol A and bisphenol F are listed, and polyesters with excellent compatibility with polyesters and V, alkylphenols that have not been pointed out as environmental hormones. Is preferred! Mono- to trimethylol compounds of these phenols, condensates thereof, or alkyl ethers thereof, preferably butyl ethers, or various modifications such as epoxy modification, oil modification, melamine modification, amide modification, and acrylic modification thereof. Can be used.
  • cross-linking agents such as epoxy resin and isocyanate compound may be used in a range that does not deteriorate the hygienic properties.
  • a curing agent (N) The response can be advanced with less heat energy, and the coating film performance is good. It is desirable to use the curing agent (N) within the range of the following formula.
  • the amount is less than the above component amount, the effect of adding the curing catalyst cannot be obtained sufficiently, and workability, retort resistance, content resistance, and extractability may not be obtained. If the amount exceeds the above component, the cross-linking reaction may cause a reverse reaction, the copolymer polyester resin may be decomposed, and the curability may be significantly reduced especially during overbeta, resulting in workability, retort resistance, Contents physical properties are reduced.
  • Examples of the above-described curing catalyst (N) used in the present invention include sulfuric acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, camphor sulfonic acid, naphthalenesulfonic acid, and their amine blocks (carotenized with amine). In addition, one or two or more of these can be used in combination. From the aspect of compatibility with hygiene and hygiene Dodecylbenzenesulfonic acid is preferred. In particular, in the case of a combination of amino rosin and a sulfonic acid catalyst, the amount of catalyst is preferably 0.01 to 0.5, and more preferably, when baking is performed at 150 to 250 ° CX for 30 seconds to 15 minutes. 0. 05 to 0.2.
  • the resin composition for can coatings of the present invention includes known inorganic pigments such as acid titanium and silica, phosphoric acid and its ester oxides, curing catalysts such as organotin compounds, Known additives such as a surface smoothing agent, an antifoaming agent and a dispersing agent can be blended.
  • the resin composition for can coating of the present invention is made into a paint in a state dissolved in a known organic solvent.
  • organic solvents used for coating include toluene, xylene, aromatic hydrocarbon compounds, ethyl acetate, butyl acetate, methyl ethyl ketone, cyclohexane, isophorone, methyl cetosolve, butinorecerosonolev.
  • it is selected from ethylene glycol monoacetate in consideration of solubility and evaporation rate.
  • the coating resin composition for the inner surface of the can of the present invention can be applied to any metal plate that can be used for beverage cans, cans for cans, their lids, caps, and the like. Free steel and aluminum.
  • the coating resin composition for the inner surface of the can of the present invention can be applied by a known coating method such as roll coater coating or spray coating to obtain the coated metal plate of the present invention.
  • Paint film thickness Is not particularly limited, but the dry film thickness is preferably in the range of 3 to 18 111, more preferably 3 to: LO / zm.
  • the baking conditions of the coating are usually in the range of about 100 to 300 ° C for about 5 seconds to about 30 seconds, and the sardine is in the range of about 150 to 250 ° C for about 1 to about 15 minutes. It is preferable that it is a grade.
  • the copolymer polyester resin (viii) used for the hot melt adhesive and the extrusion coating agent is as follows.
  • the aromatic polyvalent carboxylic acid is selected from terephthalic acid (or dimethyl terephthalic acid) and 2, 6 naphthalenedicarboxylic acid (or dimethyl ester thereof).
  • at least one or more aromatic dicarboxylic acids is 2 0: it is necessary to include L00 mol 0/0.
  • crystallinity can be imparted and various good mechanical properties can be obtained. If these aromatic dicarboxylic acids are less than 20 mol%, a composition excellent in hydrolysis resistance and blocking resistance cannot be obtained.
  • Aromatic dicarboxylic acids such as 4,4, -diphenylmethane dicarboxylic acid, 4,4, -diphenyl ether dicarboxylic acid, 4,4, -biphenyl dicarboxylic acid, 4,4 'stilbene dicarboxylic acid p-oxybenzoic acid
  • Aromatic carboxylic acids such as acid, P (hydroxyethoxy) benzoic acid, and ⁇ -hydroxynaphthoic acid are trifunctional or more aromatic polyvalent carboxylic acids such as trimellitic acid, trimesic acid, and pyromellitic acid.
  • isophthalic acid By using isophthalic acid in combination with terephthalic acid and ⁇ or 2, 6 naphthalenedicarboxylic acid, the crystallinity can be controlled and a crystalline polyester suitable for the application can be obtained.
  • 5-sodium sulfoisophthalic acid can be used at 5 mol% or less for the purpose of imparting pigment dispersibility or improving adhesion to the substrate.
  • Examples of the alicyclic dicarboxylic acid that can be used in the present invention include hexahydrophthalic anhydride, hexahydroisophthalic acid, hexahydroterephthalic acid, and tricyclodecane dicarboxylic acid. Among these, it is particularly preferable to use hexahydroterephthalic acid.
  • aliphatic dicarboxylic acids examples include succinic acid, dartaric acid, adipic acid, sebacic acid, dodecanedicarboxylic acid, and azelaic acid. Further, unsaturated dicarboxylic acids such as fumaric acid and itaconic acid can be mentioned. In particular, adipic acid, which is preferred among these, can be copolymerized to give flexibility without losing crystallinity.
  • the polyhydric alcohol ethylene glycol, diethylene glycol, 1, 4 total 50-100 mole 0/0 of one or more polyhydric alcohols selected from butanediol It is necessary to include.
  • crystallinity can be imparted and good mechanical properties can be obtained.
  • polyhydric alcohols examples include 1,2-propylene glycol, 1,3 propylene glycol, 1,5-pentanediol, 3-methylpentanediol, 1,6-hexanediol, 1,9 -Nonanediol, 2, 2, 4 Trimethyl-1,3 Pentanediol, 2 Butyl-2 Ethyl-1,3 Propanediol, Triethylene glycol, Neopentyl glycol, 1,4-Cyclohexanedimethanol, Tricyclodecane dimethanol, Bisphenol Powers including ethylene oxide or Z and propylene oxide adducts of A In particular, among these, 1,4-cyclohexanediethanol, 1,6 hexanediol is preferably used.
  • polyalkylene glycol examples include polyethylene glycol, polytetramethylene glycol, and polypropylene glycol.
  • the molecular weight of the polyalkylene glycol is preferably 500 to 3000 force S.
  • polytetramethylene glycol is particularly preferred from the viewpoints of adhesive strength and hydrolysis resistance.
  • polycarbonate diol is mentioned.
  • hydrolysis resistance is remarkably improved and it is suitable for use in harsh environments.
  • the molecular weight of polycarbonate diol is 500 to 10,000 kid.
  • Polycarbonate diol preferably contains 1,6 hexanediol as a glycol, which is an aliphatic raw material.
  • ⁇ -force prolatatone after the polyester polymerization to introduce a polyforce prolatatone skeleton.
  • polyfunctional alcohols having three or more functional groups such as glycerin, trimethylolethane, trimethylolpropane and pentaerythritol can also be used. 5 mol% or less is preferable with respect to the total strength rubonic acid component or all alcohol components, and more preferably 2 mol% or less.
  • the reduced viscosity (dlZg) of the crystalline polyester resin of the present invention is 0.3 or more, preferably 0.4 or more. If the reduced viscosity is less than 0.3, a composition having excellent adhesion may not be obtained.
  • the upper limit is not particularly limited, but is preferably 3.0 or less, more preferably 1.5 or less, from the melt viscosity during processing.
  • the method for producing the copolyester in the present invention is not particularly limited, and is a direct esterification method of a polycarboxylic acid and a polyhydric alcohol, or transesterification of an alkyl ester of a polycarboxylic acid and a polyhydric alcohol.
  • a polyhydric alcohol ester of polycarboxylic acid can be obtained by the method, and after that, it can be polymerized under normal pressure or reduced pressure to obtain a composition.
  • an ester soot catalyst or a polymerization catalyst can be used as necessary.
  • various additives, stabilizers, and other thermoplastic resins may be added to the extent that they do not impair the original properties.
  • the composition is molded into a powder, chip, tape, string, film, nonwoven fabric or the like, and is applied.
  • Adopting a method of heating and melting at a temperature above the soft softness point of the polyester between the body, a method of applying a molten polyester composition on the adherend using an adhesive applicator, cooling and solidifying it, etc. be able to.
  • the hot melt adhesive for crystalline polyester resin of the present invention exhibits excellent adhesion to metals, plastic films, wood boards and fabrics, and is also resistant to hydrolytic degradation under high temperature and high humidity. Excellent. In addition, it has an excellent feature that it does not cause blocking during coiling.
  • polyester 0.2 g was dissolved in 20 ml of black mouth form and titrated with 0.1N or 0.01N potassium hydroxide ethanol solution.
  • As the indicator phenolphthalein was used. The unit is mgKOH / g.
  • polyester 50 g was dissolved in a mixed solvent of 60 g of toluene and 60 g of 2-butanone, 50 g of 4,4, -diphenylmethane diisocyanate was added, and the mixture was reacted at 80 ° C. for 2 hours. Subsequently, the residual isocyanate group concentration in the reaction solution was quantified by titration to obtain the hydroxyl value.
  • the unit is mg KOHZg.
  • Shimadzu flow tester CFT500D manufactured by Shimadzu Corporation
  • DSC differential scanning calorimeter
  • the copolymerized polyester resin (V) used in the toner was measured by DSC-20 (Seiko Denshi Kogyo Co., Ltd.) according to the differential scanning calorimetry (DSC) measured under the following conditions. Put about 10 mg of sample in an aluminum pan, seal it with a lid, heat up to about 170 ° C in advance, hold for 5 minutes, lower it to 10 ° C, and unify the thermal history of the oil. Cool to 40 ° C using liquid nitrogen, raise the temperature to 130 ° C in 10 ° CZ minutes, and meet the intersection of the base line extension below the glass transition temperature and the tangent indicating the maximum slope at the transition. Determined by temperature.
  • NMR analysis was carried out using a Varian nuclear magnetic resonance analyzer (NMR) diemi--200 in heavy chloroform solvent, and the integral ratio was determined. In addition, analysis by gas chromatograph after alcoholysis was also used as needed.
  • NMR Varian nuclear magnetic resonance analyzer
  • the foreign matter evaluation was performed by filtration time as follows. ⁇ : Filtration time less than 5 hours
  • the filtration time exceeds 1 day, the content of fine foreign substances insoluble in the polyester increases, which leads to an increase in filter clogging during the filtration of the polyester in the polymerization process, for example, which is not preferable.
  • the copolymerized polyester resin was visually judged while it was in the form of a plate having almost the same thickness.
  • melt viscosity of the polyester resin was measured in increments of 2 ° C, and obtained from a plot with the logarithm of melt viscosity on the vertical axis and the temperature on the horizontal axis.
  • 1, 3PD 1,3-propanediol
  • NPG neopentyl alcohol
  • GL glycerin
  • IPA isophthalic acid
  • 3-Propanediol Solution of Aluminum Compound / 1,3-Propanediol Solution of Phosphorus Compound The obtained polymerization catalyst solution was charged so that the total acid components were 0.02 mol% and 0.04 mol% in terms of aluminum and phosphorus atoms, and the total 1,3PD was 669 parts, and a nitrogen gas stream was supplied. Then, while the condensed water produced was removed from the system so that the thermometer at the top of the fractionator did not exceed 100 ° C, the temperature was gradually raised to 230 ° C to carry out the esterification reaction.
  • Table 1 shows the results of 1 H-NMR analysis and various performances of the obtained copolymer polyester resin (A-1).
  • the polymerization catalyst was used for (1) Preparation Example of 1,3 Propanediol Solution of Aluminum Compound and (4) Preparation Example of 1,3 Propanediol Solution of Alkali Metal Compound.
  • the same procedure as in Example 1-i was performed except that the content was changed to 02 mol% and 0.02 mol%.
  • Table 1 shows the performances of the obtained rosin (A-2) and the coating film after the coating, coating, and baking operations using this rosin.
  • the aluminum Z-lithium polymerization catalyst is slightly inferior in weather resistance to the aluminum Z-phosphorus polymerization catalyst, but has better coating properties and appearance than the titanium polymerization catalyst. It was.
  • the polymerization catalyst was prepared in the same manner as in Example 1 except that (1) the preparation example of a 1,3 propanediol solution of an aluminum compound was used and the amount was changed to 0.1 mol% with respect to the total acid components.
  • Example 1-i Using the obtained resin (A-3), paint and coating were baked in the same manner as in Example 1-i. Table 1 shows various performances of the obtained resin and coating. In the case of an aluminum homopolymer catalyst, the polymerization activity was slightly inferior to that of an aluminum Z phosphorus polymer catalyst, but the physical properties and appearance of the coating film were within the range of use.
  • Example 4-i The copolyester was prepared in the same manner as in Example 1-i except that the charge in the synthesis of the copolyester was 1,3PD643 parts, NPG1143 parts, GL19 4 parts, IPA1660 parts, and the second stage was IPA 1660 parts. (A-4) was obtained. In addition, instead of 850 parts of Example 1-i resin (A-1) [except for the moon month here 800 ⁇ ⁇ Blocked isocyanate B-1530, 150 ⁇ made by Hyunores In the same manner as in Example 1-i, the paint and the coating were baked. Table 1 shows various performances of the obtained resin and coating.
  • Example 1 The coffin produced by the same procedure as in Example 1-i was evaluated in the same manner.
  • Table 1 shows the composition and evaluation results of the greaves.
  • Example 1-i was carried out in the same manner as Example 1 except that the polymerization catalyst was changed to titanium tetra n-butoxide. Using the obtained copolymer polyester resin (A-6), paint coating and painting were baked in the same manner as in Example 1-i. Table 1 shows the properties of the obtained resin and coating. In the case of a titanium-based polymerization catalyst, the white coating film is remarkably colored and the original white coating film cannot be obtained.
  • Example 1-i Using the same polymerization catalyst as in Example 1, IPA, terephthalic acid (TPA), 1, 3PD, NPG, and GL were charged in the same molar ratio as shown in Table 1, as in Example 1-i. Overlapped. Using the obtained copolymer polyester resin (A-7), coating, painting and baking were carried out in the same manner as in Example 1-i. Table 1 shows various performances of the obtained resin and coating. Even with an aluminum Z-phosphorus polymerization catalyst, the physical properties of the coating film decreased, and in particular, the corrosion resistance deteriorated significantly over time.
  • Resin composition (acid component) Tetraic acid 11 24 88
  • the production method of the copolymerized polyester resin (i) mainly for powder coating is as follows.
  • Fractionator for condensing water produced by nitrogen gas flow with 0.02 mol% and 0.04 mol% in terms of aluminum and phosphorus atoms, and 267 parts of total 1,3-propanediol. While removing from the system so that the temperature at the top does not exceed 100 ° C, the temperature was gradually raised to 230 ° C to carry out the esterification reaction. Condensation The amount of water produced is 9900% or more of the theoretical amount, and after cooling and cooling at 118800 ° CC, In addition, 991133 parts of isofisophthaltalic acid was charged in the same way, and similarly, the condensed condensed water formed by the nitrogen nitrogen gas gas flow was generated.
  • Example of preparation of polypolymerized catalyst catalyst (11), 11, 33--Propropapapandanediol solution of (alummimininiumium compound) Using the preparation examples of preparations of 11, (33) -propropapandin diiool solution of the larva ((44)) Aarrucakariri gold metal compound, Actual implementations except that the total acid components can be replaced with 00 .. 0022 momol%% and 00 .. 0022 momol%%, respectively. It was carried out in the same manner as Example 66--ii. .
  • the number average average molecular weight of the molecular weight is 44330000
  • the acid value is 33..66
  • the hydroxy group value is 3344..55
  • the softness ⁇ Point 112211 ° CC Gagalaras transition transition point 6600 ° CC, filtration overtime 55 hours over less than light pale yellowish yellow and transparent co-copolymerized polypopolymer Obtained stearyl lube fat.
  • the specific ratio of each monomonomer-unit unit of the resin resin fat is 11 HH——product from the product integral ratio by NNMMRR analysis.
  • the ratio of the ratio of each monomonomer unit of the obtained fats and oils was calculated from the product-integral ratio by 11 HH--NNMMRR analysis.
  • Example 33--ii [[Comparative Example 33--ii]] The same procedure as in Example 6-i was conducted except that in Example 6-i, the polymerization catalyst was changed to titanium tetra n-butoxide.
  • Example 6-i was carried out in the same manner as Example 6-i, except that the polymerization catalyst was changed to antimony trioxide.
  • the resin obtained from the antimony-based polymerization catalyst had a strength and darkness, which was the first degree of coloring, and was not transparent.
  • copolymer polyester resin (ii) used in precoat paints with an emphasis on processability is as follows.
  • the coated steel sheet was judged visually.
  • Refrigerator door packing was magnetized, left at 70 ° C for 96 hours, wiped with waste cloth and visually evaluated on 5 levels (5: no trace, 4: trace left, 3: mark left, 2: clear The traces remain, 1: the traces remain completely).
  • the coated surface of the steel sheet was measured according to JISK-5400 using a high-grade pencil specified in JIS S-6006 and judged by the presence or absence of scratches.
  • the coated steel plate was bent 180 degrees and the cracks that occurred in the bent part were observed and judged with a 10X magnifier.
  • 3T means that there is no problem when three sheets of the same thickness are sandwiched in the bent part, and OT is that there is no problem when bending 180 degrees without pinching the plate. Point.
  • the numbers are small! /, The processability is better.
  • the reflectance was measured (%) at 60 degrees on the coated surface of the steel sheet.
  • the coated steel sheet was immersed in a 10% NaOH aqueous solution for 72 hours, and the gloss retention (%) of the coated surface was measured and evaluated as alkali resistance. In this case, a polyester-based primer was used, and the evaluation was performed under the condition that no blister was generated. 7. Weather resistance
  • UV cycles were 60 cycles at 60 ° C for 4 hours and condensation at 50 ° C for 4 hours for 8 hours.
  • a stainless steel reaction kettle equipped with a stirrer, condenser, and thermometer is mixed with terephthalic acid, isophthalic acid, 3-methyl-1,3-propanediol, 1,5-pentanediol, aluminum polymerization catalyst (however, aluminum
  • the polymerization polymerization catalyst is the same as described in “Preparation example of a mixture of a 1,3-propanediol solution of an aluminum compound and a 1,3-propanediol solution of a phosphorus compound” described above.
  • the esterification reaction was carried out over 4 hours while raising the temperature to ° C.
  • Table 3 shows the analysis results and characteristics of the obtained copolymer polyester (A). However, the addition amount of the polymerization catalyst is shown in mol% with respect to the full strength rubonic acid at the time of charging.
  • the copolymerized polyester resin of the present invention having the composition shown in Tables 3 to 6 by the method according to the above synthesis example (B), (C) and (G), (H), (I) Was synthesized.
  • (D), (E), (F) and CO to (Q) are comparative copolyester resinous resins.
  • the addition amount of the polymerization catalyst is shown in mol% with respect to the full strength rubonic acid at the time of charging.
  • the composite catalyst system such as aluminum compound / phosphorus compound or aluminum compound / alkali metal compound and / or alkaline earth metal compound is the titanium compound. It was more transparent than the catalyst, and coloring was also suppressed.
  • the aluminum compound single catalyst showed the same appearance except that the polymerization activity was slightly lower than that of the composite catalyst.
  • the antimony polymerization catalyst was cloudy in addition to coloring. Tin-based polymerization catalysts are relatively transparent and less colored. However, like antimony-based polymerization catalysts, polyesters that do not contain these are desired.
  • methylated melamine trade name; Summar M40S, non-volatile content 80%, manufactured by Sumitomo Chemical Co., Ltd.
  • Tilated melamine trade name; Super Becamine J—820, nonvolatile content 60%
  • This coating composition was applied to a 0.5 mm-thick zinc iron plate to a thickness of 20 ⁇ m, and then baked at 230 ° C for 1 minute.
  • the obtained coating film had good processability and hardness, and also showed excellent alkali resistance, weather resistance and stain resistance. In addition, after 2 years of outdoor exposure, the gloss retention was 90% or more. Table 5 shows the test results.
  • Examples 2-ii, 3-ii and 4-ii to 7-ii and Comparative Examples l-ii to 3-ii and 4- are similarly performed using the coating compositions shown in Table 7 and Table 8.
  • Tables 7 and 8 show the test results of the obtained coated steel sheets. However, the blending ratio of the paint was expressed in terms of solid content.
  • the coating composition of the comparative coating composition was inferior in workability, hardness, or other characteristics.
  • the appearance of the coating film was slightly dark in Comparative Example 1-ii, slightly yellowish in Comparative Example 2-ii, and in Examples l-ii to 3-ii using an aluminum-based catalyst, especially in light colors. was good.
  • copolymerized polyester resin (iii) used in the precoat paint that places particular emphasis on blocking resistance is as follows.
  • the coated surface of the steel plate was strongly rubbed with a nail, and the occurrence of scratches was visually evaluated. (5: No scratch, 4: Slightly scratched, 3: Slightly scratched, 2: Equivalent scratch, 1: Scratched)
  • the coated steel sheet was evaluated using a DuPont impact resistance tester under the conditions of a height of 40 cm and a load of 500 g. (5: no crack, 4: slight whitening due to cracking, 3: cracking, 1: significant cracking)
  • aluminum polymerization catalyst is a solution of 2-methyl-1,3-propanediol in aluminum-aluminum compound (basic aluminum acetate) and 2-methyl-1,3-propanediol solution in phosphorus compound (Irganoxl222).
  • Catalyst type is aluminum Z-phosphorous (invented resin A) and aluminum Z-lithium is also Other than changing to melamine B), aluminum alone system (invented resin C), antimony system (comparative resin D), titanium system (comparative resin E) and tin system (comparative resin F) This was carried out in the same manner as the resin A of the present invention.
  • Table 9 shows the analysis results and characteristics of the obtained copolymer polyester resin. The coloration of the resin of the titanium-based catalyst is remarkable, but that of the composite catalyst system such as aluminum Z phosphorus, aluminum Z alkali metal and Z or alkaline earth metal is more transparent and suppresses coloring than the titanium catalyst. It was what was done.
  • the aluminum single catalyst showed the same appearance except that the polymerization activity was slightly lower than that of the composite catalyst. Further, the antimony polymerization catalyst was cloudy in addition to coloring. Tin-based polymerization catalysts are relatively transparent and have little coloration. However, like antimony-based catalysts, polyesters are desired in the field without these.
  • This coating composition was applied to a 0.5 mm thick zinc iron plate to which a polyester primer coating had been applied to a thickness of 18 m, and then baked at 230 ° C for 1 minute.
  • the obtained coating film had excellent workability and hardness, and also excellent drawing workability and stain resistance.
  • the test results are shown in Table 13. Further, the whiteness of the coating film showed the original whiteness without yellowing because of less coloring of the resin.
  • Copolymerized polyester resin 10 parts of carbon black in a solution of 100 solid parts, 20 parts of M40S (previously) 20 solid parts, 15 parts of J-820 (previously), 10% benzyl alcohol solution of p-toluenesulfonic acid 10 And 0.5 parts of polyflow S (described above) and 0.5 part of a dispersant were added and dispersed for 5 hours with a glass bead type high-speed shaker to obtain a coating composition.
  • This coating composition was applied to a 0.5 mm-thick zinc iron plate to which a polyester primer coating was applied, and then baked at 230 ° C for 1 minute.
  • the obtained coating film was excellent in gloss and had good workability, hardness and scratch resistance. In addition, it had very good blocking resistance and impact resistance. In addition, the gloss retention rate of 90% or more was maintained even after one year of outdoor exposure.
  • the test results are shown in Table 14.
  • Methylated melamine Sumimal M40S (manufactured by Sumitomo Chemical Co., Ltd.)
  • Methylated melamine Sumimal M40S (manufactured by Sumitomo Chemical Co., Ltd.)
  • Methylated melamine Sumimal M40S (manufactured by Sumitomo Chemical Co., Ltd.)
  • copolyester resin (iv) used in ply paint it is as follows.
  • the coated steel sheet was immersed in boiling water for 3 hours, and the state of the prestar on the coated surface was evaluated according to ASTM D71 4-56. When there was no abnormality, it was set to 10.
  • the coated steel sheet was subjected to a 5% NaCl salt spray test at 3, 5 ° C for 1000 hours, as described in JIS K5400, and the occurrence of blisters was visually determined. Corrosion resistance was applied to the crosscut part, 1T processed part, and end face part. The evaluation criteria are shown below.

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Abstract

L’invention concerne une résine de polyester co-polymérisée obtenue sans utiliser de catalyseur conventionnel comme un composé d’antimoine. L’invention présente également une composition en résine qui contient ladite résine de polyester co-polymérisée, un matériau de revêtement qui utilise ladite composition de résine, un toner, une résine liante, une plaque de métal revêtue, un adhésif thermofusible et une matière de revêtement d’extrusion. L’invention présente plus particulièrement une résine de polyester co-polymérisée produite en présence d’un catalyseur contenant au moins un composé aluminium. La résine de polyester co-polymérisée se caractérise par le fait que le composant acide carboxylique polyvalent qui constitue la résine de polyester co-polymérisée contient au moins 20 % en mole d’acide dicarboxylique aromatique, et que le composant alcool polyhydrique qui constitue la résine de polyester copolymérisée contient au moins un alcool appartenant au groupe formé par : éthylèneglycol, diéthylèneglycol, 1,3-propanediol, 1,4-butanediol, 2-méthyl-1,3-propanediol, des alkylèneglycols ayant entre 5 et 10 atomes de carbone, 1,4-cyclohexanediméthanol et des alcools polyhydriques dont les structures sont spécifiques.
PCT/JP2006/304857 2005-03-11 2006-03-13 Resine de polyester copolymerisee, methode de production et composition de resine contenant la resine de polyester copolymerisee WO2006095901A1 (fr)

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JP2008124238A (ja) * 2006-11-13 2008-05-29 Toyobo Co Ltd 電磁波シールド用積層体
WO2008073209A3 (fr) * 2006-12-08 2008-07-31 Eastman Chem Co Solutions de métal alcalin/alcalinoterreux et d'aluminium non-précipitantes produites à partir de diols comportant au moins deux groupes hydroxyle primaires
WO2009011301A1 (fr) * 2007-07-13 2009-01-22 Sanyo Chemical Industries, Ltd. Liant de toner et toner
WO2009156457A1 (fr) * 2008-06-24 2009-12-30 Dsm Ip Assets Bv Résine polyester modifiée
WO2010075023A1 (fr) * 2008-12-15 2010-07-01 E. I. Du Pont De Nemours And Company Copolyesters dotés d'une résistance à la déchirure améliorée
JP2011504199A (ja) * 2007-11-21 2011-02-03 エスケー ケミカルズ カンパニー リミテッド ポリエステル樹脂及びこれを含むトナー
WO2012046811A1 (fr) * 2010-10-06 2012-04-12 三洋化成工業株式会社 Liant et composition de toner
JP2013108051A (ja) * 2011-10-25 2013-06-06 Jfe Steel Corp コーティング剤、塗装鋼板の製造方法および塗装鋼板
JP2013257363A (ja) * 2012-06-11 2013-12-26 Ricoh Co Ltd トナー、及びトナーセット
JP2014218653A (ja) * 2013-04-09 2014-11-20 キヤノン株式会社 トナー用樹脂およびトナー
JP2014218654A (ja) * 2013-04-09 2014-11-20 キヤノン株式会社 トナー用樹脂およびトナー
WO2015033773A1 (fr) * 2013-09-06 2015-03-12 Ricoh Company, Ltd. Toner, révélateur et appareil de formation d'image
US10550223B2 (en) 2014-08-26 2020-02-04 Sk Chemicals Co., Ltd. Polyester resin composition and preparation method thereof
JP2021001254A (ja) * 2019-06-20 2021-01-07 東洋紡株式会社 顔料分散性、および熱安定性に優れたポリエステル樹脂
WO2023243609A1 (fr) * 2022-06-17 2023-12-21 東洋紡株式会社 Résine de polyester copolymérisée et article moulé de celle-ci, et procédé de production de résine de polyester copolymérisé
JP7445227B2 (ja) 2021-09-22 2024-03-07 東洋紡エムシー株式会社 接着剤樹脂組成物
JP7445228B2 (ja) 2021-09-22 2024-03-07 東洋紡エムシー株式会社 接着剤樹脂組成物
JP7492685B2 (ja) 2021-09-22 2024-05-30 東洋紡エムシー株式会社 接着剤樹脂組成物

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Cited By (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008124238A (ja) * 2006-11-13 2008-05-29 Toyobo Co Ltd 電磁波シールド用積層体
WO2008073209A3 (fr) * 2006-12-08 2008-07-31 Eastman Chem Co Solutions de métal alcalin/alcalinoterreux et d'aluminium non-précipitantes produites à partir de diols comportant au moins deux groupes hydroxyle primaires
WO2009011301A1 (fr) * 2007-07-13 2009-01-22 Sanyo Chemical Industries, Ltd. Liant de toner et toner
JP2011504199A (ja) * 2007-11-21 2011-02-03 エスケー ケミカルズ カンパニー リミテッド ポリエステル樹脂及びこれを含むトナー
WO2009156457A1 (fr) * 2008-06-24 2009-12-30 Dsm Ip Assets Bv Résine polyester modifiée
WO2010075023A1 (fr) * 2008-12-15 2010-07-01 E. I. Du Pont De Nemours And Company Copolyesters dotés d'une résistance à la déchirure améliorée
WO2012046811A1 (fr) * 2010-10-06 2012-04-12 三洋化成工業株式会社 Liant et composition de toner
US9052623B2 (en) 2010-10-06 2015-06-09 Sanyo Chemical Industries, Ltd. Toner binder and toner composition
JP2013108051A (ja) * 2011-10-25 2013-06-06 Jfe Steel Corp コーティング剤、塗装鋼板の製造方法および塗装鋼板
JP2013257363A (ja) * 2012-06-11 2013-12-26 Ricoh Co Ltd トナー、及びトナーセット
JP2014218653A (ja) * 2013-04-09 2014-11-20 キヤノン株式会社 トナー用樹脂およびトナー
JP2014218654A (ja) * 2013-04-09 2014-11-20 キヤノン株式会社 トナー用樹脂およびトナー
US9540483B2 (en) 2013-04-09 2017-01-10 Canon Kabushiki Kaisha Resin for toner and toner
EP2984119A4 (fr) * 2013-04-09 2016-12-21 Canon Kk Résine pour toner et toner
JP2015052698A (ja) * 2013-09-06 2015-03-19 株式会社リコー トナー、現像剤、及び画像形成装置
WO2015033773A1 (fr) * 2013-09-06 2015-03-12 Ricoh Company, Ltd. Toner, révélateur et appareil de formation d'image
US9557672B2 (en) 2013-09-06 2017-01-31 Ricoh Company, Ltd. Toner, developer, and image forming apparatus
US10550223B2 (en) 2014-08-26 2020-02-04 Sk Chemicals Co., Ltd. Polyester resin composition and preparation method thereof
US11267934B2 (en) 2014-08-26 2022-03-08 Sk Chemicals Co., Ltd. Polyester resin composition and preparation method thereof
JP2021001254A (ja) * 2019-06-20 2021-01-07 東洋紡株式会社 顔料分散性、および熱安定性に優れたポリエステル樹脂
JP7423917B2 (ja) 2019-06-20 2024-01-30 東洋紡エムシー株式会社 顔料分散性、および熱安定性に優れたポリエステル樹脂
JP7445227B2 (ja) 2021-09-22 2024-03-07 東洋紡エムシー株式会社 接着剤樹脂組成物
JP7445228B2 (ja) 2021-09-22 2024-03-07 東洋紡エムシー株式会社 接着剤樹脂組成物
JP7492686B2 (ja) 2021-09-22 2024-05-30 東洋紡エムシー株式会社 接着剤樹脂組成物
JP7492685B2 (ja) 2021-09-22 2024-05-30 東洋紡エムシー株式会社 接着剤樹脂組成物
WO2023243609A1 (fr) * 2022-06-17 2023-12-21 東洋紡株式会社 Résine de polyester copolymérisée et article moulé de celle-ci, et procédé de production de résine de polyester copolymérisé

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