WO2011052677A1 - ハイブリッド型ポリエステル樹脂、皮膜形成用樹脂組成物、ポリエステルフィルム及び繊維 - Google Patents
ハイブリッド型ポリエステル樹脂、皮膜形成用樹脂組成物、ポリエステルフィルム及び繊維 Download PDFInfo
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- WO2011052677A1 WO2011052677A1 PCT/JP2010/069158 JP2010069158W WO2011052677A1 WO 2011052677 A1 WO2011052677 A1 WO 2011052677A1 JP 2010069158 W JP2010069158 W JP 2010069158W WO 2011052677 A1 WO2011052677 A1 WO 2011052677A1
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- 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
- C08G63/91—Polymers modified by chemical after-treatment
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/507—Polyesters
-
- 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
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/695—Polyesters containing atoms other than carbon, hydrogen and oxygen containing silicon
- C08G63/6954—Polyesters containing atoms other than carbon, hydrogen and oxygen containing silicon derived from polxycarboxylic acids and polyhydroxy compounds
-
- 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
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
- C08L83/12—Block- or graft-copolymers containing polysiloxane sequences containing polyether sequences
-
- 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
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
-
- 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/30—Flame or heat resistance, fire retardancy properties
Definitions
- the present invention relates to a hybrid polyester resin imparted with high combustion resistance, a film-forming resin composition containing the hybrid-type polyester resin, and a polyester film processed with the film-forming resin composition And fibers.
- polyester resin is known for its excellent mechanical and chemical properties, so it can be used as a base material for magnetic recording materials such as magnetic tape and flexible disks, as well as for textiles for clothing and industrial use, or for photography, electrical use. Widely used as a base material for insulation, cable wrapping, condenser, vapor deposition, adhesive tape, printer ribbon and magnetic card, and for various industrial applications such as mold release for FRP, packaging and agriculture. It is used.
- the present applicant has proposed that a reactive phosphorus-containing compound is contained in the reaction system during the synthesis of the polyester (see JP 2004-67910 A). Thereby, a polyester resin to which flame retardancy is imparted while maintaining the excellent properties inherent in the polyester resin is obtained.
- the present inventors aim to further improve the flame retardancy of the polyester resin for fire prevention and the like and further to prevent fire and the like.
- the polyester resin has been improved in order to impart characteristics to the polyester resin. Then, the present inventors pay attention to the fact that when the polyester resin burns, high temperature droplets are scattered from the burned polyester resin, and if such droplets can be prevented from scattering, The idea was that even if burned, the spread of damage could be suppressed.
- the present invention has been made in view of the above points, and when used for processing on substrates such as fibers and PET films, can impart excellent flame retardancy to these substrates, and tentatively A hybrid polyester resin capable of suppressing the dispersion of high-temperature droplets even when burned, a film-forming resin composition containing the hybrid-type polyester resin, and a processing treatment are performed with the film-forming resin composition. It is an object of the present invention to provide a finished polyester film and fiber.
- the hybrid polyester resin according to the present invention includes a polyester resin and siloxane formed from silica and alkoxysilane.
- This hybrid type polyester resin retains the excellent properties inherent in the polyester resin and is imparted with extremely excellent flame retardancy by being hybridized with siloxane. Furthermore, even if this hybrid type polyester resin burns, its shape is not easily lost, and scattering of high-temperature droplets is suppressed.
- the polyester resin in the present invention preferably contains an aqueous polyester resin formed from a polyvalent carboxylic acid component, a glycol component, and a hydrophilic component (water solubility-imparting component).
- This hybrid type polyester resin has the property that it can be dispersed or dissolved in an aqueous solvent by a hydrophilic component (water-solubility-imparting component) while retaining the excellent properties inherent in the polyester resin. From the standpoints of maintainability and ease of processing of the substrate, it becomes excellent.
- the polyester resin of the present invention it is preferable that the polyester resin includes a phosphorus-containing polyester resin.
- This hybrid type polyester resin is imparted with further excellent flame retardancy while maintaining the excellent properties inherent in the polyester resin.
- the phosphorus-containing polyester resin is preferably formed from a polyvalent carboxylic acid component, a glycol component, a hydrophilic component, and a reactive phosphorus-containing compound.
- This hybrid-type polyester resin has the property that it can be dispersed or dissolved in an aqueous solvent by a hydrophilic component while retaining the excellent properties inherent in the polyester resin, and further provides excellent flame retardancy. Is done.
- the hybrid polyester resin of the present invention further contains a phosphorus flame retardant. In this case, more excellent flame retardancy is imparted to the hybrid type polyester resin.
- the film formability resin composition according to the present invention preferably contains the hybrid polyester resin.
- This film-forming resin composition not only improves the flame retardancy while retaining the excellent properties inherent in polyester resins, but also makes it difficult for its shape to collapse during combustion, causing high-temperature droplets to scatter. Is suppressed.
- This film-forming resin composition is preferably for polyester film surface processing. Excellent flame retardancy is imparted to the surface of the polyester film that has been surface-treated by this film-forming resin composition, and scattering of high-temperature droplets during combustion is suppressed.
- This film-forming resin composition is also preferably used for fiber processing. Excellent flame retardancy is imparted to the fibers that have been processed with the film forming resin composition, and scattering of high-temperature droplets during combustion is suppressed.
- the polyester film according to the present invention is preferably surface-treated with the film forming resin composition. Thereby, the flame retardance which was excellent in this polyester film is provided, and scattering of the hot droplet at the time of combustion is suppressed.
- the fiber according to the present invention is preferably treated with the film-forming resin composition. Thereby, the flame retardance which was excellent in this fiber is provided, and scattering of the hot droplet at the time of combustion is suppressed.
- the hybrid type polyester resin is manufactured through a process in which a reaction solution containing a polyester resin, silica particles, and alkoxysilane is reacted by a sol-gel method.
- the polyester resin is obtained through a process of reacting a polyvalent carboxylic acid component and a glycol component as raw materials for condensation or polycondensation.
- the polyvalent carboxylic acid component is a divalent or higher polyvalent carboxylic acid and a derivative of the polyvalent carboxylic acid, such as an anhydride, ester, acid chloride, or halide.
- a derivative of the polyvalent carboxylic acid such as an anhydride, ester, acid chloride, or halide.
- One or more compounds selected from those to be formed esteer-forming derivatives of polyvalent carboxylic acids).
- Examples of the polyvalent carboxylic acid include dicarboxylic acids such as aromatic dicarboxylic acids and aliphatic dicarboxylic acids.
- Examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, phthalic acid, diphenic acid, naphthalic acid, 1,2-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, and 2,6.
- aliphatic dicarboxylic acid examples include linear, branched and alicyclic oxalic acid, malonic acid, succinic acid, maleic acid, itaconic acid, glutaric acid, adipic acid and pimelic acid 2,2-dimethylglutaric acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, diglycolic acid, thiodipropionic acid, etc. Can be mentioned.
- polyvalent carboxylic acids and their ester-forming derivatives are used alone or in combination.
- aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, and succinic acid, adipic acid, sebacic acid, dodecanedioic acid, etc.
- Aliphatic dicarboxylic acids are preferably used from the viewpoints of easy reaction, weather resistance, durability and the like of the resulting resin. In particular, it is optimal that only aromatic dicarboxylic acids are used as the polyvalent carboxylic acid component, or that the aromatic dicarboxylic acid is the main component of the polyvalent carboxylic acid component.
- glycol components include glycol derivatives such as diacetate compounds corresponding to glycols, which react with the polyvalent carboxylic acid components to form esters (ester-forming derivatives of glycols). May be included.
- glycol examples include ethylene glycol and diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, hexaethylene glycol, heptaethylene glycol, octaethylene glycol, and other polyethylene glycols, and propylene glycol, dipropylene glycol, and tripropylene glycol.
- Polypropylene glycol such as tetrapropylene glycol, and 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2,2-dimethyl 1,3-propanediol, 2-ethyl-2-butyl-1,3-propanediol, 2-ethyl-2-isobutyl-1,3-propanedio 2,2,4-trimethyl-1,6-hexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2,2,4,4-tetra Methyl-1,3-cyclobutanediol, 4,4′-dihydroxybiphenol, 4,4′-methylenediphenol, 4,4′-isopropylidenediphenol, 1,5-
- ethylene glycol, diethylene glycol, butanediols such as 1,4-butanediol, hexanediols such as 1,6-hexanediol, and 1,4-cyclohexane Dimethanols, neopentyl glycol, bisphenol A, and the like are preferably used from the viewpoint of easy reaction, durability of the resulting resin, and the like.
- the raw material for the polyester resin contains a hydrophilic component (water-solubilizing component).
- This hydrophilic component reacts with other raw materials to form a part of the skeleton structure of the polyester resin, thereby introducing an ionic polar group resulting from the hydrophilic component into the skeleton of the polyester resin. And imparting hydrophilicity to the polyester resin.
- the polyester resin can be made aqueous and can be dispersed or dissolved in an aqueous solvent.
- hydrophilic component water solubility-imparting component
- hydrophilic components corresponding to the polyvalent carboxylic acid component include dicarboxylic acids having a metal sulfonate group, trivalent or higher polyvalent carboxylic acids such as tribasic acid anhydrides and tetrabasic acid anhydrides, and ester-forming derivatives thereof.
- dicarboxylic acids having metal sulfonate groups and ester-forming derivatives thereof include, for example, 5-sulfoisophthalic acid, 2-sulfoisophthalic acid.
- examples thereof include alkali metal salts such as acid, 4-sulfoisophthalic acid, sulfoterephthalic acid and 4-sulfonaphthalene-2,6-dicarboxylic acid, and ester-forming derivatives thereof such as esters, acid chlorides and halides thereof.
- the alkali metal is preferably sodium, potassium or lithium.
- a dicarboxylic acid having a metal sulfonate group or the like is used as a hydrophilic component, the metal sulfonate group effectively remains in the polyester resin, and excellent hydrophilicity can be imparted to the polyester resin.
- the metal sulfonate group effectively remains in the polyester resin, and excellent hydrophilicity can be imparted to the polyester resin.
- 5-sodium sulfoisophthalic acid or an ester thereof for example, sodium dimethylisophthalic acid 5-sulfonate
- a sodium sulfonate group effectively remains in the polyester resin and imparts excellent hydrophilicity to the polyester resin. be able to.
- a trivalent or higher polyvalent carboxylic acid and an ester-forming derivative thereof (hereinafter collectively referred to as a trivalent or higher polyvalent carboxylic acid) as the hydrophilic component.
- a trivalent or higher polyvalent carboxylic acid an ester-forming derivative thereof
- the polyester resin can be dispersed or dissolved in an aqueous solvent.
- trivalent or higher polycarboxylic acids examples include hemimellitic acid, trimellitic acid, trimedic acid, merophanic acid, pyromellitic acid, benzenepentacarboxylic acid, meritic acid, cyclopropane-1,2,3-tricarboxylic acid And acid, polyvalent carboxylic acids such as cyclopentane-1,2,3,4-tetracarboxylic acid and ethanetetracarboxylic acid, and ester-forming derivatives thereof.
- hydrophilic component only one kind may be used among the above-described trivalent or higher polyvalent carboxylic acids, dicarboxylic acids having a metal sulfonate group, or two or more kinds may be used in combination.
- the amount of the hydrophilic component used is preferably in the range of 1 to 60 mol% with respect to the total amount of the polyvalent carboxylic acid component. In this case, particularly excellent hydrophilicity can be imparted to the polyester resin, and good resin strength can be maintained. When the amount used is particularly in the range of 2 to 40 mol%, particularly high flame retardancy and durability can be imparted to the film formed from the film-forming composition containing the polyester resin.
- the amount of the dicarboxylic acid having a metal sulfonate group used may be in the range of 1 to 60 mol% with respect to the total amount of the polyvalent carboxylic acid component. preferable.
- the resin strength of the polyester resin is particularly improved to improve the tensile fracture strength, and when the polyester resin is used for the preparation of the film-forming composition, the polyester resin is formed from the film-forming composition. Particularly good water resistance and durability can be imparted to the film.
- the 5-sodium sulfoisophthalic acid and its ester-forming derivatives are used as the dicarboxylic acid having a metal sulfonate group.
- the total amount used is in the range of 1 to 60 mol% with respect to the total amount of the polyvalent carboxylic acid component, sufficient sodium sulfonate groups can remain in the polyester resin, and the water dispersibility excellent in the polyester resin Alternatively, water solubility can be imparted.
- the total amount of 5-sodiumsulfoisophthalic acid and its ester-forming derivative is in the range of 1 to 30 mol%, particularly excellent effects can be obtained.
- the usage amount of the trivalent or higher polyvalent carboxylic acid or the like is in the range of 1 to 60 mol% with respect to the total amount of the polyvalent carboxylic acid component. It is preferable.
- the polyester resin is produced under a polymerization condition that eliminates unnecessary crosslinking reaction, a polyester resin having a sufficient degree of polymerization and water dispersibility or water solubility can be obtained.
- the used amount of the trivalent or higher polyvalent carboxylic acid or the like is 5 to 40 mol% with respect to the total amount of the polyvalent carboxylic acid component. A range is preferable.
- the formation of the tribasic acid, the tetrabasic acid and the ester thereof when using a tribasic acid, a tetrabasic acid, or an ester-forming derivative thereof as a trivalent or higher polyvalent carboxylic acid, etc., the formation of the tribasic acid, the tetrabasic acid and the ester thereof
- the total amount of the functional derivative used is in the range of 1 to 60 mol% with respect to the total amount of the polyvalent carboxylic acid component
- the carboxyl group can be sufficiently left in the polyester resin, and the water dispersion excellent in the polyester resin is achieved. Or water solubility can be imparted.
- a particularly excellent effect can be obtained when the total amount of the tribasic acid, tetrabasic acid and their ester-forming derivatives used is in the range of 1 to 30 mol%.
- the aqueous solvent in this specification may be a mixed solvent of water and a hydrophilic solvent in addition to water alone.
- the hydrophilic solvent include alcohols such as methanol, ethanol and 2-propanol, glycol ethers such as propylene glycol monomethyl ether, ethyl cellosolve and butyl cellosolve, and cyclohexanone.
- the ratio of water and the hydrophilic solvent is not particularly limited. However, considering the stability of the polyester resin liquid and the safety of the workability environment, the hydrophilicity in the mixed solvent is not limited.
- the content of the neutral solvent is preferably in the range of 0.1 to 50% by weight.
- the aqueous polyester resin is dispersed in an aqueous solvent by being neutralized with a basic compound such as ammonia or alkanolamine as described above. Alternatively, it can be dissolved, but even if such a means is used, it is the same as above.
- the raw material of the polyester resin contains a reactive phosphorus-containing compound.
- This reactive phosphorus-containing compound reacts with other raw materials to form a part of the skeleton structure of the polyester resin, thereby providing a phosphorus atom in the skeleton of the polyester resin.
- the flame retardance of the polyester resin can be improved.
- the reactive phosphorus-containing compound a compound which can be condensed or polycondensed by reacting with at least one of the polyvalent carboxylic acid component and the glycol component can be used. Specifically, it is preferable to use a reactive phosphorus-containing compound having an ester-forming functional group in the molecule.
- the above ester-forming functional group means a functional group that reacts with another carboxyl group or hydroxyl group to form an ester bond.
- the carboxyl group is made anhydride, ester Derived from acidification, acid chlorideation, halogenation, etc., which reacts with other hydroxyl groups to form ester bonds (carboxyl ester-forming derivatives), and hydroxyl groups to acetate And those which react with other carboxyl groups to form ester bonds (ester forming inducers of hydroxyl groups).
- the ester-forming functional group is a carboxyl group or a hydroxyl group, it is preferable because good reactivity can be obtained in the production process.
- the reactive phosphorus-containing compound has one or two ester-forming functional groups in one molecule.
- an aqueous polyester resin having a sufficient degree of polymerization can be obtained when the aqueous polyester resin is produced under polymerization conditions that eliminate unnecessary crosslinking reaction.
- the reactive phosphorus-containing compound has two ester-forming functional groups, the two ester-forming functional groups are both carboxyl groups, or the two ester-forming functional groups are both hydroxyl groups. In some cases, better results are obtained.
- the reactive phosphorus-containing compound compounds represented by the following general formulas (I) to (III) are exemplified as preferable examples because they are particularly excellent in the ease of reaction, flame retardancy and the like.
- the weather resistance of the polyester resin, the stability of the film-forming resin composition prepared from the polyester resin, and the like are particularly excellent.
- R 1 to R 8 each represent a hydrogen atom or an organic group and may be the same or different.
- A represents a hydrogen atom or an organic group, and R 1 to R 8 may be the same as or may be different. However, at least one of R 1 ⁇ R 8 and a is an ester-forming functional group.
- R 9 and R 10 each represent a hydrogen atom or an organic group and may be the same or different, provided that at least one of R 9 and R 10 is an ester-forming functional group.
- R 11 to R 13 each represent a hydrogen atom or an organic group, and may be the same or different, provided that at least one of R 11 to R 13 is an ester-forming functional group.
- the compounds represented by the general formulas (I) to (III) preferably have one or two ester-forming functional groups in one molecule.
- the organic group in the general formulas (I) to (III) is selected from appropriate substituents and is not particularly limited, but a monovalent organic group having 1 to 1000 carbon atoms is preferable.
- monovalent organic groups include aliphatic hydrocarbon groups such as alkyl groups and alkenyl groups, alicyclic hydrocarbon groups such as cyclohexyl groups, aromatic hydrocarbon groups such as aryl groups, and hydrocarbon groups such as aralkyl groups. And a carboxyl group, an alkyloxy group, and the like.
- These groups may further contain a functional group.
- it may have a substituent containing an ester-forming functional group (carboxyl group, hydroxyl group, and ester-forming derivative group derived therefrom).
- the number of ester-forming functional groups present in one molecule is preferably 1 or 2.
- the compound represented by the above general formula (I) preferably has one or two ester-forming functional groups, and these ester-forming functional groups are preferably present in A which is an organic group.
- Particular preferred are those in which R 1 to R 8 are hydrogen atoms and A is an ester-forming functional group derived from a hydroxyl group, a carboxyl group, or these. Having one or two ester-forming derivative groups. In this case, the reactivity at the time of preparation of the polyester resin is improved, and the weather resistance of the obtained polyester resin and the stability of the resin composition for film formation prepared from this polyester resin are particularly excellent. Become.
- R 14 represents a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, or an alicyclic group.
- R 15 and R 16 each represent a hydrogen atom, or a linear or branched alkyl group or alicyclic group having 1 to 6 carbon atoms, and R 15 and R 16 may be the same or different. May be.
- particularly preferred compounds include compounds represented by the following chemical formulas (f) and (g).
- R 17 represents a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, or an alicyclic group.
- R 18 represents a hydrogen atom, or a linear or branched alkyl group or alicyclic group having 1 to 6 carbon atoms.
- R 18 represents a hydrogen atom, or a linear or branched alkyl group or alicyclic group having 1 to 6 carbon atoms.
- R 19 represents a hydrogen atom, or a linear or branched alkyl group or alicyclic group having 1 to 6 carbon atoms.
- the reactive phosphorus-containing compound is added to the reaction system in a state dissolved or dispersed in a monohydric alcohol such as methanol or ethanol, or a dihydric alcohol such as ethylene glycol, propylene glycol or butylene glycol. Is preferred.
- the content of phosphorus atoms derived from the reactive phosphorus-containing compound in the aqueous polyester resin is preferably adjusted to be 300 ppm or more in terms of the weight ratio with respect to the total amount of the aqueous hardly polyester resin, and the content is 500 ppm or more. More preferred.
- the amount of the reactive phosphorus-containing compound used is preferably adjusted so that the phosphorus atom content in the aqueous polyester resin falls within the above range. In this case, particularly excellent flame retardancy is imparted to the aqueous polyester resin.
- the upper limit of the amount of the reactive phosphorus-containing compound used is not particularly limited, but it is preferable to adjust the amount within the above range where the phosphorus atom content is 100000 ppm or less. In this case, the occurrence of poor polymerization or the like is prevented, and the resin properties of the aqueous polyester resin are prevented from being impaired.
- the amount of raw materials used to produce the polyester resin is such that the total number of carboxyl groups and ester-forming derivative groups contained in each raw material, and the total number of hydroxyl groups and ester-forming derivative groups are molar ratios. It is preferably adjusted to be in the range of 1: 1 to 2.5.
- an appropriate amount of a known polyfunctional compound such as pentaerythritol, trimethylolpropane, dimethylolbutanoic acid, trifunctional carboxylic acid, etc., should be used to adjust the molecular weight. Is also preferable.
- the reactive phosphorus-containing compound may act as a terminal terminator. It is preferable to use a suitable compound in combination.
- reaction components other than those described above for example, p-hydroxybenzoic acid, monovalent aliphatic alcohol, and the like can be used together.
- the polyester resin can be produced by polymerizing or polycondensing a raw material by a known polyester production method.
- the polyvalent carboxylic acid component is a polyvalent carboxylic acid and the glycol component is glycol
- a direct esterification reaction in which the polyvalent carboxylic acid and glycol are reacted in a one-step reaction is employed.
- the first is a transesterification reaction between the ester-forming derivative of the polyvalent carboxylic acid and the glycol.
- the polyester resin may be produced through a first stage reaction and a second stage reaction in which the reaction product of the first stage reaction is polycondensed.
- DMT dimethyl terephthalate
- EG ethylene glycol
- BHET bishydroxyethylene terephthalate
- the polycondensation (second stage reaction) of BHET produces polyethylene terephthalate.
- components other than the polyvalent carboxylic acid component and the glycol component are added at any time from the beginning of the first-stage reaction to the end of the second-stage reaction, and subjected to the reaction.
- the transesterification reaction which is the first stage reaction
- all the raw materials used for the production of the aqueous polyester resin may be contained in the reaction system from the beginning, and the reactive phosphorus-containing compound and the like are subjected to an ester polycondensation reaction. Sometimes it may be added to the reaction system.
- this transesterification reaction is carried out, for example, in a state in which a polyvalent carboxylic acid diester and a glycol compound are held in a reaction vessel, under an inert gas atmosphere such as nitrogen gas and under normal pressure conditions. The transesterification proceeds by gradually heating to 260 ° C.
- the polycondensation reaction as the second stage reaction is allowed to proceed within a temperature range of 160 to 280 ° C. under a reduced pressure of, for example, 6.7 hPa (5 mmHg) or less.
- the number average molecular weight of the polyester resin is preferably in the range of 5000 to 50000.
- the durability and water resistance of the polyester resin can be made particularly excellent, and a sufficient effect can be exhibited in improving hydrolysis resistance.
- this number average molecular weight is 50000 or less, when the polyester resin is dispersed or dissolved in an aqueous solvent in the film-forming resin composition, excellent solution stability can be maintained.
- the intrinsic viscosity of the polyester resin is preferably in the range of 0.05 to 1.0.
- excellent flame retardancy, durability and water resistance can be imparted to the film-forming resin composition, and the long-term storage stability of the dispersion or solution can be improved. That is, when the intrinsic viscosity is 0.05 or more, a film having particularly excellent strength can be formed from the film-forming resin composition, and when the intrinsic viscosity is 1.0 or less, the dispersion or solution Long-term storage stability can be made particularly excellent.
- the intrinsic viscosity is in the range of 0.12 to 0.9, particularly excellent effects can be obtained. Further, if the intrinsic viscosity is in the range of 0.2 to 0.9, the optimum effect can be obtained.
- a hybrid type polyester resin can be obtained by preparing a reaction solution containing such a polyester resin, silica particles, and alkoxysilane, and reacting the silica particles and alkoxysilane in the reaction solution by a sol-gel method.
- silica particles silica sol dispersed in water, an aqueous solvent, alcohol or the like can be used.
- the average particle size of the silica particles is preferably 50 nm or less, and particularly preferably 20 nm or less. In this case, the flame retardancy of the hybrid polyester resin can be particularly improved, and the transparency of the hybrid polyester resin can be maintained.
- the lower limit of the average particle size of the silica particles is not particularly limited, but is preferably 4 nm or more or 5 nm or more from the viewpoint of easy availability.
- the average particle size is a value measured by a laser diffraction scattering method using a particle size distribution measuring device.
- Alkoxysilane is represented by the formula of R n SiX 4-n .
- each R independently represents a substituted or unsubstituted hydrocarbon group or a phenyl group.
- R is, for example, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group or an octyl group; a cycloalkyl group such as a cyclopentyl group or a cyclohexyl group; a 2-phenylethyl group Aralkyl groups such as 2-phenylpropyl group and 3-phenylpropyl group; aryl groups such as phenyl group and tolyl group; alkenyl groups such as vinyl group and allyl group; chloromethyl group, ⁇ -chloropropyl group, 3, 3 Halogen-substituted hydro
- n in the formula represents an integer of 0 to 3, but it is particularly preferable that n is an integer of 0 to 2, that is, the alkoxysilane is a tetrafunctional, trifunctional or bifunctional alkoxysilane.
- tetrafunctional alkoxysilanes include tetramethoxysilane and tetraethoxysilane.
- Trifunctional alkoxysilanes include methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, propyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxy Silane etc. are mentioned.
- Examples of the bifunctional alkoxysilane include dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, and methylphenyldimethoxysilane.
- water can be used as the solvent in the reaction solution, or a mixed solvent containing water and another solvent can also be used.
- solvents include toluene, xylene, hexane, ethyl heptane acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, methyl ethyl ketoxime and the like.
- the content of the polyester resin, silica particles and alkoxysilane in the reaction solution is appropriately set.
- the content of the polyester resin is in the range of 1 to 50% by mass, and the content of the silica particles is 1 to 60 with respect to the polyester resin.
- the mass% range and the alkoxysilane content are preferably in the range of 0.3 to 20 mass% with respect to the polyester resin. In this case, it is possible to suppress the occurrence of gelation by maintaining the stability of the reaction solution, and also to improve the flame retardancy of the hybrid polyester resin and to prevent the high temperature droplets during scattering from scattering. Become.
- the stability of the reaction solution may decrease and gel may occur, and if the content of alkoxysilane is excessive, the flame retardancy of the hybrid polyester resin is improved. May not be sufficiently obtained, and if the content of silica is too small, it may be impossible to sufficiently prevent high-temperature droplets from being scattered.
- This catalyst may be an acidic catalyst or a basic catalyst.
- the acidic catalyst include organic acids such as acetic acid, chloroacetic acid, citric acid, benzoic acid, dimethylmalonic acid, formic acid, propionic acid, glutaric acid, glycolic acid, maleic acid, malonic acid, toluenesulfonic acid, and oxalic acid;
- examples thereof include inorganic acids such as hydrochloric acid, nitric acid, and halogenated silane; acidic sol fillers such as acidic colloidal silica and oxidized titania sol.
- Examples of the basic catalyst include aqueous solutions of hydroxides of alkali metals or alkaline earth metals such as sodium hydroxide and calcium hydroxide; aqueous ammonia and aqueous solutions of amines. These catalysts may be used alone or in combination of two or more.
- reaction solution may contain a phosphorus-based flame retardant.
- flame retardance of this hybrid type polyester resin can be improved by mixing a phosphorus flame retardant into the hybrid type polyester resin.
- phosphorus-based flame retardants include polyphosphates such as butyl bis (3-hydroxypropyl) phosphine oxide and ammonium polyphosphate, and guanidine phosphate derivatives.
- the amount used is preferably in the range of 1 to 40% by mass with respect to the polyester resin.
- the siloxane produced by this reaction and the polyester resin can be hybridized by advancing the sol-gel reaction of silica particles and alkoxysilane.
- the sol-gel reaction may be allowed to proceed at room temperature, or may be allowed to proceed while heating the reaction solution.
- the sol-gel reaction can proceed while the reaction solution is preferably at a temperature of 10 to 90 ° C., more preferably 20 to 80 ° C., and even more preferably 30 to 60 ° C.
- the reaction time depends on the reaction temperature, but can be, for example, in the range of 1 to 48 hours.
- the hybrid polyester resin obtained by hybridizing the polyester resin and the siloxane in this way has excellent flame retardancy while retaining the excellent properties inherent in the polyester resin, and even if it is burned temporarily. A characteristic that high temperature droplets are difficult to scatter is imparted.
- the flame retardancy of the hybrid polyester resin can be further improved.
- a hydrophilic component is used as a raw material for polyester, this hybrid polyester resin is imparted with excellent water dispersibility or water solubility.
- This hybrid type polyester resin can be used for various applications.
- this hybrid type polyester resin is excellent in durability and the like, this hybrid type polyester resin can be suitably used for the preparation of a film-forming resin composition.
- the film-forming resin composition can be applied in the state of an aqueous composition when the above-described hybrid polyester resin has excellent water dispersibility or water-solubility.
- This film-forming resin composition By using this, the work safety and the environmental conservation are excellent when the base material is processed.
- the film-forming resin composition may contain additives such as penetrants, flame retardants, antistatic agents, pigments, dyes, antioxidants, ultraviolet absorbers, antifoaming agents, and dispersion aids as necessary. May be contained.
- the film-forming resin composition is immersed in a woven fabric, a knitted fabric, a nonwoven fabric, a rug, a web or the like, a padding method, a coating method, etc.
- coating the method of apply
- the film-forming resin composition is subsequently applied to the produced PET film.
- a method is mentioned.
- a method of applying a film-forming resin composition to the surface of the polyester film at any stage of the process of forming a polyester such as PET by a conventional method is also included.
- the film formation of PET is performed through, for example, PET drying, melt extrusion, unstretched sheet formation, biaxial stretching, and heat treatment, but the film-forming resin composition is in any of the above steps.
- it is applied to the film surface by a dipping method, curtain coating method, gravure coating method, wire bar method, spray coating method, reverse coating method or die coating method.
- a coating agent such as metal, glass, paper, and wood
- an overcoat agent such as an electronic substrate
- adhesives such as anchor coating agents and ink binders
- surface treating agents for plastic films such as polyvinyl chloride and polycarbonate.
- Polyester films and fibers that have been surface-treated with a film-forming resin composition in this way are given excellent flame retardancy, and even if they are burned due to a fire, the hybrid polyester resin on the surface is less likely to collapse. , Scattering of high-temperature droplets is suppressed. For this reason, the expansion of the damage in a fire etc. is suppressed.
- Synthesis Example 2 In Synthesis Example 1, the amount of dimethylisophthalic acid used in preparing the reaction solution was 44.7 parts, the amount of sodium 5-sulfonate dimethylisophthalic acid was 29.6 parts, and the amount of ethylene glycol used was 116.8. Each part was changed. Further, 12.7 parts of diethylene glycol was added to the reaction solution. Otherwise, an aqueous polyester resin having an intrinsic viscosity of 0.57 and a number average molecular weight of 25,000 was obtained under the same conditions as in Synthesis Example 1.
- polyester resin 25 parts, 70 parts of water and 5 parts of ethylene glycol mono-t-butyl ether were added to a dissolution vessel and dissolved with stirring at a temperature of 80 to 95 ° C. over 2 hours to obtain a 25% aqueous solution B of polyester resin.
- Example 1 In a reactor, 100 parts of the polyester aqueous solution A obtained in Synthesis Example 1 above, 50 parts of water, 50 parts of methanol, 10 parts of colloidal silica (30% aqueous solution), 5 parts of ammonium polyphosphate, 0.1 part of tetraethoxysilane, and 0.3 parts of 25% aqueous ammonia was added and reacted at 25 ° C. and 500 rpm for 5 hours. Thereafter, methanol and produced alcohol were distilled off under reduced pressure to obtain an aqueous solution of a hybrid type polyester resin.
- Example 2 In Example 1, the amount of tetraethoxysilane used was changed to 1 part. Otherwise, an aqueous solution of a hybrid type polyester resin was obtained under the same conditions as in Example 1.
- Example 3 In Example 1, the amount of tetraethoxysilane used was changed to 5 parts. Otherwise, an aqueous solution of a hybrid type polyester resin was obtained under the same conditions as in Example 1.
- Example 4 In Example 1, the polyester aqueous solution B synthesized in the above Synthesis Example 2 was used in place of the polyester aqueous solution A, IPA silica sol (solid content 30%) was used in place of colloidal silica (30% aqueous solution), and ammonium polyphosphate The amount used was changed to 10 parts and the amount used of tetraethoxysilane was changed to 0.5 parts. Otherwise, an aqueous solution of a hybrid type polyester resin was obtained under the same conditions as in Example 1.
- Example 5 In Example 4, propyltrimethoxysilane was used instead of tetraethoxysilane, and the amount of ammonium polyphosphate used was changed to 5 parts. Otherwise, an aqueous solution of a hybrid polyester resin was obtained under the same conditions as in Example 4.
- Example 6 dimethyldiethoxysilane was used instead of tetraethoxysilane, and the amount of ammonium polyphosphate used was changed to 1 part. Otherwise, an aqueous solution of a hybrid polyester resin was obtained under the same conditions as in Example 4.
- Example 7 In Example 4, butyl bis (3-hydroxypropyl) phosphine oxide was used in place of ammonium polyphosphate. Otherwise, an aqueous solution of a hybrid polyester resin was obtained under the same conditions as in Example 4.
- Example 8 In Example 5, butyl bis (3-hydroxypropyl) phosphine oxide was used in place of ammonium polyphosphate. Otherwise, an aqueous solution of a hybrid type polyester resin was obtained under the same conditions as in Example 5.
- Example 9 In Example 6, butyl bis (3-hydroxypropyl) phosphine oxide was used in place of ammonium polyphosphate. Otherwise, an aqueous solution of a hybrid type polyester resin was obtained under the same conditions as in Example 6.
- Example 10 In Example 7, the amount of IPA silica sol used was changed to 1 part, and the amount of butylbutylbis (3-hydroxypropyl) phosphine oxide used was changed to 5 parts. Otherwise, an aqueous solution of a hybrid type polyester resin was obtained under the same conditions as in Example 7.
- Example 11 In Example 10, the amount of IPA silica sol used was changed to 50 parts. Otherwise, an aqueous solution of a hybrid polyester resin was obtained under the same conditions as in Example 10.
- Example 12 In Example 10, HCA-HQ (reactive phosphorus-containing compound (d) represented by the above chemical formula (d)) was used instead of butyl bis (3-hydroxypropyl) phosphine oxide, and the amount of IPA silica sol used was changed. Changed to 10 copies. Otherwise, an aqueous solution of a hybrid polyester resin was obtained under the same conditions as in Example 10.
- HCA-HQ reactive phosphorus-containing compound (d) represented by the above chemical formula (d)
- Example 13 In Example 4, 1 M HCl aqueous solution was used instead of 25% aqueous ammonia. Otherwise, an aqueous solution of a hybrid polyester resin was obtained under the same conditions as in Example 4.
- Example 14 In Example 5, 1M HCl aqueous solution was used instead of 25% aqueous ammonia. Otherwise, an aqueous solution of a hybrid type polyester resin was obtained under the same conditions as in Example 5.
- Example 15 In Example 6, 1M HCl aqueous solution was used instead of 25% aqueous ammonia. Otherwise, an aqueous solution of a hybrid type polyester resin was obtained under the same conditions as in Example 6.
- Example 16 In Example 7, the polyester aqueous solution C synthesized in the above Synthesis Example 3 was used in place of the polyester aqueous solution B, and methanol silica sol (solid content 30%) was used in place of the IPA silica sol, and butylbis (3-hydroxypropyl) phosphine The amount of oxide used was changed to 5 parts. Otherwise, an aqueous solution of a hybrid type polyester resin was obtained under the same conditions as in Example 7.
- Example 17 In Example 16, propyltrimethoxysilane was used in place of tetraethoxysilane. Otherwise, an aqueous solution of a hybrid type polyester resin was obtained under the same conditions as in Example 16.
- Example 18 dimethyldiethoxysilane was used in place of tetraethoxysilane. Otherwise, an aqueous solution of a hybrid type polyester resin was obtained under the same conditions as in Example 16.
- Example 19 In Example 16, butyl bis (3-hydroxypropyl) phosphine oxide was not used. Otherwise, an aqueous solution of a hybrid type polyester resin was obtained under the same conditions as in Example 16.
- Example 20 In Example 17, butyl bis (3-hydroxypropyl) phosphine oxide was not used. Otherwise, an aqueous solution of a hybrid type polyester resin was obtained under the same conditions as in Example 17.
- Example 21 In Example 18, butyl bis (3-hydroxypropyl) phosphine oxide was not used. Otherwise, an aqueous solution of a hybrid type polyester resin was obtained under the same conditions as in Example 18.
- Example 7 In Example 7, no tetraethoxysilane was used. Otherwise, an aqueous polyester resin solution was obtained under the same conditions as in Example 4.
- Example 7 In Example 7, no IPA silica sol was used. Otherwise, an aqueous polyester resin solution was obtained under the same conditions as in Example 4.
- Example 7 tetraethoxysilane and butyl bis (3-hydroxypropyl) phosphine oxide were not used. Otherwise, an aqueous polyester resin solution was obtained under the same conditions as in Example 4.
- Example 7 tetraethoxysilane and IPA silica sol were not used. Otherwise, an aqueous polyester resin solution was obtained under the same conditions as in Example 4.
- the flammability test was conducted on the test cloth in accordance with the 45 ° micro burner method (JIS L 1091 A-1 method) and the flame contact method (JIS L 1091 D method).
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Abstract
Description
この一般式(I)~(III)に示す化合物は、特に一分子中にエステル形成性官能基を1個又は2個有することが好ましい。
また、上記一般式(III)で表される化合物のうち、特に好適な化合物として、下記化学式(h)で表される化合物が例示される。
ポリエステル樹脂を製造する際、上記反応性リン含有化合物を、メタノール、エタノールなどの1価アルコール、エチレングリコール、プロピレングリコール、ブチレングリコールなどの2価アルコールに溶解もしくは分散した状態で反応系に添加することが好ましい。
反応器に、ジメチルテレフタル酸135.9部、ジメチルイソフタル酸35.0部、5-スルホン酸ナトリウムジメチルイソフタル酸35.5部、エチレングリコール124.2部及び触媒としてシュウ酸チタンカリウム0.1部を加えて反応溶液を調製し、これを常圧、窒素雰囲気中で攪拌混合しながら200℃に昇温した。次に、4時間かけて反応温度を260℃にまで徐々に昇温しエステル交換反応を終了させた。その後、260℃で徐々に減圧し260℃、0.67hPa(0.5mmHg)の条件下で2時間重縮合反応を行い、固有粘度0.60、数平均分子量27000の水性のポリエステル樹脂を得た。
合成例1において、反応溶液を調製する際のジメチルイソフタル酸の使用量を44.7部、5-スルホン酸ナトリウムジメチルイソフタル酸の使用量を29.6部、エチレングリコールの使用量を116.8部にそれぞれ変更した。また反応溶液には更にジエチレングリコール12.7部を加えた。それ以外は合成例1の場合と同じ条件で、固有粘度0.57、数平均分子量25000の水性のポリエステル樹脂を得た。
合成例1において、反応溶液を調製する際のジメチルテレフタル酸の使用量を48.6部、ジメチルイソフタル酸の使用量を46.6部、5-スルホン酸ナトリウムジメチルイソフタル酸の使用量を17.8部、エチレングリコールの使用量を195.3部に変更した。また反応溶液には更にジエチレングリコール12.7部、上記化学式(e)で表される反応性リン含有化合物115.5部及びトリメチロールプロパン2.7部を加えた。それ以外は合成例1の場合と同じ条件で、固有粘度0.50、数平均分子量12000の水性のポリエステル樹脂を得た。
反応器に上記合成例1で得られたポリエステル水溶液Aを100部、水50部、メタノール50部、コロイダルシリカ(30%水溶液)10部、ポリリン酸アンモニウム5部、テトラエトキシシラン0.1部及び25%アンモニア水0.3部を入れ、25℃、500rpmで5時間反応させた。その後メタノールおよび生成したアルコールを減圧溜去し、ハイブリッド型ポリエステル樹脂の水溶液を得た。
実施例1において、テトラエトキシシランの使用量を1部に変更した。それ以外は実施例1と同じ条件で、ハイブリッド型ポリエステル樹脂の水溶液を得た。
実施例1において、テトラエトキシシランの使用量を5部に変更した。それ以外は実施例1と同じ条件で、ハイブリッド型ポリエステル樹脂の水溶液を得た。
実施例1において、ポリエステル水溶液Aに代えて上記合成例2で合成したポリエステル水溶液Bを使用し、コロイダルシリカ(30%水溶液)に代えてIPAシリカゾル(固形分量30%)を使用し、ポリリン酸アンモニウムの使用量を10部、テトラエトキシシランの使用量を0.5部にそれぞれ変更した。それ以外は実施例1と同じ条件で、ハイブリッド型ポリエステル樹脂の水溶液を得た。
実施例4において、テトラエトキシシランに代えてプロピルトリメトキシシランを使用し、ポリリン酸アンモニウムの使用量を5部に変更した。それ以外は実施例4と同じ条件で、ハイブリッド型ポリエステル樹脂の水溶液を得た。
実施例4において、テトラエトキシシランに代えてジメチルジエトキシシランを使用し、ポリリン酸アンモニウムの使用量を1部に変更した。それ以外は実施例4と同じ条件で、ハイブリッド型ポリエステル樹脂の水溶液を得た。
実施例4において、ポリリン酸アンモニウムに代えてブチルビス(3-ヒドロキシプロピル)ホスフィンオキサイドを使用した。それ以外は実施例4と同じ条件で、ハイブリッド型ポリエステル樹脂の水溶液を得た。
実施例5において、ポリリン酸アンモニウムに代えてブチルビス(3-ヒドロキシプロピル)ホスフィンオキサイドを使用した。それ以外は実施例5と同じ条件で、ハイブリッド型ポリエステル樹脂の水溶液を得た。
実施例6において、ポリリン酸アンモニウムに代えてブチルビス(3-ヒドロキシプロピル)ホスフィンオキサイドを使用した。それ以外は実施例6と同じ条件で、ハイブリッド型ポリエステル樹脂の水溶液を得た。
実施例7において、IPAシリカゾルの使用量を1部、ブチルブチルビス(3-ヒドロキシプロピル)ホスフィンオキサイドの使用量を5部に変更した。それ以外は実施例7と同じ条件で、ハイブリッド型ポリエステル樹脂の水溶液を得た。
実施例10において、IPAシリカゾルの使用量を50部に変更した。それ以外は実施例10と同じ条件で、ハイブリッド型ポリエステル樹脂の水溶液を得た。
〔実施例12〕
実施例10において、ブチルビス(3-ヒドロキシプロピル)ホスフィンオキサイドに代えて、HCA-HQ(上記化学式(d)で表される反応性リン含有化合物(d))を使用し、IPAシリカゾルの使用量を10部に変更した。それ以外は実施例10と同じ条件で、ハイブリッド型ポリエステル樹脂の水溶液を得た。
実施例4において、25%アンモニア水に代えて1MのHCl水溶液を使用した。それ以外は実施例4と同じ条件で、ハイブリッド型ポリエステル樹脂の水溶液を得た。
実施例5において、25%アンモニア水に代えてを1MのHCl水溶液を使用した。それ以外は実施例5と同じ条件で、ハイブリッド型ポリエステル樹脂の水溶液を得た。
実施例6において、25%アンモニア水に代えて1MのHCl水溶液を使用した。それ以外は実施例6と同じ条件で、ハイブリッド型ポリエステル樹脂の水溶液を得た。
実施例7において、ポリエステル水溶液Bに代えて上記合成例3で合成したポリエステル水溶液Cを使用し、IPAシリカゾルに代えてメタノールシリカゾル(固形分量30%)を使用し、ブチルビス(3-ヒドロキシプロピル)ホスフィンオキサイドの使用量を5部に変更した。それ以外は実施例7と同じ条件で、ハイブリッド型ポリエステル樹脂の水溶液を得た。
実施例16において、テトラエトキシシランに代えてプロピルトリメトキシシランを使用した。それ以外は実施例16と同じ条件で、ハイブリッド型ポリエステル樹脂の水溶液を得た。
実施例16において、テトラエトキシシランに代えてジメチルジエトキシシランを使用した。それ以外は実施例16と同じ条件で、ハイブリッド型ポリエステル樹脂の水溶液を得た。
実施例16において、ブチルビス(3-ヒドロキシプロピル)ホスフィンオキサイドを使用しなかった。それ以外は実施例16と同じ条件で、ハイブリッド型ポリエステル樹脂の水溶液を得た。
実施例17において、ブチルビス(3-ヒドロキシプロピル)ホスフィンオキサイドを使用しなかった。それ以外は実施例17と同じ条件で、ハイブリッド型ポリエステル樹脂の水溶液を得た。
実施例18において、ブチルビス(3-ヒドロキシプロピル)ホスフィンオキサイドを使用しなかった。それ以外は実施例18と同じ条件で、ハイブリッド型ポリエステル樹脂の水溶液を得た。
上記合成例1で合成したポリエステル水溶液Aをそのまま使用した。
上記合成例2で合成したポリエステル水溶液Bをそのまま使用した。
上記合成例3で合成したポリエステル水溶液Cをそのまま使用した。
実施例7において、テトラエトキシシランを使用しなかった。それ以外は実施例4と同じ条件で、ポリエステル樹脂の水溶液を得た。
実施例7において、IPAシリカゾルを使用しなかった。それ以外は実施例4と同じ条件で、ポリエステル樹脂の水溶液を得た。
実施例7において、テトラエトキシシランおよびブチルビス(3-ヒドロキシプロピル)ホスフィンオキサイドを使用しなかった。それ以外は実施例4と同じ条件で、ポリエステル樹脂の水溶液を得た。
実施例7において、テトラエトキシシランおよびIPAシリカゾルを使用しなかった。それ以外は実施例4と同じ条件で、ポリエステル樹脂の水溶液を得た。
各実施例で得られたハイブリッド型ポリエステル樹脂の水溶液、及び各比較例で得られたポリエステル樹脂の水溶液を用い、これを用いてポリエステルトロピカル布をパディング法にて加工し、これを110℃で5分間乾燥させた後、180℃で1分間キュア処理を施して、試験布を得た。
Claims (8)
- 以下の構成を含むハイブリッド型ポリエステル樹脂
- ポリエステル樹脂
- シリカとアルコキシシランから形成されるシロキサン。 - 請求項1に記載のハイブリッド型ポリエステル樹脂であって、上記ポリエステル樹脂は、多価カルボン酸成分、グリコール成分及び、親水性成分から形成される水性ポリエステル樹脂を含む。
- 請求項1または2に記載のハイブリッド型ポリエステル樹脂であって、上記ポリエステル樹脂は、リン含有ポリエステル樹脂を含む。
- 請求項3に記載のハイブリッド型ポリエステル樹脂であって、上記リン含有ポリエステル樹脂は多価カルボン酸成分、グリコール成分、親水性成分、および反応性リン含有化合物から形成される。
- リン系難燃剤をさらに含有する請求項1から4のいずれか1項に記載のハイブリッド型ポリエステル樹脂。
- 請求項1乃至5のいずれか一項に記載のハイブリッド型ポリエステル樹脂を含有する皮膜形成用樹脂組成物。
- 請求項6に記載の皮膜形成用樹脂組成物により表面処理されたポリエステルフィルム。
- 請求項6に記載の皮膜形成用樹脂組成物により処理された繊維。
Priority Applications (4)
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US13/505,277 US9873978B2 (en) | 2009-11-02 | 2010-10-28 | Hybrid-type polyester resin, resin composition for formation of film, and polyester film and textile |
CN201080049236.4A CN102656206B (zh) | 2009-11-02 | 2010-10-28 | 混合型聚酯树脂、被膜形成用树脂组合物、聚酯膜以及纤维 |
KR1020127014372A KR101399535B1 (ko) | 2009-11-02 | 2010-10-28 | 하이브리드형 폴리에스테르 수지, 피막 형성용 수지 조성물, 폴리에스테르 필름 및 섬유 |
JP2011538477A JP5658678B2 (ja) | 2009-11-02 | 2010-10-28 | ハイブリッド型ポリエステル樹脂、皮膜形成用樹脂組成物、ポリエステルフィルム、繊維及びハイブリッド型ポリエステル樹脂の製造方法 |
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JP2009252225 | 2009-11-02 | ||
JP2009-252225 | 2009-11-02 |
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WO2011052677A1 true WO2011052677A1 (ja) | 2011-05-05 |
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PCT/JP2010/069158 WO2011052677A1 (ja) | 2009-11-02 | 2010-10-28 | ハイブリッド型ポリエステル樹脂、皮膜形成用樹脂組成物、ポリエステルフィルム及び繊維 |
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US (1) | US9873978B2 (ja) |
JP (1) | JP5658678B2 (ja) |
KR (1) | KR101399535B1 (ja) |
CN (1) | CN102656206B (ja) |
TW (1) | TWI457396B (ja) |
WO (1) | WO2011052677A1 (ja) |
Cited By (1)
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WO2019082768A1 (ja) * | 2017-10-25 | 2019-05-02 | 富士フイルム株式会社 | コート剤、防曇膜、防曇膜の製造方法、及び積層体 |
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FR3030550B1 (fr) | 2014-12-22 | 2018-08-17 | Saint-Gobain Adfors | Composition aqueuse de liant pour fibres et produits fibreux obtenus. |
CN107936824A (zh) * | 2017-11-30 | 2018-04-20 | 明光市泰丰新材料有限公司 | 一种耐候高粘环保防火涂料及其制备方法 |
KR101986583B1 (ko) * | 2018-03-19 | 2019-06-10 | 한국신발피혁연구원 | 기능성 선박 갑판 피복용 열경화성 수지 조성물 |
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2010
- 2010-10-28 US US13/505,277 patent/US9873978B2/en not_active Expired - Fee Related
- 2010-10-28 JP JP2011538477A patent/JP5658678B2/ja not_active Expired - Fee Related
- 2010-10-28 WO PCT/JP2010/069158 patent/WO2011052677A1/ja active Application Filing
- 2010-10-28 KR KR1020127014372A patent/KR101399535B1/ko active IP Right Grant
- 2010-10-28 CN CN201080049236.4A patent/CN102656206B/zh not_active Expired - Fee Related
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TWI457396B (zh) | 2014-10-21 |
JP5658678B2 (ja) | 2015-01-28 |
US9873978B2 (en) | 2018-01-23 |
CN102656206B (zh) | 2014-07-30 |
CN102656206A (zh) | 2012-09-05 |
KR20120101432A (ko) | 2012-09-13 |
TW201124466A (en) | 2011-07-16 |
US20120277381A1 (en) | 2012-11-01 |
KR101399535B1 (ko) | 2014-05-27 |
JPWO2011052677A1 (ja) | 2013-03-21 |
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