JP5297085B2 - Water-based polyester resin hybridized with layered silicate, resin composition for film formation, polyester film and fiber - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an aqueous polyester resin improved with its application property and solving the issues of working environment and environment maintenance caused by a solvent by making the polyester resin as an aqueous solution, without invading base materials in the case of using it for processing fibers, PET films or the like, and also equipping excellent flame retardance. <P>SOLUTION: This aqueous polyester resin is produced through the process of reacting for the condensation or polycondensation of a polycarboxylic acid component, glycol component and water solubility-imparting component in the presence of a layered silicate. The aqueous polyester resin is imparted with a property of dispersing or dissolving in an aqueous medium by the water solubility-imparting component. Also, the flame retardance is imparted by making it a nano-composite with the layered silicate. Further, by nano-composite formation with the layered silicate, its form becomes hardly collapsible on burning and the scattering of liquid droplets at a high temperature is inhibited. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

The present invention relates to a water-based polyester resin hybridized with a layered silicate , which can be dispersed or dissolved in an aqueous solvent, and which prevents scattering of high-temperature droplets during combustion, and a water-based polyester hybridized with this layered silicate. The present invention relates to a resin composition for film formation containing a resin, and a polyester film and fibers that have been processed with the resin composition for film formation.

  As is well known, 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.

  In recent years, there has been an increasing demand for improving the fire resistance of synthetic fibers and various plastic products from the viewpoint of fire prevention, but conventional polyester resins have been insufficient in terms of fire resistance. For this reason, flame retarding has been attempted by adding a flame retardant typified by a halogenated organic compound or an antimony compound at the time of polyester production.

  However, these flame retardants have the problem of generating toxic gases when they come into contact with flames. For this reason, it has been proposed to add hydrated metal compounds such as aluminum hydroxide and magnesium hydroxide. In order to obtain sufficient flame retardancy, it is necessary to add a large amount, and the original excellent properties of the polyester resin are lost.

  Thus, in order to solve these problems, a method of adding or copolymerizing a specific phosphorus compound as a flame retardant during polyester production has been proposed (see Patent Documents 1 to 3).

  However, many of these phosphorus-containing polyester resins are hardly soluble in general-purpose organic solvents such as toluene and xylene, and solutions of phosphorus-containing polyester resins for processing such as fibers and PET films using these general-purpose organic solvents, In order to obtain a dispersion, the degree of polymerization had to be extremely low, and it was difficult to maintain the original characteristics of the polyester resin. For this reason, when maintaining the original properties of the polyester resin while maintaining a high degree of polymerization of such a phosphorus-containing polyester resin, when applying by coating as a substrate processing resin such as fibers and PET film Organic solvents having high solubility such as dioxane, DMF, HFIP, OCP and the like must be used. Although these solvents have high solubility, there are problems from the viewpoint of working environment and environmental conservation.

  In addition, when an organic solvent is used, there is a problem that the processed substrate, such as fiber and PET film itself, is eroded. However, the phosphorus-containing polyester resin does not have dispersibility or solubility in water, and the aqueous solvent is used as a solvent. This solvent could not be used.

In order to solve these problems, the present applicant has proposed that a water-soluble imparting component and a reactive phosphorus-containing compound are contained in the reaction system during the synthesis of polyester (see Patent Document 4). ). As a result, an aqueous polyester resin that is imparted with flame retardancy and can be processed by an aqueous system while retaining the excellent properties inherent in the polyester resin is obtained.
JP-A-6-16796 JP 2001-139784 A JP 2001-163962 A JP 2004-67910 A

  As described above, the flame retardancy of the polyester resin has been promoted. However, the present inventors have achieved not only the addition of flame retardancy but also the further prevention of fire while achieving the water-based polyester resin. The polyester resin has been improved in order to impart characteristics to the polyester resin. And the present inventors pay attention to the fact that even 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 the coating property is improved by making the polyester resin water-based, and the working environment caused by the solvent and the problem of environmental conservation can be solved. An aqueous polyester resin hybridized with a layered silicate that does not attack these substrates even when used for processing on a substrate such as a PET film, and even when burnt, the scattering of high-temperature droplets is suppressed, It is an object of the present invention to provide a film-forming resin composition containing an aqueous polyester resin hybridized with the layered silicate, and a polyester film and fibers processed with the film-forming resin composition.

The aqueous polyester resin hybridized with the layered silicate according to the present invention is produced through a process in which a polyvalent carboxylic acid component, a glycol component, and a water-solubilizing component are reacted in the presence of the layered silicate and condensed or polycondensed. It is characterized by being made. For this reason, the aqueous polyester resin hybridized with the layered silicate is imparted with the property that it can be dispersed or dissolved in an aqueous solvent by the water-solubilizing component while retaining the excellent properties inherent in the polyester resin. . In addition, by making a nanocomposite with a layered silicate, flame retardancy is improved, and even when burned, the shape is difficult to collapse and scattering of high temperature droplets is suppressed.

  The water-solubilizing component may correspond to either a polyvalent carboxylic acid component or a glycol component.

The usage-amount of the said water solubility provision component is the range of 1-60 mol% with respect to the total amount of the usage-amount of the said polyhydric carboxylic acid component and a water solubility provision component . In this case, sufficient water dispersibility or water solubility is imparted to the aqueous polyester resin, and good resin strength is maintained.

The amount of the layered silicate, area by der of 0.1 to 15% by weight relative to the polyester resin. In this case, the stability of the aqueous dispersion of the aqueous polyester resin containing layered silicate is improved, and excellent strength and transparency are imparted to the film formed from the aqueous polyester resin hybridized with the layered silicate. .

  The layered silicate is preferably at least one selected from natural products and synthetic products. In this case, an aqueous polyester resin in which the layered silicate and the polyester resin are effectively hybridized is obtained.

  The layered silicate may be an organic layered silicate. In this case, the compatibility between the layered silicate and the polyester resin is improved, and the hybridization between the two is promoted. In this case, it is desirable to use a dispersion solvent suitable for the organic layered silicate.

Further, the water-imparting component, a dicarboxylic acid having a metal sulfonate group, tribasic acids, tetrabasic acids, or including a least one selected from ester-forming derivatives thereof. In this case, the metal sulfonate group effectively remains in the aqueous polyester resin, and excellent hydrophilicity is imparted to the aqueous polyester resin.

  The dicarboxylic acid having a metal sulfonate group is at least one selected from 5-sodium sulfoisophthalic acid and ester-forming derivatives thereof. Use of the 5-sodium sulfoisophthalic acid and ester-forming derivatives thereof The total amount 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, the sodium sulfonate group effectively remains in the water-based polyester resin, so that the water-based polyester resin is given particularly excellent hydrophilicity, and the water-dispersibility particularly excellent in the water-based polyester resin hybridized with the layered silicate. Or water solubility is provided.

  Further, the total amount of the tribasic acid, the tetrabasic acid and their ester-forming derivatives that are water-soluble imparting components may be in the range of 1 to 60 mol% with respect to the total amount of the polyvalent carboxylic acid component. preferable. In this case, the carboxyl group effectively remains in the aqueous polyester resin, thereby imparting particularly excellent hydrophilicity to the aqueous polyester resin, and particularly excellent water dispersibility or water solubility in the aqueous polyester resin hybridized with the layered silicate. Sex is imparted.

  Moreover, it is preferable to use at least 1 type selected from trimellitic acid and its ester-forming derivative as a tribasic acid which is a water solubility provision component. In this case, the carboxyl group effectively remains in the aqueous polyester resin, and further excellent hydrophilicity is imparted to the aqueous polyester resin.

The resin composition for film formation according to the present invention is characterized by containing an aqueous polyester resin hybridized with the layered silicate as described above. For this reason, this film-forming resin composition is dispersed in an aqueous solvent by a water-soluble imparting component in an aqueous polyester resin hybridized with the layered silicate in the composition while retaining the excellent properties inherent in the polyester resin. Or the property of being soluble is given. In addition, since this water-based polyester resin is made into a nanocomposite with a layered silicate, not only flame retardancy is improved, but the shape of the water-based polyester resin is not easily broken during combustion, and scattering of high-temperature droplets is suppressed.

  This film-forming resin composition is preferably for polyester film surface processing. In this case, 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.

  The film-forming resin composition is also preferably used for fiber processing. In this case, not only the flame retardancy of the fiber that has been processed with the film-forming resin composition is improved, but the shape of the fiber is less likely to collapse during combustion, and high-temperature droplets are prevented from scattering.

  The polyester film according to the present invention is characterized by being subjected to a surface treatment with the film forming resin composition. For this reason, this polyester film not only improves flame retardancy, but also its shape is less likely to collapse during combustion, and high temperature droplets are prevented from scattering.

  The fiber according to the present invention is characterized by being processed by the above-mentioned resin composition for film formation. For this reason, this fiber not only improves flame retardancy, but also its shape is less likely to collapse during combustion, and high temperature droplets are prevented from scattering.

According to the present invention, the aqueous polyester resin hybridized with the layered silicate is given the property of being dispersible or soluble in an aqueous solvent in addition to the excellent properties inherent in the polyester resin. The hybrid water-based polyester resin and the film-forming resin composition containing the water-based polyester resin hybridized with this layered silicate can be applied in the state of an aqueous composition, thus providing occupational safety and environmental safety. And it is excellent from the viewpoint of the ease of processing of the substrate. Moreover, the flame retardancy of the aqueous polyester resin hybridized with the layered silicate is improved, and even if it is burned, its shape is difficult to collapse, and high-temperature droplets are prevented from scattering, and the combustion resistance is enhanced. Moreover, the outstanding flame resistance is provided to the polyester film and fiber which were processed with the resin composition for film formation containing the aqueous polyester resin hybridized with this layered silicate .

  Hereinafter, the best mode for carrying out the present invention will be described.

  The aqueous polyester resin according to the present invention is obtained through a step of reacting a polyvalent carboxylic acid component, a glycol component, and a water-solubilizing component in the presence of a layered silicate for condensation or polycondensation.

  In addition, when the raw material of the water-based polyester resin is classified as a polyvalent carboxylic acid component, a glycol component, and a water-solubility imparting component, the polyvalent carboxylic acid component and the glycol component correspond to the water-solubility imparting component. Is also included.

  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. It comprises one or more compounds selected from those that form (ester-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. -Naphthalenedicarboxylic acid and the like, and examples of the aliphatic dicarboxylic acid include linear, branched and alicyclic oxalic acid, malonic acid, succinic acid, maleic acid, itaconic acid, glutaric acid, adipic acid, 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.

  These polyvalent carboxylic acids and ester-forming derivatives thereof are used alone or in combination. Among these polyvalent carboxylic acids and ester-forming derivatives thereof, aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and 2,6-naphthalenedicarboxylic acid, and succinic acid, adipic acid, sebacic acid, dodecanedioic acid, etc. Aliphatic dicarboxylic acids are preferably used in terms of ease of reaction, weather resistance of the resulting resin, durability, and the like. In particular, it is optimal that only aromatic dicarboxylic acids are used as the polyvalent carboxylic acid component not corresponding to the water-solubilizing component, or that the aromatic dicarboxylic acid is the main component of the polyvalent carboxylic acid component.

  In addition to glycol, the glycol component is a glycol derivative such as a diacetate compound corresponding to glycol, which reacts with the polyvalent carboxylic acid component to form an ester (an ester-forming derivative of glycol). May also be included.

  Examples of the glycol 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-propanediol 2,2,4-trimethyl-1,6-hexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2,2,4,4-tetramethyl -1,3-cyclobutanediol, 4,4'-dihydroxybiphenol, 4,4'-methylenediphenol, 4,4'-isopropylidenediphenol, 1,5-dihydroxynaphthalene, 2,5-dihydroxynaphthalene, 2 , 2-bis (4-hydroxyphenyl) propane (bisphenol A), bisphenol S, and the like.

  These glycols and their ester-forming derivatives are used singly or in combination. Among these glycols and their ester-forming derivatives, 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 water-solubilizing component reacts with at least one of polyvalent carboxylic acid, glycol and ester-forming derivatives thereof in the raw material of the aqueous polyester resin to constitute a part of the skeleton structure of the aqueous polyester resin. At this time, hydrophilicity can be imparted to the aqueous polyester resin by introducing an ionic polar group resulting from the water-solubilizing component into the skeleton of the aqueous polyester resin, and the aqueous polyester resin can be dispersed or dissolved in an aqueous solvent. It is what shall be.

  Examples of such water-solubilizing components 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. Can be mentioned.

  Among these water-solubilizing components, dicarboxylic acids having a metal sulfonate group and ester-forming derivatives thereof (hereinafter collectively referred to as dicarboxylic acids having a metal sulfonate group, etc.) include, for example, 5-sulfoisophthalic acid, 2-sulfo Examples include alkali metal salts such as isophthalic acid, 4-sulfoisophthalic acid, sulfoterephthalic acid, 4-sulfonaphthalene-2,6-dicarboxylic acid, and ester-forming derivatives thereof such as esters, acid chlorides and halides. In order to impart good water dispersibility or water solubility to the aqueous polyester resin, the alkali metal is preferably sodium, potassium or lithium.

  When a dicarboxylic acid having a metal sulfonate group or the like is used as a water solubility-imparting component, the metal sulfonate group effectively remains in the aqueous polyester resin and excellent hydrophilicity is imparted. In particular, when 5-sodium sulfoisophthalic acid or an ester thereof (for example, sodium 5-sulfonate dimethylisophthalic acid) is used as a water-solubilizing component, the sodium sulfonate group effectively remains in the aqueous polyester resin and has excellent hydrophilicity. Sex is imparted.

  When a trivalent or higher polyvalent carboxylic acid and an ester-forming derivative thereof (hereinafter collectively referred to as trivalent or higher polyvalent carboxylic acid, etc.) are used as the water-solubilizing component, When the aqueous polyester resin is prepared, after the reaction is completed in a state in which the carboxyl group resulting from the trivalent or higher polyvalent carboxylic acid or the like remains in the skeleton, the residual carboxyl group may be, for example, ammonia, alkanolamine, alkali By neutralizing with a basic compound such as a metal compound, the aqueous polyester resin can be dispersed or dissolved in an aqueous solvent.

  Examples of the trivalent or higher polyvalent carboxylic acid include hemimellitic acid, trimellitic acid, trimedic acid, merophanic acid, pyromellitic acid, benzenepentacarboxylic acid, meritic acid, cyclopropane-1,2,3-tricarboxylic acid Examples thereof include polycarboxylic acids such as acid, cyclopentane-1,2,3,4-tetracarboxylic acid and ethanetetracarboxylic acid, and ester-forming derivatives thereof. Among these, especially when trimellitic anhydride, pyromellitic anhydride and their ester-forming derivatives are used, the three-dimensional crosslinking of the aqueous polyester resin is sufficiently suppressed, and the carboxyl group after the polycondensation reaction remains effectively. This is preferable.

  When at least one of such trivalent or higher polyvalent carboxylic acids, particularly tribasic acid anhydrides, tetrabasic acid anhydrides and ester-forming derivatives thereof, is used as a water-solubilizing component, In addition, the carboxyl group remains effectively, and excellent hydrophilicity is imparted.

  As the water-solubility-imparting 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.

  When a water-soluble imparting component corresponding to a polyvalent carboxylic acid component such as a dicarboxylic acid having a metal sulfonate group or a trivalent or higher-valent polycarboxylic acid is used, the amount of the water-soluble imparting component used is a polyvalent carboxylic acid. It is preferable that it is the range of 1-60 mol% with respect to the total amount of an acid component. In this case, particularly excellent hydrophilicity is imparted to the aqueous polyester resin, and excellent water dispersibility or water solubility is imparted to the aqueous polyester resin hybridized with the layered silicate, and good resin strength is maintained. Moreover, if the said usage-amount is especially the range of 2-40 mol%, especially high flame retardance, durability, etc. are provided to the film | membrane formed from the film-forming composition containing water-based polyester resin.

  When a dicarboxylic acid having a metal sulfonate group or the like is used as the water-solubilizing component, the amount of the dicarboxylic acid having a metal sulfonate group is in the range of 1 to 60 mol% based on the total amount of the polyvalent carboxylic acid component. It is preferable. In this case, the water-based polyester resin has particularly good resin strength such as tensile fracture strength, and has particularly good water resistance and durability when used in a film-forming composition.

  In particular, when one or more selected from 5-sodium sulfoisophthalic acid and its ester-forming derivatives are used as the dicarboxylic acid having a metal sulfonate group, this 5-sodium sulfoisophthalic acid and its ester-forming properties are used. When the total amount of the derivative 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 remain in the aqueous polyester resin and hybridized with the layered silicate. Excellent water dispersibility or water solubility is imparted to the aqueous polyester resin. A particularly excellent effect is obtained when the total amount of 5-sodiumsulfoisophthalic acid and its ester-forming derivative is in the range of 1 to 30 mol%.

  In addition, when a trivalent or higher polyvalent carboxylic acid or the like is used as the water solubility-imparting component, the usage amount of the trivalent or higher polyvalent carboxylic acid or the like is in the range of 1 to 60 mol% based on the total amount of the polyvalent carboxylic acid component It is preferable that In this case, when the aqueous polyester resin is produced under a polymerization condition that eliminates unnecessary crosslinking reaction, an aqueous polyester resin having a sufficient degree of polymerization and water dispersibility or water solubility can be obtained. When only a trivalent or higher polyvalent carboxylic acid or the like is used as the water solubility-imparting component, the usage amount of the trivalent or higher polyvalent carboxylic acid or the like is 5 to 40 mol relative to the total amount of the polyvalent carboxylic acid component. % Is preferable.

  In particular, when a tribasic acid, a tetrabasic acid, or an ester-forming derivative thereof is used as a trivalent or higher polyvalent carboxylic acid, the tribasic acid, tetrabasic acid, or ester thereof When the total amount of the formable derivative used is in the range of 1 to 60 mol% with respect to the total amount of the polyvalent carboxylic acid component, sufficient carboxyl groups remain in the aqueous polyester resin and hybridized with the layered silicate. Excellent water dispersibility or water solubility is imparted to the aqueous polyester resin. A particularly excellent effect is obtained when the total amount of the tribasic acid, tetrabasic acid, and these ester-forming derivatives used is in the range of 1 to 30 mol%.

  The aqueous solvent in this specification includes not only water but also a mixed solvent of water and a hydrophilic solvent. Examples of the hydrophilic solvent include alcohols such as methanol, ethanol and 2-propanol, glycol ethers such as propylene glycol monomethyl ether, ethyl cellosolve and butyl cellosolv, and cyclohexanone. In the mixed solvent of water and a hydrophilic solvent, 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, it is 0 in the mixed solvent. It is preferable that 1 to 50% by weight of a hydrophilic solvent is contained.

  In the aqueous polyester resin of the present invention, when a trivalent or higher polyvalent carboxylic acid or the like is used as a water-solubilizing component, it is neutralized with a basic compound such as ammonia or alkanolamine as described above. As a result, the aqueous polyester resin can be dispersed or dissolved in the aqueous solvent. Even when such a means is used, the same as described above.

  The blending amounts of the polyvalent carboxylic acid component, the glycol component and the water-solubilizing component are as follows: the total number of carboxyl groups and ester-forming derivative groups contained in each component, and the total number of hydroxyl groups and ester-forming derivative groups Is preferably adjusted so that the molar ratio is in the range of 1: 1 to 2.5. In this case, trivalent or higher polyvalent carboxylic acid or the like which is a water-solubilizing component is regarded as dicarboxylic acid, and the blending amount is calculated.

  In preparing the aqueous polyester resin, an appropriate amount of a known polyfunctional compound such as pentaerythritol, trimethylolpropane, dimethylolbutanoic acid, trifunctional carboxylic acid or the like is used to adjust the molecular weight. It is also preferable.

  Moreover, as reaction components other than the above, for example, p-hydroxybenzoic acid, monovalent aliphatic alcohol, and the like can be used together.

  The layered silicate is used for nanocompositing the aqueous polyester resin according to the present invention. As the layered silicate, various smectites having swelling properties and ion exchange ability, swelling fluorine mica, swelling mica and the like are used. This layered silicate may be either a natural product or a synthetic product. The layered silicate may be used alone or in combination of two or more.

  The layered silicate may be an organic layered silicate in which cations existing between crystal layers are ion-exchanged with organic ions such as quaternary ammonium ions. When organic layered silicate is used, it is desirable to use a dispersion solvent suitable for the organic layered silicate.

  The amount of layered silicate used when the aqueous polyester resin is prepared is set as appropriate. In particular, the amount used may be in the range of 0.1 to 15% by mass with respect to the total amount of the aqueous polyester resin produced. preferable. In this case, in addition to the effects of improving the flame retardancy of the aqueous polyester resin and suppressing the scattering of high-temperature droplets during combustion, the stability of the aqueous dispersion of the aqueous polyester resin containing the layered silicate is improved and the aqueous The film strength and transparency formed from the polyester resin are improved.

  Further, the size of the layered silicate such as the particle diameter is not particularly limited, but the particle diameter is preferably 1 μm or less, more preferably 100 nm or less.

  The aqueous polyester resin of the present invention is produced by polymerizing or polycondensing a polyvalent carboxylic acid component, a glycol component, and a water-solubilizing component by a known polyester production method. For example, when 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.

  Further, for example, when the polyvalent carboxylic acid component is an ester-forming derivative of a polyvalent carboxylic acid and the glycol component is glycol, the first is a transesterification reaction between the ester-forming derivative of the polyvalent carboxylic acid and the glycol. The aqueous 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. For example, when dimethyl terephthalate (DMT) is used as the polyvalent carboxylic acid component and ethylene glycol (EG) is used as the glycol component, bishydroxyethylene terephthalate (BHET) is obtained by transesterification (first stage reaction) between DMT and EG. ) And polyethylene terephthalate is produced by polycondensation of BHET (second stage reaction). In this case, 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 method for producing an aqueous polyester resin that undergoes the first-stage reaction and the second-stage reaction will be described more specifically. In the transesterification which is the first stage reaction, all raw materials used for the production of the aqueous polyester resin may be contained in the reaction system from the beginning. In this transesterification reaction, for example, a dicarboxylic acid diester and a glycol compound are held in a reaction vessel, and gradually heated to 150 to 260 ° C. under an inert gas atmosphere such as nitrogen gas under normal pressure conditions. Then, the transesterification reaction proceeds.

  The polycondensation reaction which is 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.

  In the first stage reaction and the second stage reaction, conventionally known titanium, antimony, lead, zinc, magnesium, calcium, manganese, alkali metal compounds, etc. may be added to the reaction system at any time as a catalyst. .

  In the process of producing the aqueous polyester resin as described above, the condensation or polycondensation of the polyvalent carboxylic acid component, the glycol component, and the water solubility-imparting component proceeds in the presence of the layered silicate. For example, when an aqueous polyester resin is produced by a one-step reaction (direct esterification reaction), a layered silicate is contained in a reaction system containing a polyvalent carboxylic acid component, a glycol component and a water solubility-imparting component. In the state, condensation or polycondensation of the polyvalent carboxylic acid component, the glycol component and the water-solubilizing component is allowed to proceed. In addition, when the aqueous polyester resin is produced by the two-stage reaction of the first-stage reaction and the second-stage reaction, a layered silicate is added to the reaction system at any timing such as before or after the first-stage reaction. In this state, the second stage reaction is allowed to proceed.

  Addition of the layered silicate to the reaction system is performed by an appropriate method. For example, a water-dispersed layered silicate such as water-dispersible bentonite is first dispersed in water to prepare an aqueous dispersion. At this time, the layered silicate particles swell and the interlayer distance in the crystal increases. The layered silicate is added to the reaction system, for example, by dropping the aqueous dispersion into the reaction system. When organic layered silicate is used, a dispersion is prepared by dispersing the organic layered silicate in an appropriate organic solvent. Also in this case, the organic layered silicate particles swell and the distance between the crystals increases. The organic layered silicate is added to the reaction system, for example, by dropping the dispersion into the reaction system.

  When the condensation or polycondensation of the polyvalent carboxylic acid component, the glycol component and the water-solubilizing component proceeds in the presence of the layered silicate in this way, a peelable nanocomposite in which the layered silicate is separated and dispersed is obtained. An insertion type nanocomposite in which a molecular chain of a polyester resin is inserted between layers of a layered silicate is formed.

  The aqueous polyester resin nanocomposited with the layered silicate in this way is given the property of being dispersible or soluble in an aqueous solvent while maintaining the excellent properties inherent in the polyester resin. In addition, this water-based polyester resin is imparted with flame retardancy, and further has the property that high-temperature droplets are unlikely to scatter even if burnt.

  The aqueous polyester resin according to the present invention is used for various applications. In particular, as described above, the aqueous polyester resin has characteristics such as excellent durability and can be dispersed or dissolved in an aqueous solvent. Therefore, the aqueous polyester resin is suitable for the preparation of a film-forming resin composition. Used for. In addition, when aqueous polyester resin is used for preparation of the resin composition for film formation, it is preferable that the number average molecular weights of the said aqueous polyester resin are the range of 5000-50000. Thus, when the number average molecular weight is 5000 or more, the durability and water resistance of the water-based polyester resin are particularly excellent, and a sufficient effect is exhibited for improving hydrolysis resistance. Moreover, when this number average molecular weight is 50000 or less, when the aqueous polyester resin is dispersed or dissolved in an aqueous solvent in the resin composition for film formation, excellent solution stability is maintained.

  Moreover, when aqueous polyester resin is used for preparation of the film forming resin composition, the intrinsic viscosity of this aqueous polyester resin is preferably in the range of 0.05 to 1.0. In this case, excellent flame retardancy, durability and water resistance are imparted to the film-forming resin composition, and the long-term storage stability of the dispersion or solution is improved. That is, when the intrinsic viscosity is 0.05 or more, a film having particularly excellent strength is formed from the film-forming resin composition, and when the intrinsic viscosity is 1.0 or less, the dispersion or solution is stored for a long time. Stability is particularly excellent. In particular, particularly excellent effects can be obtained when the intrinsic viscosity is in the range of 0.12 to 0.9. Furthermore, an optimum effect is obtained when the intrinsic viscosity is in the range of 0.2 to 0.9.

  Since the film-forming resin composition according to the present invention contains the water-based polyester resin, it can be applied in the state of an aqueous composition. By using this film-forming resin composition, the base material is processed. Occupational safety and environmental conservation are excellent. 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.

  As a treatment method when the resin composition for film formation according to the present invention is used for the treatment of textile products, for example, the resin composition for film formation is immersed in a woven fabric, a knitted fabric, a nonwoven fabric, a rug, a web or the like. Examples thereof include a method of applying by a padding method, a coating method, etc., a method of applying an aqueous polyester resin to a yarn by a sizing machine in the same manner as a warp gluing method, a method of subjecting the treated yarn to weaving, and the like.

  Moreover, as a usage method when this film-forming resin composition is used for the surface treatment of a polyester film of a PET film, for example, a film-forming resin composition is subsequently applied to the produced PET film. The method of doing is mentioned. In addition, for example, 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. In the latter case, 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. For example, 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.

  Furthermore, as a use of the film-forming resin composition containing the aqueous polyester resin according to the present invention, in addition to the uses exemplified above, coating agents for metals, glass, paper, wood, etc., and overcoating for electronic substrates, etc. Examples of the coating agent include adhesives such as an anchor coating agent and an ink binder, and uses as a surface treatment agent for plastic films such as polyvinyl chloride and polycarbonate.

  As described above, the polyester film or fiber subjected to the surface treatment with the film-forming resin composition is imparted with flame retardancy, and even if it is burned by a fire or the like, the surface water-based polyester resin is less likely to collapse, Droplet scattering is suppressed. For this reason, the expansion of the damage in a fire etc. is suppressed.

  Hereinafter, the present invention will be described in more detail based on specific examples. However, the present invention is not limited to these examples. Note that “parts” and “%” used below are all based on weight unless otherwise specified.

Example 1
Water dispersible bentonite (“Bengel Bright 23” manufactured by Hojun Co., Ltd.) is used as the layered silicate, 13.5 parts of this layered silicate and 300 parts of water are mixed, and 5000 rpm, 30 minutes using a homomixer. The mixture was stirred under conditions to prepare an aqueous dispersion of layered silicate.

  Also, in the reaction vessel, 179.4 parts of dimethyl terephthalic acid (DMT), 46.2 parts of dimethyl isophthalic acid (DMI), 47.0 parts of sodium dimethylisophthalic acid (SIPM), ethylene glycol (EG) 163.0 parts and 0.1 parts of potassium potassium oxalate as a catalyst were added, and the temperature was raised to 200 ° C. while stirring and mixing in a normal pressure and nitrogen atmosphere. Next, the reaction temperature was gradually raised to 260 ° C. over 3 hours to complete the transesterification reaction.

  Thereafter, the aqueous dispersion of the layered silicate was added dropwise to the reaction system while stirring the reaction system in a temperature range of 130 to 180 ° C. at 200 rpm. During this time, the water evaporated was discharged out of the system.

  Thereafter, 0.08 part of antimony trioxide was added to the reaction system, and then the pressure was gradually reduced while maintaining the reaction system at 250 ° C., and maintained at 250 ° C. and 0.67 hPa (0.5 mmHg) for 2 hours. As a result, the polycondensation reaction was advanced to obtain an aqueous polyester resin.

  25 parts of the obtained aqueous polyester resin and 75 parts of water were mixed in a dissolution tank and stirred at a temperature of 80 to 95 ° C. for 2 hours to dissolve the aqueous polyester resin in water. Thereby, a 25% aqueous solution of an aqueous polyester resin was obtained.

(Example 2)
In Example 1, “Bengel Bright 25” manufactured by Hojun Co., Ltd. was used in place of “Bengel Bright 23” manufactured by Hojung Co., Ltd. as the layered silicate. The other conditions were the same as in Example 1 to obtain a 25% aqueous solution of an aqueous polyester resin.

(Example 3)
In Example 1, the amount of layered silicate used in the preparation of the aqueous dispersion of layered silicate was changed to 21.6 parts, and the amount of water used was changed to 500 parts. The other conditions were the same as in Example 1 to obtain a 25% aqueous solution of an aqueous polyester resin.

Example 4
In Example 1, the amount of layered silicate used in the preparation of the aqueous dispersion of layered silicate was changed to 27.0 parts, and the amount of water used was changed to 700 parts. The other conditions were the same as in Example 1 to obtain a 25% aqueous solution of an aqueous polyester resin.
(Example 5)
In Example 1, the amount of layered silicate used in the preparation of the aqueous dispersion of layered silicate was 16.0 parts, the amount of dimethyl terephthalate used was 82.0 parts, and the use of sodium dimethylisophthalic acid 5-sulfonate The amount was changed to 195.8 parts. The other conditions were the same as in Example 1 to obtain a 25% aqueous solution of an aqueous polyester resin.
(Example 6)
A water dispersible bentonite (“Bengel Bright 23” manufactured by Hojun Co., Ltd.) is used as the layered silicate, 13.8 parts of this layered silicate and 300 parts of water are mixed, and 5000 rpm, 30 minutes using a homomixer. The mixture was stirred under conditions to prepare an aqueous dispersion of layered silicate.

  Further, 171.7 parts of dimethyl terephthalic acid, 46.2 parts of dimethyl isophthalic acid, 163.0 parts of ethylene glycol and 0.1 part of titanium potassium oxalate as a catalyst are added to the reaction vessel, and atmospheric pressure and nitrogen atmosphere are added. The temperature was raised to 200 ° C. with stirring and mixing. Next, the reaction temperature was gradually raised to 260 ° C. over 4 hours to complete the transesterification reaction.

  Thereafter, the reaction system was cooled to 80 ° C. or less, and the aqueous dispersion of the layered silicate was added to the reaction system. Next, the temperature of the reaction system was raised to 100 ° C. to evaporate all the water in the reaction system. Next, after adding 38.1 parts of trimellitic anhydride to the reaction system, the reaction system was gradually depressurized while being kept at 250 ° C., and the conditions were 250 ° C. and 0.67 hPa (0.5 mmHg). The polycondensation reaction was advanced by holding for 2 hours to obtain an aqueous polyester resin having an acid value of 50.2, an intrinsic viscosity of 0.37, and a number average molecular weight of 7700.

  25 parts of the obtained aqueous polyester resin, 73.7 parts of water, and 1.3 parts of 25% aqueous ammonia are mixed in a dissolution tank and stirred at a temperature of 80 to 95 ° C. for 2 hours while stirring. As a result, the aqueous polyester resin was dissolved in water. Thereby, a 25% aqueous solution of an aqueous polyester resin was obtained.

(Example 7)
In Example 6, the amount of dimethyl terephthalic acid used was changed to 184.6 parts, and 28.8 parts of pyromellitic anhydride was used instead of trimellitic anhydride. The other conditions were the same as in Example 6 to obtain a 25% aqueous solution of an aqueous polyester resin.

(Example 8)
In Example 6, the amount of layered silicate used in the preparation of the aqueous dispersion of layered silicate was 14.8 parts, the amount of dimethylterephthalic acid used was 82.0 parts, and the amount of trimellitic anhydride used was 127. Changed to 0 parts. The other conditions were the same as in Example 6 to obtain a 25% aqueous solution of an aqueous polyester resin.

Example 9
A water dispersible bentonite (“Bengelbright 23” manufactured by Hojun Co., Ltd.) is used as the layered silicate, 13.8 parts of this layered silicate and 300 parts of water are mixed, and 5000 rpm, 30 minutes using a homomixer. The mixture was stirred under conditions to prepare an aqueous dispersion of layered silicate.

  Further, 174.3 parts of dimethylterephthalic acid, 46.2 parts of dimethylisophthalic acid, 23.5 parts of sodium dimethylisophthalic acid, 163.0 parts of ethylene glycol, and titanium oxalate as a catalyst as a catalyst are contained in a reaction vessel. 0.1 parts of potassium was added, and the temperature was raised to 200 ° C. while stirring and mixing in a normal pressure and nitrogen atmosphere. Next, the reaction temperature was gradually raised to 260 ° C. over 4 hours to complete the transesterification reaction.

  Thereafter, the reaction system was cooled to 80 ° C. or less, and the aqueous dispersion of the layered silicate was added to the reaction system. Next, the temperature of the reaction system was raised to 100 ° C. to evaporate all the water in the reaction system. Next, after adding 20.3 parts of trimellitic anhydride to the reaction system, the reaction system was gradually depressurized while being kept at 250 ° C., and the conditions were 250 ° C. and 0.67 hPa (0.5 mmHg). The polycondensation reaction was advanced by holding for 2 hours to obtain an aqueous polyester resin having an acid value of 50.2, an intrinsic viscosity of 0.37, and a number average molecular weight of 7700.

  25 parts of the obtained aqueous polyester resin, 73.7 parts of water, and 1.3 parts of 25% aqueous ammonia are mixed in a dissolution tank and stirred at a temperature of 80 to 95 ° C. for 2 hours while stirring. As a result, the aqueous polyester resin was dissolved in water. Thereby, a 25% aqueous solution of an aqueous polyester resin was obtained.

(Example 10)
In Example 9, the amount of dimethyl terephthalic acid used was changed to 179.4 parts, and 17.3 parts of pyromellitic anhydride was used instead of trimellitic anhydride. Other conditions were the same as in Example 9, and a 25% aqueous solution of an aqueous polyester resin was obtained.

(Comparative Example 1)
In Example 1, an aqueous dispersion of layered silicate was not prepared, and an aqueous viscosity of layered silicate was not added to the reaction system, but the other conditions were the same as in Example 1, and the intrinsic viscosity was 0.40. An aqueous polyester resin having an average molecular weight of 8000 was produced, and a 25% aqueous solution of the aqueous polyester resin was obtained using this aqueous polyester resin.

(Comparative Example 2)
In Example 1, an aqueous polyester resin was produced under the same conditions as in Example 1 except that the aqueous dispersion of layered silicate was not added to the reaction system. Water was added to this water-based polyester resin and water dispersible bentonite (“Bengel Bright 23” manufactured by Hojun Co., Ltd.) to obtain a 25% aqueous solution of the water-based polyester resin having the same concentration as in Example 1.

(Combustion test)
Using a 25% aqueous solution of the aqueous polyester resin obtained in each Example and Comparative Example, the polyester tropical cloth was processed by a padding method, dried at 110 ° C. for 5 minutes, and then 1 ° C. at 180 ° C. A curing treatment was performed for a minute to obtain a test cloth.

  The test cloth was subjected to a flammability test in accordance with a flame contact method (JIS L 1091 D method), and the number of times of flame contact required until the test cloth burned was measured.

  Further, when the test cloth burned by this flammability test, it was confirmed whether or not a high temperature droplet was dropped from the test cloth.

  The results are shown in Table 1.

  As is clear from the above results, in Examples 1 to 10, it was confirmed that the number of flame contact was large and the flame retardancy was high.

  Further, in Comparative Examples 1 and 2, when the test cloth burned, high temperature droplets dropped downward, whereas in Examples 1 to 10, such dripping did not occur even when burned. Therefore, in Examples 1-10, it was confirmed that an effect is exhibited also in the suppression of the spread of the flame at the time of fire, for example.

(X-ray diffraction)
Using an X-ray diffraction measurement device “SWXD-FK” manufactured by Rigaku Corporation, the powder X-ray diffraction measurement of the aqueous polyester resin obtained in each Example was performed. A diffraction peak corresponding to the interplanar spacing was not confirmed, and it was confirmed that a nanocomposite structure in which the layered silicate was separated and dispersed was formed in the aqueous polyester resin in each Example.

Claims (11)

A polyvalent carboxylic acid component, a glycol component, and a water-solubilizing component are water polyester resins hybridized with a layered silicate produced through a process of condensation or polycondensation by reaction in the presence of the layered silicate,
The water-solubility-imparting component contains one or more selected from dicarboxylic acids having a metal sulfonate group, tribasic acid, tetrabasic acid, or ester-forming derivatives thereof, and the amount of the water-solubility-imparting component used is Ri range der of 1-60 mol% based on the total amount of the amount of the polycarboxylic acid component and a water-imparting components,
The layered amount of silicate, an aqueous polyester resin total amount with respect to 0.1 to 15% by weight layered silicate and wherein the range der Rukoto of the hybridized aqueous polyester resin. The aqueous polyester resin hybridized with the layered silicate according to claim 1 , wherein the layered silicate is one or more selected from natural products and synthetic products. 3. The aqueous polyester resin hybridized with the layered silicate according to claim 1 or 2 , wherein the layered silicate is an organic layered silicate. The dicarboxylic acid having a metal sulfonate group is at least one selected from 5-sodium sulfoisophthalic acid and ester-forming derivatives thereof, and the amount of 5-sodium sulfoisophthalic acid and ester-forming derivatives used thereof is The aqueous polyester resin hybridized with the layered silicate according to any one of claims 1 to 3 , wherein the total amount is in the range of 1 to 60 mol% with respect to the total amount of the polyvalent carboxylic acid component. . The total amount of tribasic acid, tetrabasic acid and their ester-forming derivatives used is in the range of 1 to 60 mol% with respect to the total amount of the polyvalent carboxylic acid component. An aqueous polyester resin hybridized with the layered silicate according to any one of the above. The aqueous polyester hybridized with the layered silicate according to any one of claims 1 to 3, wherein at least one selected from trimellitic acid and an ester-forming derivative thereof is used as a tribasic acid. resin. A resin composition for film formation, comprising an aqueous polyester resin hybridized with the layered silicate according to any one of claims 1 to 6 . The resin composition for forming a film according to claim 7 , wherein the resin composition is for polyester film surface processing. The resin composition for film formation according to claim 7 , which is used for fiber processing. A polyester film, which has been subjected to a surface treatment with the film-forming resin composition according to claim 7 or 8 . A fiber that has been processed with the film-forming resin composition according to claim 7 or 9 .