JP2011190348A - Soluble copolymerized polyester resin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a copolymerized polyester having heat resistance, i.e., a glass transition temperature of 100°C or higher and being soluble in a general-purpose solvent. <P>SOLUTION: The copolymerized polyester resin comprises dicarboxylic acid component (A) and glycol component (B), and in the copolymerized polyester resin, the copolymerization ratio of an aromatic dicarboxylic acid relative to the component (A) is 80 mol% or higher, the copolymerization ratio of bisphenoxy ethanol fluorene relative to the component (B) is 30-80 mol%, and the copolymerization ratio of a specific glycol relative to the component (B) is 20-70 mol%. The copolymerized polyester resin has a number average molecular weight of 8,000 or more and a glass transition temperature of 100°C or higher. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a soluble copolyester resin having excellent heat resistance.

  Copolyester resins are used in various applications including coating applications and adhesive applications because the glass transition temperature and molecular weight can be freely controlled. However, if the glass transition temperature is designed to be high for improving the heat resistance, the solubility in a general-purpose solvent is lowered, and if the crystallinity is designed to be lowered for improving the solubility, the heat resistance is lowered. Therefore, it is very difficult to produce a copolyester having good solvent solubility and simultaneously having a glass transition temperature of 100 ° C. or higher.

  On the other hand, plastics have been actively applied to optical materials. Among them, polyesters using bisphenoxyethanol fluorene (hereinafter sometimes abbreviated as BPEF) are excellent in heat resistance, optical properties, and moldability. Therefore, it is attracting attention.

  In Patent Documents 1 to 5, polyesters copolymerized with BPEF as a molding material, particularly polyesters for optical materials, are proposed, but they are soluble in halogen-containing solvents such as methylene chloride, but are not limited to toluene or 2-butanone. Therefore, it is difficult to use in coating and adhesive applications. Patent Document 6 proposes a polyester copolymerized with BPEF for powder coating, but it has a low glass transition temperature and does not dissolve in general-purpose solvents. It was difficult. Further, Patent Document 7 proposes a polyester copolymerized with BPEF for use in paints and adhesives. However, since the glass transition temperature is 100 ° C. or lower, there is a problem that the coating film melts when exposed to water vapor. . Patent Document 8 proposes a polyester containing BPEF, methyl naphthalene dicarboxylate, dimethyl sodium 5-sulfoisophthalate, and ethylene glycol as an aqueous dispersion resin. However, the intrinsic viscosity of the resin is 0.53 dL. Since it was relatively low at / g or less, workability was poor, and it was difficult to use in coating applications and adhesive applications.

Japanese Patent Laid-Open No. 06-49186 Japanese Patent Laid-Open No. 06-184288 JP 08-109249 A JP 08-269178 A Japanese Patent Laid-Open No. 11-060706 JP-A-11-217520 JP 2001-2905 A JP 2009-242461 A

  An object of the present invention is to solve the above-mentioned problems and to provide a copolyester having a heat resistance of a glass transition temperature of 100 ° C. or higher and soluble in a general-purpose solvent.

  As a result of intensive studies, the present inventor has found that the above problem can be solved by using a specific amount of a specific glycol component, and has reached the present invention.

That is, the gist of the present invention is as follows.
(1) A copolymer polyester resin comprising a dicarboxylic acid component (A) and a glycol component (B), wherein the copolymerization ratio of the aromatic dicarboxylic acid to the component (A) is 80 mol% or more, and the bis to the component (B). The copolymerization ratio of phenoxyethanol fluorene is 30 to 80 mol%, the copolymerization ratio of the glycol represented by the general formula (1) to the component (B) is 20 to 70 mol%, the number average molecular weight is 8000 or more, and the glass transition temperature. Is a copolyester resin having a temperature of 100 ° C. or higher.
(In the formula, R ¹ represents an alkyl group having 1 to 2 carbon atoms, R ² represents one selected from hydrogen and an alkyl group having 1 to 2 carbon atoms, and m and n satisfy m + n = 1, 2. Represents an integer of 0 to 2.)
(2) Copolyester resin as described in (1) which contains 50 mol% or less isosorbide and / or tricyclodecane dimethanol as a copolymerization component with respect to 100 mol% of glycol component (B).
(3) A polyester solution containing 10% by mass or more of the copolyester resin according to (1) or (2), wherein the solvent of the solution is selected from the group consisting of cyclohexanone, 2-butanone and toluene A polyester solution that is a solvent of more than one species.
(4) A paint or coating agent using the polyester solution described in (3).

  According to the present invention, a copolyester having a glass transition temperature of 100 ° C. or more and heat resistance and soluble in a general-purpose solvent is provided. The solution in which this copolyester is dissolved can be used for coating applications and adhesive applications, and its industrial utility value is extremely high.

  Hereinafter, the present invention will be described in detail.

  The copolyester resin of the present invention is mainly composed of a dicarboxylic acid component (A) and a glycol component (B).

  As the dicarboxylic acid component (A), it is necessary to copolymerize an aromatic carboxylic acid. Examples of the aromatic carboxylic acid include terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, 4,4'-dicarboxybiphenyl, 5-sodium sulfoisophthalic acid and the like. Of these, terephthalic acid and isophthalic acid, which are highly versatile, are preferred.

  The copolymerization amount of the aromatic carboxylic acid with respect to the dicarboxylic acid component (A) needs to be 80 mol% or more, and preferably 90 mol% or more. When the copolymerization amount of the aromatic carboxylic acid is less than 80 mol%, the heat resistance of the copolymerized polyester resin is lowered, and the processability is deteriorated.

  Examples of other dicarboxylic acids constituting the dicarboxylic acid component (A) include oxalic acid, malonic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, octadecanedioic acid, and eicosanedioic acid. Saturated aliphatic dicarboxylic acid, fumaric acid, maleic acid, itaconic acid, mesaconic acid, citraconic acid and other unsaturated aliphatic dicarboxylic acids, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2- Examples thereof include cyclohexanedicarboxylic acid and alicyclic dicarboxylic acid of 2,5-norbornenedicarboxylic acid. These may be anhydrous.

  As the glycol component (B), it is necessary to copolymerize BPEF represented by the formula (2). BPEF can be obtained from JFE Chemical Company or Osaka Gas Chemical Company.

  The copolymerization amount of BPEF with respect to the glycol component (B) needs to be 30 to 80 mol%, preferably 40 to 75 mol%, and more preferably 40 to 70 mol%. When the copolymerization amount of BPEF is less than 30 mol%, the glass transition temperature becomes lower than 100 ° C. On the other hand, if the copolymerization amount of BPEF exceeds 80 mol%, it is difficult to obtain a high molecular weight polymer because the melt viscosity becomes high, and it is difficult to dissolve in a general-purpose solvent.

  As the glycol component (B), it is necessary to further copolymerize a monomer represented by the general formula (1) (hereinafter abbreviated as “monomer (1)”).

(In the formula, R ¹ represents an alkyl group having 1 to 2 carbon atoms, R ² independently represents one selected from hydrogen and an alkyl group having 1 to 2 carbon atoms, m and n are m + n = 1, Represents an integer of 0 to 2 satisfying 2.)

  As the monomer (1), 1,2-propanediol, 2-methyl-1,2-propanediol, 1,2-butanediol, 2-methyl-1,2-butanediol, 2-ethyl-1,2 -Butanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol (neopentyl glycol), 2-ethyl-1,3-propanediol, 2-methyl-2- Ethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 3-methyl-1,3-butanedidiol, 3-methyl-1,3-butanediol, 1,3-pentane Examples thereof include diol, 3-methyl-1,3-pentanediol, 3-ethyl-1,3-pentanediol and the like. Among these, 1,2-propanediol, 2-methyl-1,3-propanediol, and neopentyl glycol are preferable from the viewpoint of versatility and solvent solubility.

  The copolymerization amount of the monomer (1) with respect to the glycol component (B) is required to be 20 to 70 mol%, preferably 25 to 50 mol%, and more preferably 30 to 50 mol%. When the copolymerization amount of the monomer (1) is less than 20 mol%, the solubility is deteriorated. On the other hand, when the copolymerization amount of the monomer (1) exceeds 70 mol%, the glass transition temperature is lower than 100 ° C. This is not preferable.

  Further, as a glycol component (B), 1,4: 3,6-dianhydro-D-sorbitol (hereinafter sometimes abbreviated as “isosorbide”) and / or tricyclodecane dimethanol is soluble. This is preferable because the glass transition temperature can be further improved while maintaining the above.

Isosorbide is represented by formula (3).
Isosorbide can be easily obtained from sugars and starch. For example, isosorbide can be obtained by hydrogenating D-glucose and performing a dehydration reaction. Isosorbide can be obtained from Rocket.

Tricyclodecane dimethanol is represented by the general formula (4).
Examples of tricyclodecane dimethanol include 3 (4), 8 (9) -bis (hydroxymethyl) -tricyclo (5.2.1.0 ^2.6 ) decane (hereinafter abbreviated as “TCD alcohol”) and the like. Is mentioned. TCD alcohol can be obtained from OXEA.

  The copolymerization amount of isosorbide and tricyclodecane dimethanol is preferably 50 mol% or less, more preferably 10 to 40 mol%, more preferably 10 to 30 mol, based on the glycol component (B). More preferably, it is made into%.

  Examples of other diol components constituting the glycol component (B) include ethylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 2-amino-2-ethyl-1 , 3-propanediol, 2-amino-2-methyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 1,5 -Pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, diethylene glycol, triethylene glycol, dipropylene glycol, tri Aliphatic glycols such as propylene glycol, bisphenol A, bisphenol S, bisphenol C Alicyclic ring such as bisphenol Z, bisphenol AP, ethylene oxide adduct or propylene oxide adduct of 4,4'-biphenol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol Group glycol, polyethylene glycol, polypropylene glycol.

  The copolymerized polyester resin of the present invention may be copolymerized with a hydroxycarboxylic acid depending on the purpose such as imparting appropriate flexibility and adjusting the glass transition temperature.

  Examples of the hydroxycarboxylic acid component include p-hydroxybenzoic acid, m-hydroxybenzoic acid, o-hydroxybenzoic acid, lactic acid, oxirane, β-propiolactone, β-butyrolactone, γ-butyrolactone, δ-valerolactone, ε- Caprolactone, glycolic acid, 2-hydroxybutyric acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 2-hydroxyisobutyric acid, 2-hydroxy-2-methylbutyric acid, 2-hydroxyvaleric acid, 3-hydroxyvaleric acid, 4-hydroxy Examples include valeric acid, 5-hydroxyvaleric acid, 6-hydroxycaproic acid, 10-hydroxystearic acid, and among them, ε-caprolactone having versatility is preferable.

  The copolymerization amount of hydroxycarboxylic acid with respect to all carboxylic acid components is preferably 30 mol% or less. If the proportion of the hydroxycarboxylic acid component exceeds 30 mol%, the glass transition temperature may be lower than 100 ° C. The “total carboxylic acid component” is a dicarboxylic acid component (A), a hydroxycarboxylic acid component, a monocarboxylic acid component, or a trivalent or higher carboxylic component that can be used as a constituent component of the copolymer polyester resin of the present invention. Means the sum.

  If it is a small amount, a tri- or higher functional carboxylic acid component or alcohol component may be added to the copolymer polyester resin as a copolymer component.

  Trifunctional or higher carboxylic acid components include trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic acid, and trimesic acid. And aliphatic carboxylic acids such as 1,2,3,4-butanetetracarboxylic acid.

  Examples of the tri- or higher functional alcohol component include glycerol, trimethylolpropane, trimethylolethane, pentaerythritol, α-methylglucose, mannitol, sorbitol and the like.

  These do not necessarily need to be used alone, but can be used by adding a plurality of types depending on the properties to be imparted to the resin. The copolymerization amount of the tri- or higher functional monomer is suitably about 0.2 to 5 mol% with respect to the total carboxylic acid component or the total alcohol component. If the copolymerization amount of the tri- or higher functional monomer is less than 0.2 mol%, the added effect does not appear, and if the copolymerization amount exceeds 5 mol%, the gelation point is exceeded at the time of polymerization. It may become. The “total alcohol component” means the total of the glycol component (B), hydroxycarboxylic acid component, monoalcohol component, trihydric or higher alcohol component that can be used as the constituent component of the polyester of the present invention.

  In the copolyester, a monocarboxylic acid may be copolymerized within a range not exceeding 1 mol% with respect to the total carboxylic acid component, and within a range not exceeding 1 mol% with respect to the total alcohol component. Monoalcohol may be copolymerized. Examples of monocarboxylic acids include lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, benzoic acid, p-tert-butylbenzoic acid, cyclohexane acid, 4-hydroxyphenyl stearic acid, and the like. Examples of the alcohol include octyl alcohol, decyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, and 2-phenoxyethanol.

  Copolyester resin can be manufactured by a well-known method combining the said monomer. For example, a method comprising an esterification reaction and a polycondensation reaction can be mentioned.

  In the esterification reaction, all monomer components and / or low polymers thereof are reacted by heating and melting under an inert atmosphere. The reaction time is preferably 2.5 to 10 hours, and more preferably 4 to 6 hours.

  The polycondensation reaction is carried out under reduced pressure until the glycol component is distilled off from the esterified product obtained by the esterification reaction until the desired molecular weight is reached. The reaction temperature for polycondensation is preferably 250 to 300 ° C, more preferably 270 to 300 ° C. When the reaction temperature is within this range, the copolymer polyester of the present invention having a high melt viscosity can be sufficiently stirred, and the polymerization time can be shortened. The degree of vacuum is preferably 130 Pa or less. If the degree of vacuum is low, the polycondensation time may be long. It is preferable to gradually reduce the pressure over 60 to 180 minutes until the atmospheric pressure reaches 130 Pa or less.

  In the esterification reaction and polycondensation reaction, a catalyst is used as necessary. Catalysts include organic titanate compounds such as tetrabutyl titanate, alkali metals such as zinc acetate and magnesium acetate, acetates of alkaline earth metals, organotin compounds such as antimony trioxide, hydroxybutyltin oxide, and tin octylate. Can be mentioned. The amount of the catalyst used is preferably 1.0% by mass or less with respect to the mass of the resin produced.

  When a desired acid value or hydroxyl value is imparted to the copolymerized polyester resin, a polybasic acid component or a polyvalent glycol component is further added following the polycondensation reaction, and depolymerization is performed in an inert atmosphere. be able to.

  The number average molecular weight of the copolyester resin needs to be 8,000 or more, and preferably 10,000 or more. When the number average molecular weight is less than 8,000, the processability is poor, and the coating film is broken when coated, which is not preferable.

  The glass transition temperature of the copolyester resin needs to be 100 ° C. or higher, and more preferably 110 ° C. or higher. When the glass transition temperature is lower than 100 ° C., the coating film melts when exposed to water vapor, which is not preferable.

  The number average molecular weight of the copolyester can be adjusted to the above range by controlling the polymerization time and the depolymerization amount. The glass transition temperature can be adjusted to the above range by appropriately selecting a combination of monomers to be copolymerized. When tricyclodecane dimethanol, isosorbide and BPEF are copolymerized, the glass transition temperature tends to be high, and when monomer (1) is copolymerized, the glass transition temperature tends to be low.

  Since the copolymerized polyester resin of the present invention is excellent in solubility in a solvent, it can be dissolved in various general-purpose solvents and used as a polyester solution. At 25 ° C., the solution concentration is preferably 10% by mass or more, more preferably 10 to 50% by mass, and further preferably 25 to 40% by mass. When the polyester solution concentration is less than 10% by mass, workability when used as a paint or a coating agent is lowered. The upper limit of the solution concentration is not particularly limited, but 50% by mass or less is preferable so that the viscosity of the solution does not become too high. Examples of the solvent to be used include cyclohexanone, 2-butanone, toluene and the like. These may be used alone or in combination of two or more. Of these, the combination of cyclohexanone, 2-butanone and toluene is preferred because of its high solubility. When 2-butanone and toluene are used in combination, the mass ratio of the two is not particularly limited, but is preferably in the range of 80/20 to 20/80.

  In the copolymerized polyester resin of the present invention, if necessary, a curing agent, an ultraviolet absorber, a release agent, a lubricant, various additives, a pigment such as titanium oxide, zinc white, carbon black, a pigment dispersant, a dye, Polyester resins, urethane resins, olefin resins, acrylic resins, alkyd resins, cellulose derivatives, and the like can be blended.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. The physical properties of the copolymer polyester resin were measured by the following method.

(1) Resin composition
^{It was determined by 1} H-NMR analysis (manufactured by JEOL Datum, 500 MHz).
(2) Number average molecular weight The number average molecular weight is determined by GPC analysis (liquid feeding unit LC-10ADvp type and UV-visible spectrophotometer SPD-6AV type manufactured by Shimadzu Corporation), detection wavelength: 254 nm, solvent: chloroform, polystyrene conversion ).

(3) Glass transition temperature 10 mg of the copolyester resin was used as a sample, and measurement was performed using a DSC (Differential Scanning Calorimetry) apparatus (DSC7 manufactured by PerkinElmer Co., Ltd.) at a temperature rising rate of 10 ° C./min. An intermediate value of two bending point temperatures derived from the glass transition in the temperature rising curve was determined, and this was defined as the glass transition temperature (Tg).
(4) Dissolution performance In a glass container, 10 g of resin pellets and 90 g of 2-butanone / toluene mixed solvent (mass ratio 1/1) were placed, and shaken at 25 ° C. for 6 hours using a paint shaker, and the dissolution state was observed. . Those that were dissolved were designated as “◯”, and those that did not dissolve were designated as “x”. Moreover, the same test was done using cyclohexanone as a solvent. When it became "(circle)" with any solvent, it was considered that there was a dissolution performance.

(5) Workability Toluene prepared in (4) on a PET film (50 μm, manufactured by Unitika Co.) substrate using a desktop coating device (manufactured by Yasuda Seiki, film applicator No. 542-AB, bar coater) The coating solution was coated with the / 2-butanone mixed solvent solution and then heated in an oven set at 100 ° C. for 1 minute to form a coated film having a thickness of about 10 μm on the substrate. When dissolved in cyclohexanone instead of being dissolved in the toluene / 2-butanone mixed solvent in (4), coating is performed in the same manner as in the case of using the toluene / 2-butanone mixed solvent except that the oven temperature is set to 150 ° C. A film was prepared. The obtained coated film was bent in the direction of 180 °, and when the coating film was not broken, “◯” was given, and when the coating film was broken, “X” was given.
(6) Water vapor resistance The coating film prepared in (5) was exposed to steam heated to 100 ° C. for 30 seconds, and the state of the coating film was observed. When the coating film was not melted, the water vapor resistance was “◯”, and when the coating film was melted, the water vapor resistance was “x”.

Example 1
1661 parts by mass of terephthalic acid, 2193 parts by mass of BPEF, 885 parts by mass of neopentyl glycol, 2.7 parts by mass of trimelliol propane (terephthalic acid: BPEF: neopentyl glycol: trimethylolpropane = 100: 50: 85: 0.2 (mole) The mixture consisting of the ratio)) was controlled in an autoclave at 0.3 MPa and 260 ° C. for 3 hours while stirring, and then the esterification reaction was carried out at normal pressure and 260 ° C. for 3 hours after releasing the pressure. . Next, the temperature was raised to 270 ° C., 6.8 parts by mass of tetrabutyl titanate (20 × 10 ⁻⁴ mol per mol of terephthalic acid) was added as a catalyst, and the pressure of the system was gradually reduced. The polycondensation reaction was carried out. Polycondensation was performed until an appropriate viscosity was obtained, and a pelletized copolyester was obtained using a strand cutter.

Examples 2 to 13 and Comparative Examples 1 to 5
A copolyester resin was obtained in the same manner as in Example 1 except that the monomer used and the charged composition were changed.

  Tables 1 and 2 show the charged resin composition, final resin composition and characteristic values of the resin.

  In each of Examples 1 to 13, the glass transition temperature was 100 ° C. or higher, and the glass transition temperature was dissolved in a general-purpose solvent, and the heat resistance and dissolution performance were good. All of the coating films produced using the solution were excellent in processability, and even when exposed to water vapor, the coating film did not melt and the water vapor resistance was good.

On the other hand, Comparative Example 1 had a low BPEF copolymerization amount and a large copolymerization amount of monomer (1), so that the glass transition temperature did not reach 100 ° C. and the heat resistance and water vapor resistance were low. .
Since the comparative example 2 had much copolymerization amount of BPEF, the melt | dissolution performance was bad and could not produce a coating film.
In Comparative Example 3, since the copolymerization amount of the aromatic carboxylic acid was small, the glass transition temperature did not reach 100 ° C., and the heat resistance and water vapor resistance were low.
In Comparative Example 4, since the copolymerization amount of the monomer (1) was small, the dissolution performance was poor and a coating film could not be produced.
In Comparative Example 5, since the molecular weight was lower than 8000, the coating film could be produced, but the processability was poor.

Claims (4)

A copolymer polyester resin comprising a dicarboxylic acid component (A) and a glycol component (B), wherein the copolymerization ratio of the aromatic dicarboxylic acid to the component (A) is 80 mol% or more, and the bisphenoxyethanol fluorene to the component (B). The copolymerization ratio is 30 to 80 mol%, the copolymerization ratio of the glycol represented by the general formula (1) to the component (B) is 20 to 70 mol%, the number average molecular weight is 8000 or more, and the glass transition temperature is 100 ° C. Copolyester resin as described above.
(In the formula, R ¹ represents an alkyl group having 1 to 2 carbon atoms, R ² represents one selected from hydrogen and an alkyl group having 1 to 2 carbon atoms, and m and n satisfy m + n = 1, 2. Represents an integer of 0 to 2.) The copolymerized polyester resin according to claim 1, comprising 50 mol% or less of isosorbide and / or tricyclodecane dimethanol as a copolymerization component with respect to 100 mol% of the glycol component (B). A polyester solution containing 10% by mass or more of the copolyester resin according to claim 1 or 2, wherein the solvent of the solution is one or more solvents selected from the group consisting of cyclohexanone, 2-butanone, and toluene. A polyester solution. A paint or coating agent using the polyester solution according to claim 3.