JP2012007154A - Polyester resin, process for producing polyester resin and aqueous liquid of polyester resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyester resin that has a high refractive index and can be easily made compatible with an aqueous solvent.SOLUTION: The polyester resin includes (A) a polyol component containing 50 mol% or more of (A1) a specific fluorene compound and (B) a carboxylic acid component and is produced by bonding a carboxyl group derived from (C) a carboxylic acid anhydride to a molecular terminal. Preferably, the polyester resin has a number average molecular weight of 300-10,000 and an acid value of 10-100 mgKOH/g.

Description

  The present invention relates to a polyester-based resin, and more particularly, a polyester-based resin having a high refractive index and containing a carboxyl group that can be easily rendered aqueous with respect to an aqueous solvent, a method for producing a polyester-based resin, and an aqueous polyester-based resin It is about liquid.

  Conventionally, polyester films have been used as forming materials such as packaging materials, magnetic cards, magnetic tapes, magnetic disks, printing materials and the like. As the polyester film, for example, a thermoplastic polyester such as polyethylene terephthalate (PET) or a copolymer thereof mixed with other resins as necessary is melt-extruded and molded, and then biaxially stretched. Heat-fixed ones are used. Such a polyester film is excellent in various physical properties such as mechanical strength, heat resistance, and chemical resistance, but has a problem that it is difficult to attach a paint, an adhesive, ink, etc. because of its high orientation. .

  For this reason, conventionally, the adhesion of paints and the like has been improved by providing a film formed by applying an aqueous dispersion of a polyester resin on the surface of a polyester film.

  By the way, in recent years, in an optical film application etc., forming an easily-adhesive film on the surface of a polyester film and bonding it to another film having a different refractive index has been performed. In this case, in order to obtain an optical film with less distortion, it is required to increase the refractive index of the easy-adhesive film to reduce the difference in refractive index from a polyester film such as PET as a base material. It is becoming.

  As means for reducing the difference in refractive index, for example, a polyvalent carboxylic acid component containing 2,6-naphthalenedicarboxylic acid or a methyl ester thereof and a polyol component containing bis (4- (hydroxyethoxy) phenyl) fluorene are used. It has been proposed to form a polyester film by polymerization (see Patent Document 1).

  However, although the polyester resin obtained by the proposal of the above-mentioned Patent Document 1 has a high refractive index, it is not sufficiently satisfactory with respect to water dispersibility related to the preparation of a film-forming material. In order to solve such problems, a 2,6-naphthalenedicarboxylic acid, a polyvalent carboxylic acid component containing a specific amount of a dicarboxylic acid having a metal sulfonate group, and a polyol component containing a specific amount of a fluorene-based compound are used together. A polyester resin obtained by polymerization has been proposed (see Patent Document 2).

Japanese Patent Laid-Open No. 10-110091 JP 2009-242461 A

  However, since the polyester resin proposed by the above-mentioned Patent Document 2 is produced by batch preparation of a metal sulfonate group-containing dicarboxylic acid or a trivalent or higher polyvalent carboxylic acid together with other dicarboxylic acid components and diol components, There is a risk of thickening or gelling during the reaction. Further, since the polyester resin proposed by Patent Document 2 has a large molecular weight, it is difficult to make it water-based even when it is made water-based, and there remains a problem in terms of preparing an aqueous liquid.

  The present invention has been made in view of such circumstances, and provides a polyester-based resin having a high refractive index and capable of being easily made aqueous with respect to an aqueous solvent, a method for producing a polyester-based resin, and an aqueous polyester-based resin liquid. Is the purpose.

  Accordingly, the present inventors have made extensive studies in order to obtain a polyester-based resin in which the formed coating film has a high refractive index, and can be easily made water-based with respect to an aqueous solvent and can be easily formed by coating. It was. As a result, a structure having a carboxyl group derived therefrom by binding a carboxylic acid anhydride to the molecular terminal of a polyester resin composed of a polyol component and a carboxylic acid component containing a specific amount of the fluorene compound having the specific structure. As a result, the present inventors have found that the polyester resin has a high refractive index and can be easily made aqueous with respect to an aqueous solvent.

  That is, when a polyester resin is prepared using a large amount of a fluorene compound, since the fluorene compound usually has hydrophobicity, it has been difficult to make the resulting polyester resin water-soluble. As described above, it was found that by making a polyester resin having a structure having a carboxyl group derived therefrom by binding a carboxylic acid anhydride to the molecular terminal, it becomes easy to make it water-based. Also, in the production of polyester resins, if a large amount of fluorene compound is added together with other acid components and polyol components and subjected to polycondensation reaction, there are problems in production such as thickening and gelation. Although it remains, it has been found that these can be improved by the production method of the present invention.

The present invention is a polyester resin comprising a polyol component (A) and a carboxylic acid component (B) containing 50 mol% or more of a fluorene compound (A1) represented by the following general formula (1), A polyester resin in which a carboxyl group derived from a carboxylic acid anhydride (C) is bonded to a terminal is a first gist.

Moreover, this invention is a method of manufacturing the said polyester-type resin, Comprising: The polyol component (A) and carboxylic acid which contain 50 mol% or more of fluorene type compounds (A1) represented by following General formula (1) After the polyester polyol (I) is prepared by copolymerization with the component (B), a carboxylic acid anhydride (C) is added to the polyester polyol (I) to react with the molecular end of the polyester polyol (I). The manufacturing method of the polyester-type resin which combines the said carboxylic acid anhydride (C) makes it a 2nd summary.

  The third gist of the present invention is an aqueous polyester resin solution obtained by dissolving or dispersing the polyester resin in an aqueous solvent.

  Thus, the present invention comprises a polyol component (A) containing 50 mol% or more of the fluorene compound (A1) represented by the above general formula (1) and a carboxylic acid component (B), and has a carboxyl group at the molecular end. It is a polyester-based resin formed by bonding carboxyl groups derived from the acid anhydride (C). For this reason, it can be easily made aqueous with respect to an aqueous solvent, and has a high refractive index. Therefore, an aqueous polyester resin solution obtained by dissolving or dispersing this in an aqueous solvent can be applied to, for example, a polyester film as a base material to form a good film, and the resulting film and polyester film can be formed. It is possible to reduce the difference in refractive index between the two.

The description of the constituent requirements described below is an example (representative example) of the embodiment of the present invention, and is not limited to these contents.
Hereinafter, the present invention will be described in detail.

<Polyester resin>
The polyester resin of the present invention comprises a polyol component (A) containing 50 mol% or more of a fluorene compound (A1) represented by the following general formula (1) and a carboxylic acid component (B), and its molecular terminal. And a carboxyl group derived from a carboxylic acid anhydride.

  The polyester resin of the present invention includes, for example, [α] a polyol component (A) containing 50 mol% or more of the fluorene compound (A1) represented by the general formula (1), a carboxylic acid component (B), Polyester polyol (I) is copolymerized, and the carboxylic acid anhydride is bonded to the molecular terminal of the polyester polyol (I) by addition reaction of the carboxylic acid anhydride with the polyester polyol (I). It can adjust by making the carboxyl group derived from an acid anhydride exist. In addition, [β] a polyol component (A) containing 50 mol% or more of the fluorene compound (A1) represented by the general formula (1) and a carboxylic acid component (B) are copolymerized. The polyester resin of the present invention can also be prepared by esterifying a polyester resin and a monool obtained by addition reaction of a carboxylic acid anhydride at the end of the polyol component (A). In the present invention, the method [α] is particularly preferable in terms of productivity and reaction control.

<Polyol component (A)>
The polyol component (A) contains 50 mol% or more of the fluorene compound represented by the general formula (1), preferably contains 70 mol% or more of the fluorene compound, more preferably The fluorene compound is contained in an amount of 80 mol% or more, particularly preferably 100 mol% of the fluorene compound, that is, the polyol component (A) is composed of only the fluorene compound. If the content of the fluorene compound is too small, it tends to be difficult to obtain a sufficiently high refractive index.

As the fluorene compound (A1) represented by the general formula (1), R ₁ is preferably a methylene group or an ethylene group. R ₂ , R ₃ , R ₄ , and R ₅ are preferably hydrogen, a methyl group, and an ethyl group, and hydrogen is particularly preferable. As this fluorene compound, bisphenoxyethanol fluorene is preferably used from the viewpoint of easy availability.

In the said polyol component (A), a dihydric alcohol is mention | raise | lifted as a polyol component used other than the fluorene type compound represented by General formula (1). Examples of the dihydric alcohol include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 2,4-dimethyl-2-ethylhexane-1,3-diol, , 2-dimethyl-1,3-propanediol (neopentyl glycol), 2-ethyl-2-butyl-1,3-propanediol, 2-ethyl-2-isobutyl-1,3-propanediol, 1,3 -Butadiol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 2,2,4-trimethyl-1,6-hexanediol, etc. Aliphatic diols, 1,2-cyclohexanedimethanol, 1,3-cyclohexane Alicyclic diols such as methanol, 1,4-cyclohexanedimethanol, spiroglycol, tricyclodecane dimethanol, adamantanediol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 4,4 ′ -Thiodiphenol, 4,4'-methylenediphenol, 4,4 '-(2-norbornylidene) diphenol, 4,4'-dihydroxybiphenol, o-, m- and p-dihydroxybenzene, 4,4' And aromatic diols such as isopropylidenephenol, 4,4'-isopropylidenebis (2,6-cyclophenol) 2,5-naphthalenediol, and p-xylenediol. These may be used alone or in combination of two or more.
Among them, aliphatic diols such as diethylene glycol and dipropylene glycol, and alicyclic diols such as 1,2 cyclohexane dimethanol, 1,3 cyclohexane dimethanol, 1,4 cyclohexane dimethanol, spiroglycol, tricyclodecane dimethanol, adamantane Diols are preferably used, more preferably aliphatic diols, and particularly preferably diethylene glycol.

  In addition to the above dihydric alcohols, trivalent or higher polyhydric alcohols such as pentaerythritol, dipentaerythritol, tripentaerythritol, glycerin, trimethylolpropane, trimethylolethane, 1, 3, 6 -Hexanetriol, adamantanetriol, etc. can also be used together.

<Carboxylic acid component (B)>
Examples of the carboxylic acid component (B) include terephthalic acid, isophthalic acid, benzylmalonic acid, 1,4-naphthalic acid, diphenic acid, 4,4′-oxybenzoic acid, and 2,5-naphthalenedicarboxylic acid. Aromatic dicarboxylic acid, malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, trimethyladipic acid, pimelic acid, 2,2-dimethylglutaric acid, azelaic acid, zebacic acid, fumaric acid, maleic acid, itacone Acids, aliphatic dicarboxylic acids such as thiodipropionic acid, diglycolic acid, 1,3-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid , 2,5-norbornane dicarboxylic acid, adamantane dicarboxylic acid, etc. Carboxylic acid, and the like. These may be esters, chlorides, acid anhydrides, etc. and include, for example, dimethyl 1,4-cyclohexanedicarboxylate, dimethyl 2,6-naphthalenedicarboxylate, dimethyl isophthalate, dimethyl terephthalate and diphenyl terephthalate. These may be used alone or in combination of two or more.
Among these, succinic acid that is an aliphatic dicarboxylic acid, 2,5-naphthalenedicarboxylic acid that is an aromatic dicarboxylic acid, terephthalic acid, isophthalic acid, and esters thereof are preferably used, and more preferably aliphatic dicarboxylic acids. Particularly preferred is a low molecular weight aliphatic dicarboxylic acid from the viewpoint that the content of bisphenoxyethanol fluorene (BPEF) in the polyester resin can be increased, more preferred are succinic acid and succinic anhydride, and particularly preferred is succinic anhydride. It is an acid.

  Further, in addition to the above dicarboxylic acids, trivalent or higher polyvalent carboxylic acids such as trimellitic acid, pyromellitic acid, adamantanetricarboxylic acid, trimesic acid and the like can be used.

  In addition to the polyol component (A) and the carboxylic acid component (B), a sulfonate group can be introduced into the resin during the condensation reaction. Examples of the condensation component used when introducing the sulfonate group include 5-sodiosulfoisophthalic acid and 5-potassium sulfoisophthalic acid.

<Polyester polyol (I)>
The polyester polyol (I) used in the present invention includes, for example, a polyol component (A) and a carboxylic acid component (B) containing 50 mol% or more of the fluorene compound (A1) represented by the general formula (1). Can be obtained by polycondensation reaction.

  As a manufacturing method of the said polyester polyol (I), for example with respect to the said carboxylic acid component (B), 0.8-3.0 times mole, Preferably it is 1.0-2.7 times mole, More preferably 1.1 to 2.5 moles of the polyol component (A) is charged into the reactor together with the catalyst, and the temperature is usually raised to 140 to 280 ° C, preferably 170 to 275 ° C, more preferably 180 to 250 ° C, and dehydration condensation. The method of performing is mentioned. In the above reaction, an inert solvent such as methyl acetate, benzene, acetone, xylene, or toluene may be used as necessary.

  As said polyester polyol (I), it is preferable that a number average molecular weight is 300-8000, More preferably, it is 350-3000, Most preferably, it is 400-2000. If the number average molecular weight is too small, there is a tendency to cause repelling during coating, while if it is too large, gelation, aqueousization becomes difficult, and coating unevenness tends to occur.

In the present invention, the number average molecular weight is calculated from the acid value and the hydroxyl value by the following formula.
Number average molecular weight = 56.11 × 1000 × 2 / (acid value + hydroxyl value)

  Moreover, as said polyester polyol (I), it is preferable that a hydroxyl value is 20-500 mgKOH / g, More preferably, it is 30-400 mgKOH / g, Most preferably, it is 50-300 mgKOH / g. If the hydroxyl value is too small, it becomes difficult to bond the carboxyl group derived from the carboxylic acid anhydride (C), and it tends to be difficult to make it aqueous with respect to the aqueous solvent. If it is too large, the molecular weight decreases. There is a tendency to repel during coating. The hydroxyl value of the polyester polyol (I) can be measured according to JIS K0070.

  The carboxylic acid anhydride (C) used for the addition reaction with the polyester polyol (I) may have any structure as long as it has at least one carboxylic acid anhydride structure, such as carboxylic acid monoanhydride and carboxylic acid dianhydride. An anhydride such as, for example, is used, and a tetracarboxylic dianhydride is preferable from the viewpoint of reactivity and water dispersibility upon aqueous formation.

  Specific examples of these carboxylic acid anhydrides (C) include, for example, the anhydrides exemplified as the carboxylic acid component (B), trimellitic anhydride, 1,2,4,5-benzenetetracarboxylic acid dicarboxylic acid. Anhydride (pyromellitic anhydride), 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-pentanetetracarboxylic dianhydride, 3,3 ', 4,4' -Benzophenone tetracarboxylic dianhydride, 5- (2,5 dioxotetrahydrofurfuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 5- (2,5-dioxotetrahydrofur Furyl) -3-cyclohexene-1,2-dicarboxylic anhydride, 4-methylcyclohexene-1,2,3-tricarboxylic anhydride, cyclopentanetetracarboxylic dianhydride, 2, , 6,7-Naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, ethylene glycol bistrimellitic dianhydride, 2,2 ', 3,3'-diphenyltetra Examples thereof include carboxylic dianhydrides, thiophene-2,3,4,5-tetracarboxylic dianhydrides, ethylenetetracarboxylic dianhydrides, and the like. Among them, 1,2,4,5-benzenetetracarboxylic dianhydrides (Pyromellitic anhydride), 5- (2,5dioxotetrahydrofurfuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, etc. are preferably used. These may be used alone or in combination of two or more.

  The amount of the carboxylic acid anhydride (C) used in the addition reaction is preferably 1 to 50 mol%, more preferably 3 to 30 mol%, particularly preferably 5 to 5%, based on the polyester polyol (I). 25 mol%. If the amount of the carboxylic acid anhydride (C) used is too small, it tends to be difficult to make it water-based, and if it is too much, it tends to cause repellency or uneven coating.

  In the addition reaction, a solvent is not necessarily required, but the reaction is preferably started at 230 ° C. or less, preferably 190 to 210 ° C., more preferably 180 to 200 ° C. Therefore, when the viscosity of the reaction product at such a temperature is too high, a solvent necessary for facilitating stirring may be used. Examples of the solvent include ester solvents such as methyl acetate, ethyl acetate, butyl acetate, methyl acetoacetate and ethyl acetoacetate, ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone, benzene, toluene, xylene, butyl cellosolve and butyl cellosolve acetate. And aromatic solvents such as methanol, ethanol and propyl alcohol, and dimethylformamide.

  The above addition reaction proceeds even at room temperature, but it is usually preferable to proceed the reaction at 170-210 ° C. over 0.5-4 hours. A particularly preferable temperature is 170 to 200 ° C., and a particularly preferable reaction time is 1 to 3 hours. In order to further increase the molecular weight to some extent, it is preferable that the polyester polyol is subjected to dehydration condensation at 180 to 250 ° C., and then gradually cooled to proceed the reaction at 170 to 210 ° C. for 0.5 to 4 hours. More preferably, the reaction is allowed to proceed at 170 to 200 ° C. over 1 to 3 hours.

  The polyester resin having a carboxyl group at the molecular end of the present invention thus obtained preferably has a number average molecular weight of 300 to 10,000, more preferably 400 to 5,000, particularly preferably 450 to 2,000. If the number average molecular weight of the polyester-based resin is too small, repelling and coating unevenness tend to occur at the time of coating, and if it is too large, it will gel, make it difficult to make it water-based, or generate coating lines. Such a tendency is seen. In addition, the measurement of a number average molecular weight applies to the measuring method of the above-mentioned polyester polyol (I).

  Moreover, the acid value of the polyester-type resin which has a carboxyl group in the molecular terminal of this invention is 10-100 mgKOH / g normally, Preferably it is 20-80 mgKOH / g, Most preferably, it is 25-70 mgKOH / g. If the acid value is too small, it tends to be difficult to make it water-based, while if it is too large, repellency during coating or water resistance tends to deteriorate. The acid value is measured according to JIS K0070.

  The glass transition temperature (Tg) of the polyester resin having a carboxyl group at the molecular end of the present invention is usually 40 to 200 ° C, preferably 70 to 180 ° C, and particularly preferably 80 to 175 ° C. If the glass transition temperature is too high, the coating film after drying tends to be hard and cracks tend to occur when winding the coating film. If it is too low, the coating film is wound after winding the coating film (on the coated surface). Adhesion occurs) and rewinding tends to be difficult.

<< Aqueous polyester resin liquid >>
A polyester resin aqueous solution can be obtained by using a polyester resin having a carboxyl group at the molecular end of the present invention and dissolving or dispersing it in an aqueous solvent.

  Examples of the aqueous solvent include water or water mixed with a hydrophilic organic solvent and ammonia as a neutralizing agent. Examples of the hydrophilic organic solvent include those that can be mixed with water such as alcohols such as acetone, methanol, ethanol, isopropyl alcohol, butyl cellosolve, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, ethylene glycol monotertiary butyl ether. can give. In particular, butyl cellosolve, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, and isopropyl alcohol are preferably used. In the case of using an organic solvent, the ratio of the organic solvent to the entire aqueous solvent is appropriately set depending on the application and the like, but for example, it is preferably 30% by weight or less of the entire aqueous medium.

  The polyester resin aqueous liquid of the present invention includes, for example, an anionic surfactant as necessary for the purpose of improving wettability with respect to the polyester film when the polyester resin aqueous liquid is applied to the polyester film. A surfactant such as a nonionic surfactant can be added. Specific examples of the surfactant include polyoxyethylene alkylphenyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, glycerin fatty acid ester, fatty acid metal soap, alkyl sulfate, alkyl sulfonate, and alkyl sulfosuccinate. Quaternary ammonium chloride, alkylamine hydrochloride, sodium dodecylbenzenesulfonate, and the like. These may be used alone or in combination of two or more.

  Furthermore, you may add various additives, such as an antistatic agent, a filler, a ultraviolet absorber, a lubricant, and a coloring agent, to the polyester resin aqueous liquid of the present invention as necessary.

  The aqueous polyester resin liquid of the present invention can be produced, for example, as follows. That is, the polyester resin aqueous liquid can be prepared by putting the obtained polyester resin into the aqueous solvent and dissolving or dispersing it. Alternatively, the polyester-based resin aqueous liquid can be prepared by adding the obtained polyester-based resin and the hydrophilic organic solvent to water and dissolving or dispersing them.

  The temperature condition for dissolving or dispersing in the aqueous solvent is usually 40 to 100 ° C, more preferably 60 to 100 ° C, and particularly preferably 70 to 90 ° C.

  The time for dissolving or dispersing in the aqueous solvent is usually 30 to 240 minutes, more preferably 60 to 180 minutes, and particularly preferably 60 to 120 minutes.

  The usage-amount of the said aqueous solvent is suitably set so that it may become the solid content density | concentration of a desired polyester resin aqueous liquid. The solid content concentration of the polyester resin aqueous liquid of the present invention is appropriately adjusted so as to ensure good dispersibility of the polyester resin and to form a good film by the coating film forming step. However, it is preferably 1 to 30% by weight, more preferably 5 to 30% by weight, and particularly preferably 10 to 20% by weight. If the solid content concentration is too low, repelling tends to occur at the time of coating, and if it is too high, it becomes difficult to make it water-based, or the stability of the aqueous solution tends to decrease and layer separation tends to occur.

  An example of the use of the aqueous polyester resin liquid of the present invention is, for example, an embodiment in which a film is formed by applying the aqueous liquid to a polyester film and heating and drying to form a coated polyester film. The coated polyester film may be further stretched.

  Examples of the polyester film include a film made of polyethylene terephthalate (PET), polyethylene-2,6-naphthalate, polybutylene terephthalate, and a copolymer obtained by copolymerizing these with other copolymer components. The polyester film may be either an unstretched film or a stretched film. Among them, a stretched film is preferably used, and a biaxially stretched film is particularly preferable.

  The coated polyester film thus obtained is excellent in heat resistance, water resistance, etc., and can be used for magnetic cards, magnetic disks, printing materials, graphic materials, photosensitive materials, etc., and particularly suitably used for optical film applications. be able to.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist. In the examples, “parts” and “%” mean weight basis unless otherwise specified.

[Example 1]
Into a reactor equipped with a nitrogen introduction tube, a thermometer, a stirrer, and a rectifying column, 229.2 parts (0.94 mol) of naphthalenedicarboxylic acid dimethyl ester (NDCM) as a carboxylic acid component (B), a polyol component (A ) Bisphenoxyethanol fluorene (BPEF) 658.3 parts (1.50 mol), dibutyltin oxide (DBTO) 0.2 parts, and zinc acetate 0.2 parts as a catalyst, the temperature was raised to 70-240 ℃ Polyester polyol (I) was produced by reacting for 8 hours while distilling off methanol or water.

  Subsequently, after cooling to 200 ° C., 112.6 parts (0.52 mol) of pyromellitic anhydride (PMAn) is charged as the carboxylic acid anhydride (C) and reacted at 170 ° C. for 2 hours while dissolving. Thus, a polyester resin having a carboxyl group at the molecular end was obtained.

[Example 2]
147.5 parts (1.48 mol) of succinic anhydride (SuAn) as the carboxylic acid component (B), 743.3 parts (1.70 mol) of bisphenoxyethanol fluorene (BPEF) and diethylene glycol (polyol component (A)) DEG) 31.3 parts (0.30 mol), 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid as carboxylic anhydride (C) 77.9 parts (0.30 mol) of acid anhydride (manufactured by DIC, EPICLON B-4400) was used. Otherwise in the same manner as in Example 1, a polyester resin having a carboxyl group at the molecular end was obtained.

Example 3
113.5 parts (0.68 mol) of isophthalic acid (IPA) as the carboxylic acid component (B), 748.8 parts (1.71 mol) of bisphenoxyethanol fluorene (BPEF) and diethylene glycol (DEG) as the polyol component (A) ) 3.6 parts (0.03 mol) and 134.1 parts (0.61 mol) of pyromellitic anhydride (PMAn) were used as the carboxylic acid anhydride (C). Otherwise in the same manner as in Example 1, a polyester resin having a carboxyl group at the molecular end was obtained.

Example 4
161.2 parts (0.66 mol) of naphthalenedicarboxylic acid dimethyl ester (NDCM) as the carboxylic acid component (B), 720.8 parts (1.64 mol) of bisphenoxyethanol fluorene (BPEF) as the polyol component (A) and 2.8 parts (0.03 mol) of diethylene glycol (DEG) and 115.2 parts (0.53 mol) of pyromellitic anhydride (PMAn) were used as the carboxylic acid anhydride (C). Otherwise in the same manner as in Example 1, a polyester resin having a carboxyl group at the molecular end was obtained.

[Comparative Example 1] <Content of fluorene compound is less than 50 mol%>
In a reactor equipped with a nitrogen introduction tube, a thermometer, a stirrer, and a rectifying column, 286.9 parts (2.87 mol) of succinic anhydride (SuAn) as a carboxylic acid component (B) and a polyol component (A ) 440.0 parts (1.00 mol) of bisphenoxyethanol fluorene (BPEF) and 121.7 parts (1.15 mol) of diethylene glycol (DEG), 0.2 parts of dibutyltin oxide (DBTO) as a catalyst, and zinc acetate The polyester polyol (I) was produced by charging 0.2 part, heating up at 70-240 degreeC, and reacting for 8 hours, distilling off methanol or water.

  Subsequently, after cooling to 200 ° C., 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride as carboxylic anhydride (C) A polyester resin having a carboxyl group at the molecular end was obtained by charging 151.5 parts (0.57 mol) (Epiclon B-4400, manufactured by DIC) and reacting at 170 ° C. for 2 hours while dissolving. .

[Comparative Example 2] <No use of carboxylic anhydride (C)>
Into a reactor equipped with a nitrogen introduction tube, a thermometer, a stirrer, and a rectifying column, 234.9 parts (0.96 mol) of dimethyl naphthadicarboxylate (NDCM) and dimethyl terephthalate (carboxylic acid component (B)) 31.3 parts (0.16 mol) of DMT) and 47.8 g (0.16 mol) of dimethyl sodium 5-sulfoisophthalate (SIPM), and bisphenoxyethanol fluorene (BPEF) 424.5 as the polyol component (A) Parts (0.97 mol), ethylene glycol (EG) 130.2 parts (2.10 mol), diethylene glycol (DEG) 51.4 parts (0.48 mol), and dibutyltin oxide (DBTO) 0 as a catalyst. .2 parts and 0.2 parts of zinc acetate are charged, the temperature is raised to 70 to 240 ° C., and methanol or water is distilled off. To produce a polyester resin by performing reaction for 8 hours.

[Comparative Example 3] <Batch preparation of carboxylic anhydride (C)>
Naphthalenedicarboxylic acid dimethyl ester (NDCM) 289.1 parts (1.18 mol), dimethyl terephthalate (DMT) 28.8 parts (0.15 mol) and 5- (2,5- 39.1 parts (0.15 mol) of dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride (DIC Corporation, EPICLON B-4400) and polyol component (A) 519.6 parts (1.18 mol) of bisphenoxyethanol fluorene (BPEF), 91.9 parts (1.48 mol) of ethylene glycol (EG), and 31.4 parts (0.30 mol) of diethylene glycol (DEG) ) Was used. Otherwise, a polyester resin was prepared in the same manner as in Comparative Example 2. The obtained polyester resin is 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride corresponding to the carboxylic acid anhydride (C). Was charged together with the other carboxylic acid components and subjected to the reaction, so that the carboxyl group was incorporated into the main chain of the polyester resin and gelled in the production.

  In the polyester-based resin thus prepared, each component raw material used and the amount used are shown in Table 1 below.

  The physical properties of the polyester polyol and polyester resin thus prepared were measured according to the following method, and the results are shown in Table 2 below. Moreover, the compounding ratio (mol%) of each component raw material used is combined with Table 2 of a postscript, and is shown.

[Measurement of physical properties of polyester polyol]
1) Number average molecular weight of polyester polyol It measured according to the above-mentioned measuring method.

2) Hydroxyl value of polyester polyol The hydroxyl value of the obtained polyester polyol was measured according to JIS K0070.

[Measurement of physical properties of polyester resin]
1) Number average molecular weight of polyester resin Measured according to the measurement method described above.

2) Acid value of polyester-based resin The acid value of the obtained polyester resin was measured according to JIS K0070.

3) Glass transition temperature (Tg) of polyester resin
The test piece was heated and cooled at a rate of 10 ° C./min from room temperature, the calorific value was measured with a differential scanning calorimeter, two extension lines were drawn on the endothermic curve or exothermic curve, and 1 between the extension lines. The temperature at the intersection of the / 2 straight line and the endothermic curve or exothermic curve was defined as the glass transition temperature (Tg).

[Preparation of aqueous polyester resin solution]
Using each polyester resin obtained, a polyester resin aqueous solution was prepared as follows. First, 800 parts of water was charged into a reactor equipped with a nitrogen introduction tube, a thermometer, a stirrer, and a cooling tower, and 150 parts of a polyester resin and 50 parts of butyl cellosolve were added while stirring. After the addition, the temperature was raised to 70 ° C., 11.4 parts of 28% ammonia water was added, and the mixture was dissolved at an inner temperature of 90 ° C. for 2 hours. A polyester resin aqueous liquid (aqueous dispersion) having

  Using the polyester-based resin aqueous solution thus obtained, characteristic evaluations [water solubility, aqueous solution stability, heat and humidity resistance, refractive index (D line), Abbe number, birefringence) were performed according to the following methods. The results are also shown in Table 2 below.

[Water solubility]
In preparing the polyester resin aqueous liquid (aqueous dispersion) in Examples and Comparative Examples, ○ when the polyester resin was sufficiently dissolved or dispersed in the aqueous solvent, and the polyester resin dissolved or dispersed in the aqueous solvent The case where it was impossible to prepare a polyester resin aqueous liquid (aqueous dispersion) was marked with x.

[Aqueous solution stability]
Using a polyester resin aqueous solution (water dispersion) having a solid content concentration (% by weight) shown in Table 2 below, when stored in a thermostatic bath at 60 ° C. for one month, a uniform state is obtained without phase separation. The case where it was held was indicated as ◯, and the case where it was phase separated was indicated as ×.

[Moisture and heat resistance]
Polyethylene terephthalate (PET) film (adhesive PET film) (PET film thickness 100 μm) obtained by applying the polyester resin aqueous liquid (aqueous dispersion) obtained in Examples and Comparative Examples and drying (coating thickness 1 μm) ) Was prepared. Next, an ultraviolet curable resin composition comprising the following blending components is prepared, and the ultraviolet curing is performed so that the film thickness after curing using a bar coater is 10 μm on the film-forming surface of the easy-adhesion PET film. The mold resin composition was uniformly applied. After the application, the ultraviolet curable resin composition was irradiated by irradiating ultraviolet rays at 400 mJ / cm 2 using a high-pressure mercury lamp having an irradiation intensity of 120 W / cm set at 20 cm height after drying at 80 ° C. for 3 minutes. Cured to form a hard coat layer.

The sample thus prepared was left in a constant temperature and humidity chamber of 75 ° C. × 90% relative humidity for 300 hours, and then the adhesion evaluation shown below was performed. That is, 100 crosscuts were formed on the sample, and cellophap (registered trademark) manufactured by Nichiban Co., Ltd. was applied to the surface of the easy-adhesion PET film, pressed strongly with a finger, and then rapidly peeled off in the 90 ° direction and remained. The following three-level evaluation was performed according to the number. In the following evaluations, “Good” indicates good adhesion.
○: 100/100 (remaining number / measured number)
Δ: 80/100 or more, less than 100/100 ×: less than 80/100 <UV curable resin composition>
Urethane acrylate for hard coat (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., purple light UV-7600B)
25 parts methyl ethyl ketone / methyl isobutyl ketone [= 1/1 (mixed weight ratio)] 75 parts photopolymerization initiator (Irga Cure 184, manufactured by Nagase Sangyo Co., Ltd.) 3 parts

[Measurement evaluation of refractive index, Abbe number, birefringence]
The polyester resin aqueous liquids (aqueous dispersions) obtained in Examples and Comparative Examples were coated on a 100 μm biaxially stretched polyethylene terephthalate (PET) film using a bar coater, and heated at 100 ° C. for 20 minutes. A measurement sample (coating dry film thickness of about 1 μm) was prepared by drying. Then, the optical properties [refractive index (D line), Abbe number, birefringence] of the measurement sample were measured using an optical thin film measurement system (Scientific Computing international, optical thin film measurement system FilmTek 3000).

  From the above results, it can be seen that the example products have good evaluation results for both water solubility and aqueous solution stability, and have excellent aqueous properties. Furthermore, it can be seen that appropriate measurement results were obtained for all of the refractive index (D-line), Abbe number, and birefringence, and that a high refractive index was achieved.

  On the other hand, the Comparative Example 1 product in which the content of the fluorene compound in the polyol component (A) falls below a specific range was satisfactory with respect to the water-repellent properties, but there was no problem. Inferior, the refractive index (D line) was low, and a high refractive index could not be obtained. Moreover, the comparative example 2 product which did not use a carboxylic acid anhydride did not melt | dissolve in an aqueous solvent at the time of preparing polyester-type resin aqueous liquid, but could not obtain polyester-type resin aqueous liquid. Therefore, it has become impossible to perform other measurement evaluations. And the product of the comparative example 3 which used the carboxylic acid anhydride for preparation of polyester polyol, and the carboxyl group was integrated in the principal chain of the polyester-type resin was gelatinized in manufacture of the polyester-type resin. Therefore, an aqueous polyester resin solution could not be prepared.

  The polyester resin aqueous liquid obtained by dissolving or dispersing the polyester resin of the present invention in an aqueous medium is used for optical materials such as coating materials for various substrates, especially polyester films, and prism layers of light guide plates. A film with a film formed using the aqueous liquid is used for a magnetic card, a magnetic disk, a printing material, a graphic material, a photosensitive material, and the like.

Claims (8)

A polyester resin comprising a polyol component (A) and a carboxylic acid component (B) containing 50 mol% or more of a fluorene compound (A1) represented by the following general formula (1), and having a carboxylic acid at the molecular end A polyester resin comprising a carboxyl group derived from an anhydride (C) bonded thereto.

  A polyester polyol (I) comprising a polyol component (A) and a carboxylic acid component (B) containing 50 mol% or more of the fluorene compound (A1) represented by the general formula (1), and a carboxylic acid anhydride (C And a carboxyl group derived from the carboxylic acid anhydride (C) at the molecular end.   The polyester resin according to claim 1 or 2, wherein the number average molecular weight is 300 to 10,000.   Acid value is 10-100 mgKOH / g, The polyester-type resin as described in any one of Claims 1-3 characterized by the above-mentioned.   The polyester-based resin according to any one of claims 2 to 4, wherein the polyester polyol (I) has a number average molecular weight of 300 to 8000 and a hydroxyl value of 20 to 500.   The polyester resin according to any one of claims 2 to 5, wherein the amount of the carboxylic acid anhydride (C) used is 1 to 50 mol% with respect to the polyester polyol (I). A method for producing a polyester resin according to any one of claims 1 to 6, wherein the polyol component contains 50 mol% or more of the fluorene compound (A1) represented by the following general formula (1). (A) and a carboxylic acid component (B) are copolymerized to prepare a polyester polyol (I), and then the polyester polyol (I) is subjected to an addition reaction with the carboxylic acid anhydride (C) to produce the polyester polyol (I). A process for producing a polyester resin, characterized in that the carboxylic acid anhydride (C) is bonded to the molecular ends of I).

  A polyester resin aqueous solution obtained by dissolving or dispersing the polyester resin according to any one of claims 1 to 6 in an aqueous solvent.