JP6149436B2 - Unsaturated crystalline polyester resin - Google Patents

Description

  The present invention relates to an unsaturated crystalline polyester resin.

  As a resin material, for example, an unsaturated crystalline polyester resin having an unsaturated double bond is known.

  For example, Patent Document 1 discloses a step of polycondensing an alcohol component containing an α, ω-linear aliphatic diol having 2 to 8 carbon atoms and a carboxylic acid component containing an unsaturated aliphatic dicarboxylic acid compound; A step of obtaining a crystalline polyester by adding one or more selected from a compound having a catechol skeleton and a compound having a hydroquinone skeleton and a radical polymerization initiator during or after the condensation polymerization reaction. A method for producing a reactive polyester is described.

  Patent Document 2 describes a crystalline unsaturated polyester using a biomass-derived raw material in part or all, and describes that an unsaturated dibasic acid and its acid anhydride are used as an organic acid component. .

JP 2011-132333 A Japanese Patent Application Laid-Open No. 2011-184583

  An object of the present invention is to provide a photopolymerizable unsaturated crystalline polyester resin having a low melting point.

In the invention according to claim 1, the unsaturated aliphatic dicarboxylic acid and the unsaturated aliphatic diol are polycondensed, the melting point is in the range of 40 ° C. or higher and 90 ° C. or lower, and the weight average molecular weight is 10,200 or higher. The unsaturated aliphatic diol is an unsaturated crystalline polyester resin that is a mixture of a cis isomer and a trans isomer.

  In the invention according to claim 2, the unsaturated aliphatic dicarboxylic acid is an unsaturated aliphatic dicarboxylic acid having 4 to 8 carbon atoms, and the unsaturated aliphatic diol is an unsaturated aliphatic carboxylic acid having 2 to 8 carbon atoms. The unsaturated crystalline polyester resin according to claim 1, which is an aliphatic diol.

  According to the invention of claim 1, the melting point is low and the photopolymerizable unsaturated crystallinity is lower than that of the unsaturated crystalline polyester resin obtained by condensation polymerization of unsaturated aliphatic dicarboxylic acid and saturated aliphatic diol. A polyester resin is provided.

  According to the invention of claim 2, the unsaturated aliphatic dicarboxylic acid is not an unsaturated aliphatic dicarboxylic acid having 4 to 8 carbon atoms, and the unsaturated aliphatic diol is an unsaturated fat having 2 to 8 carbon atoms. An unsaturated crystalline polyester resin having a low melting point and a photopolymerization property is provided as compared with a case where it is not a group diol.

  Embodiments of the present invention will be described below. This embodiment is an example for carrying out the present invention, and the present invention is not limited to this embodiment.

<Unsaturated crystalline polyester resin>
The unsaturated crystalline polyester resin according to this embodiment is a crystalline polyester resin obtained by polycondensation of an unsaturated aliphatic dicarboxylic acid and an unsaturated aliphatic diol. In addition, in the case of the polymer which copolymerized other components with respect to the polyester principal chain, when other components are 50 mass% or less, this copolymer is also called a polyester resin.

  Examples of unsaturated aliphatic dicarboxylic acids include fumaric acid, maleic acid, citraconic acid, glutaconic acid, itaconic acid, 3-hexenedioic acid, muconic acid, traumatic acid, and the like, and anhydrides thereof, and lower Examples thereof include, but are not limited to, alkyl esters. Of these, unsaturated aliphatic dicarboxylic acids having 4 to 8 carbon atoms are preferable, and unsaturated aliphatic dicarboxylic acids having 4 to 6 carbon atoms are preferable from the viewpoint of photopolymerization and the like.

  Examples of unsaturated aliphatic diols include, but are not limited to, 2-butene-1,4-diol. Of these, unsaturated aliphatic diols having 2 to 8 carbon atoms are preferable, and unsaturated aliphatic diols having 4 to 8 carbon atoms are preferable from the viewpoint of photopolymerization and the like. The unsaturated aliphatic diol may be one of geometric isomers (cis isomer and trans isomer) or a mixture of geometric isomers (cis isomer and trans isomer). And a trans isomer). By being a mixture of geometric isomers (cis isomer and trans isomer), there are advantages such as easy control of the melting point of the resin.

  The weight average molecular weight of the crystalline polyester resin having an unsaturated double bond according to this embodiment is, for example, in the range of 3,000 to 200,000. When the weight average molecular weight of the crystalline polyester resin having an unsaturated double bond is less than 3,000, the UV reactivity may be deteriorated, and when it exceeds 200,000, the melting point may be increased.

  The weight average molecular weight (Mw) is measured by gel permeation chromatography (GPC). The molecular weight measurement by GPC is performed with a THF solvent using LC-10AD manufactured by Shimadzu Corporation as a measuring apparatus, using a column (KF-805L manufactured by Showa Denko KK). The weight average molecular weight is calculated from the measurement result using a molecular weight calibration curve prepared with a monodisperse polystyrene standard sample.

  There is no restriction | limiting in particular as a manufacturing method of the crystalline polyester resin which has an unsaturated double bond, What is necessary is just to manufacture with the general polyester polymerization method which makes a dicarboxylic acid component and a diol component react. Specific examples include Fischer's esterification method and transesterification method. Moreover, you may use metal catalysts, such as palladium, tin, and titanium.

  In the present embodiment, “crystallinity” of “crystalline resin” refers to having a clear endothermic peak rather than a step-like endothermic change in differential scanning calorimetry (DSC) of the resin. Specifically, in differential scanning calorimetry (DSC) using a differential scanning calorimeter (equipment name: DSC-60 type) manufactured by Shimadzu Corporation equipped with an automatic tangential processing system, a temperature increase rate of 10 ° C./min. A “clear” endothermic peak is assumed when the temperature from the onset point to the top of the endothermic peak is 10 ° C. or less when the temperature is raised at. The point of the flat part of the baseline in the DSC curve and the point of the flat part of the falling part from the base line are specified, and the intersection of the tangents of the flat part between the two points is set as an “onset point” by the automatic tangent processing system. Desired.

  The melting point of the crystalline polyester resin having an unsaturated double bond according to this embodiment is in the range of 40 ° C. to 90 ° C., and preferably in the range of 50 ° C. to 80 ° C. When the melting point of the crystalline polyester resin having an unsaturated double bond is less than 40 ° C., it becomes liquid at room temperature or the like, and when it exceeds 90 ° C., the viscosity is remarkably increased. The melting point of the crystalline polyester resin is determined from the above “endothermic peak”.

  Of the dicarboxylic acids used, unsaturated aliphatic dicarboxylic acids may be used in combination with unsaturated cyclic aliphatic dicarboxylic acids such as aliphatic dicarboxylic acids and cyclohexene dicarboxylic acids, rosin or rosin-modified products, etc. It is preferable that 80 mol% or more of unsaturated aliphatic dicarboxylic acid is contained from points, such as maintaining.

  Of the diols to be used, an unsaturated aliphatic diol and an aliphatic diol may be used in combination, but from the standpoint of maintaining crystallinity, the unsaturated aliphatic diol may contain 80 mol% or more. preferable.

  Examples of the aliphatic dicarboxylic acid include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelic acid, sebacic acid, 1,9-nonanedicarboxylic acid, and 1,10-decanedicarboxylic acid. 1,11-undecanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, 1,13-tridecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 1,16-hexadecanedicarboxylic acid, 1,18-octadecanedicarboxylic acid, etc. , These acid anhydrides, and lower alkyl esters thereof, but are not limited thereto.

  Examples of the aliphatic diol include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8- Octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,18- Examples include, but are not limited to, octadecanediol and 1,20-eicosanediol.

  In the crystalline polyester resin having an unsaturated double bond according to this embodiment, the proportion of the component derived from the unsaturated aliphatic dicarboxylic acid is, for example, from 80 mol% to 100 mol%, and derived from the unsaturated aliphatic diol. The ratio of the component to perform is 80 mol% or more and 100 mol% or less, for example.

The structure of the crystalline polyester resin having an unsaturated double bond according to the present embodiment includes, for example, ¹ H-NMR spectrum measurement, ¹³ C-NMR spectrum measurement, IR spectrum measurement, MASS spectrum measurement, GPC (gel permeation chromatography). ) Etc.

  The crystalline polyester resin having an unsaturated double bond according to the present embodiment includes, for example, a binder resin for toner for developing an electrostatic charge image, a curable ink, a lacquer, an adhesive, a semiconductor, a solar cell sealing material, and the like. Used as By using the crystalline polyester resin having an unsaturated double bond according to this embodiment as a binder resin for an electrostatic charge image developing toner, a photocurable toner such as UV curable resin can be obtained. Further, the electrostatic image developing toner using the crystalline polyester resin having an unsaturated double bond according to this embodiment is excellent in low-temperature fixability and excellent in mechanical properties such as scratch resistance.

  Hereinafter, although an example and a comparative example are given and the present invention is explained more concretely in detail, the present invention is not limited to the following examples.

[Example 1]
<Synthesis of unsaturated crystalline polyester resin 1>
Trans-3-hexenedioic acid (45 parts by mass, manufactured by Tokyo Chemical Industry Co., Ltd.), cis, trans mixed-2-butene-1,4-diol (26 parts by mass, molar ratio cis: trans = 28: 72, Tokyo Chemical Industry) Kogyo Co., Ltd.) and ORGATICS TC-400 (0.50 parts by mass, manufactured by Matsumoto Fine Chemicals Co., Ltd.) as a catalyst were placed in a three-necked flask and heated and stirred at 180 ° C. for 2 hours in a nitrogen stream. Further, the mixture was heated and stirred at 700 Pa and 180 ° C. for 4 hours. After completion of the reaction, the reaction solution was poured into a beaker (630 parts by mass of methanol) to precipitate crystals. The crystals were collected by suction filtration and washed with 400 parts by mass of methanol. The crystals were vacuum dried at 30 ° C. for 18 hours to obtain 47 parts by mass of unsaturated crystalline polyester resin 1. The melting point was 71 ° C. When this resin was measured by GPC (gel permeation chromatography) LC-10AD manufactured by Shimadzu Corporation at a flow rate of 1 mL / min and a polystyrene calibration curve, the weight average molecular weight was 11,600. When the ¹ H-NMR spectrum of the resin was measured with a Varian, 300 MHz, CDCl ₃ solution, δ 5.8 ppm (m, 2H, trans butenediol = CH—CH =), 5.7 ppm (m, 2H, The results of hexenedioic acid = CH—CH =), 4.7 ppm (m, 4H, cis butenediol-CH ₂ —), 3.1 ppm (m, 4H, hexenedioic acid —CH ₂ —) were obtained, and The structure was confirmed.

[ Comparative Example 3 ]
<Synthesis of unsaturated crystalline polyester resin 2>
Trans-3-hexenedioic acid (3.0 parts by mass, manufactured by Wako Pure Chemical Industries, Ltd.), cis-2-butene-1,4-diol (1.8 parts by mass, manufactured by Tokyo Kasei Kogyo Co., Ltd.), ORGATICS TC -400 (0.033 parts by mass, manufactured by Matsumoto Fine Chemicals) was placed in a three-necked flask and heated and stirred at 180 ° C. for 4 hours under a nitrogen stream. Furthermore, the mixture was heated and stirred at 200 ° C. to 700 Pa and 180 ° C. for 4 hours. After completion of the reaction, the reaction solution was poured into a beaker (80 parts by mass of methanol) to precipitate crystals. The crystals were collected by suction filtration and washed with 80 parts by mass of methanol. The crystals were vacuum dried at 20 ° C. for 18 hours to obtain 70 parts by mass of unsaturated crystalline polyester resin 2. The melting point was 48 ° C. The weight average molecular weight of this resin was 13,500. When a ¹ H-NMR spectrum of the resin was measured with a Varian, 300 MHz, CDCl ₃ solution, δ 5.7 ppm (s, 2 H, trans butenediol = CH), 5.7 ppm (t, 6 H, hexenedioic acid) = CH-CH =, cis) , 4.7ppm (d, 4H, cis butenediol _{-CH 2 -), 3.1ppm (m} , 8H, hexenedioic acid -CH ₂ -) results were obtained, the following structure It was confirmed that.

[ Comparative Example 4 ]
<Synthesis of unsaturated crystalline polyester resin 3>
Fumaric acid (61 parts by mass, manufactured by Wako Pure Chemical Industries, Ltd.), cis-2-butene-1,4-diol (44 parts by mass, manufactured by Tokyo Chemical Industry Co., Ltd.), ORGATICS TC-400 (0.80 parts by mass, Matsumoto Fine Chemicals Co., Ltd.) was placed in a three-necked flask and heated and stirred at 180 ° C. for 2 hours under a nitrogen stream. The mixture was further heated and stirred at 700 Pa and 180 ° C. for 3 hours. After completion of the reaction, the reaction solution was poured into a beaker (1200 parts by mass of methanol) to precipitate crystals. The crystals were collected by suction filtration and washed with 400 parts by mass of methanol. The crystals were vacuum dried at 40 ° C. for 18 hours to obtain 70 parts by mass of unsaturated crystalline polyester resin 3. The melting point was 85 ° C. The weight average molecular weight of this resin was 10,200. When the ¹ H-NMR spectrum of the resin was measured with a Varian, 300 MHz, CDCl ₃ solution, δ 6.8 ppm (s, 2 H, fumaric acid = CH), 5.8 ppm (m, 2 H, ═CH), The result of 4.7 ppm (d, 4H, cis-butenediol-CH ₂ —) was obtained, and the following structure was confirmed.

[Comparative Example 1]
<Synthesis of unsaturated crystalline polyester resin 4>
Fumaric acid (58 parts by mass, manufactured by Wako Pure Chemical Industries, Ltd.), 1,6-hexanediol (56 parts by mass, manufactured by Tokyo Kasei Kogyo Co., Ltd.), ORGATIC TC-400 (0.70 parts by mass, manufactured by Matsumoto Fine Chemicals) Was placed in a three-necked flask and heated and stirred at 180 ° C. for 2 hours under a nitrogen stream. The mixture was further heated and stirred at 700 Pa and 180 ° C. for 3 hours. After completion of the reaction, the reaction solution was poured into a beaker (1200 parts by mass of methanol) to precipitate crystals. The crystals were collected by suction filtration and washed with 400 parts by mass of methanol. The crystals were vacuum-dried at 40 ° C. for 18 hours to obtain 40 parts by mass of unsaturated crystalline polyester resin 4. The melting point was 106 ° C. The weight average molecular weight of this resin was 8,200. When the ¹ H-NMR spectrum of the resin was measured with a Varian, 300 MHz, CDCl ₃ solution, δ 6.8 ppm (s, 2 H, ═CH—CH =), 4.2 ppm (t, 4 H, —OCH _2). The results of −), 1.4 ppm, 1.6 ppm (m, 8H, —CH ₂ —) were obtained, and the following structure was confirmed.

[Comparative Example 2]
<Synthesis of unsaturated crystalline polyester resin 5>
Sebacic acid (64 parts by mass, manufactured by Wako Pure Chemical Industries, Ltd.), cis, trans mixed-2-butene-1,4-diol (26 parts by mass, molar ratio cis: trans = 32: 68, manufactured by Tokyo Chemical Industry Co., Ltd.) Orgatics TC-400 (0.50 parts by mass, manufactured by Matsumoto Fine Chemicals) was placed in a three-necked flask and heated and stirred at 180 ° C. for 2 hours under a nitrogen stream. Further, the mixture was heated and stirred at 200 to 700 Pa and 180 ° C. for 3 hours. After completion of the reaction, the reaction solution was poured into a beaker (600 parts by mass of methanol) to precipitate crystals. The crystals were collected by suction filtration and washed with 240 parts by mass of methanol. This crystal was vacuum-dried at 40 ° C. for 18 hours to obtain 65 parts by mass of unsaturated crystalline polyester resin 5. The melting point was 61 ° C. The weight average molecular weight of this resin was 9,500. When the ¹ H-NMR spectrum of the resin was measured with a Varian, 300 MHz, CDCl ₃ solution, δ 5.85 ppm (m, 2H, transbutenediol = CH—CH =), 5.75 ppm (m, 2H, cis butenediol = CH-CH =), 4.7ppm (d, 4H, cis butenediol _{-CH 2 -), 4.6ppm (d} , 4H, trans butenediol _{-CH 2 -), 2.35ppm (m} , 8H, sebacic acid _{- (O =) C-CH} 2 -), 1.6ppm (m, 8H, sebacic acid _{- (O =) C-CH} 2 -CH 2 -), 1.3ppm (m, 16H, sebacic acid -CH 2 _-) results were obtained, it was confirmed that the following structure.

<Evaluation>
[Melting point]
The melting point was determined by differential scanning calorimetry (DSC). The temperature was raised to 200 ° C. at 10 ° C./min with a differential scanning calorimeter (product name: DSC-50) manufactured by Shimadzu Corporation, then cooled with liquid nitrogen, heated again at 10 ° C./min, and then absorbed. The maximum peak was taken as the melting point. The results are shown in Table 1.

As for UV reactivity, 83 parts by mass of unsaturated crystalline polyester resin, 10 parts by mass of thiol compound (manufactured by Showa Denko KK, trade name: Karenz MTPE-1, tetrafunctional, pentaerythritol), photopolymerization initiator 7 parts by mass (trade name Irgacure 819, manufactured by BASF Corporation) was mixed, and these were made into a 5% by mass solution with THF. This 5% THF solution was dropped on a petri dish, and then the THF was removed at 90 ° C. on a hot plate to form a film to 100 mg / cm ² . A cured film was produced by UV irradiation at 90 ° C. with ultraviolet light of 6.4 mW / cm ² for 60 seconds and a distance of 10 cm from the light source. The haze value of the obtained UV cured film was measured using a Nippon Denshoku Industries Co., Ltd. product, a haze meter (NDH2000 type) under the condition that all rays were transmitted to the petri dish. It was judged that the lower the haze value, the more transparent the film and the better the UV reactivity. Evaluation was made according to the following criteria. The results are shown in Table 1.
○: Haze value 0.1 or more and less than 10 Δ: Haze value 10 or more and less than 30 ×: Haze value 30 or more

  As described above, the resin of the example had a lower melting point and excellent photopolymerization than the resin of the comparative example.

Claims (2)

The unsaturated aliphatic dicarboxylic acid and the unsaturated aliphatic diol are polycondensed, the melting point is in the range of 40 ° C. or higher and 90 ° C. or lower, and the weight average molecular weight is 10,200 or higher.
The unsaturated crystalline polyester resin, wherein the unsaturated aliphatic diol is a mixture of a cis isomer and a trans isomer.   The unsaturated aliphatic dicarboxylic acid is an unsaturated aliphatic dicarboxylic acid having 4 to 8 carbon atoms, and the unsaturated aliphatic diol is an unsaturated aliphatic diol having 2 to 8 carbon atoms. The unsaturated crystalline polyester resin according to claim 1.