KR20120106987A - Partially esterified epoxy resin and process for production thereof - Google Patents

Abstract

The present invention provides a method for producing a partial esterified epoxy resin, a partial esterified epoxy resin, and its use, which can remove the catalyst residue to a predetermined value or less by relatively simple means, and are excellent in storage stability and electrical properties. . A method of producing a partially esterified epoxy resin comprising a step of reacting a polyfunctional epoxy resin with (meth) acrylic acid in the presence of a polymer supported basic catalyst, and a step of removing the polymer supported basic catalyst to obtain a partial esterified epoxy resin. . Furthermore, in the presence of a polymer supported basic catalyst, a partially esterified epoxy obtained by reacting (meth) acrylic acid with a polyfunctional epoxy resin and removing the polymer supported basic catalyst, wherein the content of basic atoms derived from the polymer supported basic catalyst is 50 ppm or less. Resin.

Description

Partial esterification epoxy resin and its manufacturing method {PARTIALLY ESTERIFIED EPOXY RESIN AND PROCESS FOR PRODUCTION THEREOF}

The present invention relates to a partially esterified epoxy resin obtained by reacting a polyfunctional epoxy resin with (meth) acrylic acid in the presence of a polymer supported basic catalyst and a method for producing the same.

The partially esterified epoxy resin can be polymerized by active energy rays such as ultraviolet rays, heat, or both means, and mechanical strength is exhibited at room temperature even if not completely cured. Therefore, partially esterified epoxy resin is used effectively as raw materials, such as sealing material of a product which requires positioning in a process. Specifically, it is used as raw materials, such as the sealing material of an liquid crystal panel, an electrical component coating material, and the like.

Particularly, as a raw material of the sealing material used for the processing process which requires the precision of micrometer unit like a liquid crystal panel, a partially esterified epoxy resin is used effectively. The sealing material containing a partially esterified epoxy resin as a raw material can restrict the position shift at the time of processing to the minimum, and can form a liquid crystal panel.

However, when the partial esterification epoxy resin contains a large amount of impurities such as catalyst residues used in the production of the partial esterification epoxy resin, curing proceeds gradually with the remaining catalyst, causing thickening and gelation to occur, and storage. Stability is lowered.

In order to remove the remaining catalyst, the method of washing | cleaning a partial esterified epoxy resin using organic solvents, such as methanol, is proposed (patent document 1).

Moreover, in order to improve storage stability, the method of oxidizing and inactivating the catalyst which remain | survives in a partially esterified epoxy resin is proposed (patent document 2, 3).

A method of treating a catalyst composed of a tertiary phosphine derivative remaining in a partially esterified epoxy resin with a strong acidic ion exchange resin has been proposed. (Patent Document 4).

In addition, the method of improving the storage stability of a partially esterified epoxy resin is proposed by using tertiary amine as a catalyst and adding a polymerization inhibitor (patent document 5).

Japanese Patent Laid-Open No. 5-295087 Japanese Patent Laid-Open No. 5-320312 Japanese Patent Laid-Open No. 2002-145984 Japanese Patent Laid-Open No. 11-12345 Japanese Patent Laid-Open No. 2004-244543

However, in the method of removing the catalyst used at the time of washing | cleaning like patent document 1, the washing process using a solvent needs to be repeated several times, and the partial ester which is sufficiently high purity from a viewpoint of the electrical property mentioned later still. It is difficult to obtain a hydrogenated epoxy resin.

In addition, as in Patent Literatures 2 to 3, as a method of oxidizing and deactivating the catalyst, the catalyst deactivated remains in the partially esterified epoxy resin, and the coloring problem and the problem of lowering the electrical characteristics are improved. It is not.

As in Patent Literature 4, as a method of removing a catalyst using a strongly acidic ion exchange resin, it is necessary to use an auxiliary solvent such as dimethyl diglycol in order to efficiently remove the catalyst, and the production cost increases for the solvent removal. In addition, it is difficult to obtain a sufficiently high purity partially esterified epoxy resin from the viewpoint of electrical properties.

In addition, as in the method of adding the polymerization inhibitor, as in Patent Document 5, since the deactivated catalyst and the polymerization inhibitor remain in the partially esterified epoxy resin, there is no improvement in the problem of lowering the electrical properties.

In such a prior art, the storage stability has been substantially succeeded and commercialized. However, in the field of dropping sealing materials for liquid crystal panels, the characteristics required for the sealing materials have also been accompanied by the recent higher image quality and higher performance of liquid crystal displays. It's getting stricter.

MEANS TO SOLVE THE PROBLEM In order to improve the characteristic calculated | required by the dripping sealing material for liquid crystal panels, these inventors focused on the electrical property of the partial esterified epoxy resin which is a main component of a sealing material, and earnestly examined, and the electrical property of a partial esterified epoxy resin and a raw material epoxy resin was examined. It is preferable that the characteristic does not change as much as possible, and in order to do so, it has been found that it is necessary to remove impurities derived from the basic catalyst remaining in the partially esterified epoxy resin, and the present invention has been reached.

In the method for producing a liquid crystal panel by the dropping method, the sealing material is UV cured and heat cured while being in contact with the liquid crystal in an uncured state. Therefore, when impurities, such as a catalyst residue and a polymerization inhibitor, remain in a partial esterification epoxy resin, the impurity etc. derived from a catalyst elute and diffuse from a sealing material to a liquid crystal panel in the process of hardening, and the electrical characteristics of a liquid crystal panel Causes deterioration.

The drive frequency of a liquid crystal panel is currently 30-120 Hz, and the liquid crystal panel using the drive frequency of 240 Hz is developed recently. Thus, since a liquid crystal panel is an electric field drive type device, when the impurity eluted from the sealing material to the liquid crystal panel becomes an electric field response substance which can respond in the range of 240 Hz from a direct current | flow region, it is large in the characteristic of a liquid crystal panel. affect.

Changes in liquid crystal panel characteristics are broadly divided and shown as changes in electrical characteristics and display characteristics. The change of the electrical characteristic of a liquid crystal panel can be confirmed by the change of the voltage retention which power consumption relates. Voltage retention is related to the leakage current of a liquid crystal panel, and changes with presence of charged particles, such as an ionic substance eluted to a liquid crystal panel.

The change in the display characteristics of the liquid crystal panel is caused by, for example, luminance unevenness of the liquid crystal panel to which the response speed relates. The luminance nonuniformity of a liquid crystal panel arises in connection with the characteristic peculiar to a liquid crystal which has dielectric anisotropy and a threshold voltage, and is influenced by the presence of charged particles, such as an ionic substance eluted to a liquid crystal panel, and dielectric dipoles.

The electrical characteristics and display characteristics of such a liquid crystal panel can be evaluated by measuring a dielectric characteristic. If impurities in the partially esterified epoxy resin are present as electric field response materials (dielectric materials and charged particles), the dielectric properties (impedance, capacitance and phase angle θ) are changed when the frequency is changed in the range of 240 Hz from the direct current region. .

In the dielectric characteristics, impedance represents resistance to an alternating current signal, in other words, current flows easily, and a decrease in impedance results from an increase in leakage current and a drop in voltage retention.

Capacitance in dielectric characteristics indicates that capacitance, in other words, electricity is easily accumulated. The capacitance depends on the space charge polarization and the orientation polarization of the dielectric material sandwiched by the electrodes, and the change in the numerical value of the capacitance indicates a change in the holding capacitance of the liquid crystal single cell, and indicates a variation in the characteristics of the liquid crystal panel.

In the dielectric characteristic, the phase angle θ represents the phase difference between the voltage and the current. When the phase angle is shifted from -90 ° to 0 °, it indicates that energy loss is occurring, and the change in the phase angle θ is caused by a decrease in the voltage holding ratio and a delay in the response speed.

The change in the dielectric properties of such a liquid crystal panel can be predicted by measuring the dielectric properties (impedance, capacitance and phase angle θ) of the partially esterified epoxy resin used as the raw material of the sealing material.

Since the partially esterified epoxy resin has a structure having a vinyl group, an ester bond, a hydroxyl group, or the like, the polarity is increased, and when the measurement temperature is high, the impedance is lowered, the capacitance is increased, and the phase angle θ is shifted. Therefore, the dielectric properties (impedance, capacitance and phase angle θ) of the partially esterified epoxy resin to be measured can be confirmed by comparing the dielectric properties of the raw material resin or the pure partially esterified epoxy resin with various measurement temperatures. . When the dielectric properties (impedance, capacitance and phase angle θ) of the partial esterified epoxy resin to be compared are small with respect to the dielectric properties of the reference raw material resin or the pure partially esterified epoxy resin, the electrical characteristics are excellent. It can be confirmed that it is a partially esterified epoxy resin.

In order to obtain the partial esterified epoxy resin excellent in electrical characteristics, it is required to manufacture the partial esterified epoxy resin of much higher purity than what is obtained by the conventional method. In order to realize this, the present inventors, in the method of producing a partially esterified epoxy resin by reacting a polyfunctional epoxy resin with (meth) acrylic acid, using a polymer supported basic catalyst and filtering the polymer supported basic catalyst after the reaction. By centrifugation and removal, a high-purity partially esterified epoxy resin having excellent electrical properties is obtained, and in particular, it is found that storage stability is also excellent without adding a polymerization inhibitor, thereby completing the present invention.

That is, this invention is as follows.

[1] a partial ester comprising the step of reacting a polyfunctional epoxy resin with (meth) acrylic acid in the presence of a polymer-supported basic catalyst, and a step of removing the polymer-supported basic catalyst to obtain a partial esterified epoxy resin. Process for the production of hydrogenated epoxy resins.

[2] The method for producing a partially esterified epoxy resin according to the above [1], wherein the basic catalyst of the polymer-supported basic catalyst is a trivalent organophosphorus compound and / or an amine compound.

[3] In the step of reacting the polyfunctional epoxy resin with (meth) acrylic acid, [1] or [1] or 10 to 90 equivalent% of (meth) acrylic acid is reacted with 1 equivalent of the epoxy group of the polyfunctional epoxy resin. The manufacturing method of the partially esterified epoxy resin as described in 2].

[4] The method for producing a partially esterified epoxy resin according to any one of [1] to [3], wherein filtration or centrifugation is used in the step of removing the polymer-supported basic catalyst.

[5] obtained by reacting (meth) acrylic acid with a polyfunctional epoxy resin in the presence of a polymer-supported basic catalyst and removing the polymer-supported basic catalyst, wherein the content of basic atoms derived from the polymer-supported basic catalyst is 50 ppm or less; Partially esterified epoxy resin.

[6] A curable composition comprising the partially esterified epoxy resin according to the above [5].

According to the present invention, by removing the polymer-supported basic catalyst by a relatively simple physical means, a method for producing a partial esterified epoxy resin having excellent electrical properties and excellent storage stability even without adding a polymerization inhibitor, partial esterification An epoxy resin and the curable composition using the same can be provided.

1 is a graph showing a relationship between a measurement frequency and an impedance at 25 ° C. of a raw material resin and a partially esterified epoxy resin (Example 1, Comparative Example 1).
FIG. 2 is a graph showing the relationship between the measurement frequency and the capacitance at 25 ° C. of the raw material resin and the partially esterified epoxy resin (Example 1, Comparative Example 1). FIG.
3 is a graph showing the relationship between the measurement frequency and phase angle θ at 25 ° C. of the raw material resin and the partially esterified epoxy resin (Example 1, Comparative Example 1).
4 is a graph showing the relationship between the measurement frequency and the impedance at 50 ° C. of the raw material resin and the partially esterified epoxy resin (Example 1, Comparative Example 1).
5 is a graph showing the relationship between the measurement frequency and the capacitance at 50 ° C. of the raw material resin and the partially esterified epoxy resin (Example 1, Comparative Example 1).
6 is a graph showing the relationship between the measurement frequency and phase angle θ at 50 ° C. of the raw material resin and the partially esterified epoxy resin (Example 1, Comparative Example 1).
7 is a graph showing the relationship between the measurement frequency and the impedance at 80 ° C of the raw material resin and the partially esterified epoxy resin (Example 1, Comparative Example 1).
8 is a graph showing the relationship between the measurement frequency and the capacitance at 80 ° C of the raw material resin and the partially esterified epoxy resin (Example 1, Comparative Example 1).
9 is a graph showing the relationship between the measurement frequency and phase angle θ at 80 ° C. of the raw material resin and the partially esterified epoxy resin (Example 1, Comparative Example 1).
FIG. 10 is a graph showing the relationship between the content of phosphorus atoms and capacitance contained in each resin at each frequency. FIG.
11 is a graph showing the relationship between the content of phosphorus atoms contained in each resin at each frequency and the phase angle θ.

EMBODIMENT OF THE INVENTION Hereinafter, preferred embodiment of this invention is described.

The present invention provides a partial ester comprising a step of reacting a polyfunctional epoxy resin with (meth) acrylic acid in the presence of a polymer supported basic catalyst, followed by removing a polymer supported basic catalyst to obtain a partially esterified epoxy resin. It is a manufacturing method of a oxidized epoxy resin.

Although a polyfunctional epoxy resin will not be specifically limited if it is an epoxy resin which has two or more epoxy groups in 1 molecule, The following compounds are mentioned as a polyfunctional epoxy resin.

As polyfunctional epoxy resins, polyhydric compounds such as polyalkylene glycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, dimethylol propane, trimethylol propane, spiroglycol, glycerin and the like And aliphatic polyvalent glycidyl ether compounds obtained by reacting alcohols with epichlorohydrin.

As a polyfunctional epoxy resin, aromatic diols, such as bisphenol A, bisphenol S, bisphenol F, bisphenol AD, and aromatic polyhydric glycol obtained by reacting them with ethylene glycol, propylene glycol, alkylene glycol-modified diol, and epichlorohydrin A cyl ether compound is mentioned.

As a polyfunctional epoxy resin, aromatic dicarboxylic acids, such as aliphatic polyhydric glycidyl ester compound obtained by reacting aromatic dicarboxylic acid, such as adipic acid and itaconic acid, with epichlorohydrin, isophthalic acid, terephthalic acid, and pyromellitic acid; And aromatic polyvalent glycidyl ester compounds obtained by reacting epichlorohydrin.

And aromatic polyvalent glycidylamine compounds obtained by reacting epichlorohydrin with aromatic amines such as diaminodiphenylmethane, aniline, and methaxylylenediamine.

Examples of the polyfunctional epoxy resin include hydantoin-type polyvalent glycidyl compounds obtained by reacting hydantoin and its derivatives with epichlorohydrin.

As a polyfunctional epoxy resin, the phenol resin derived from phenol or cresol, formaldehyde, the phenol obtained by making a novolak resin, and epichlorohydrin react, and a novolak-type polyhydric glycidyl ether compound are mentioned.

It does not specifically limit as (meth) acrylic acid, For example, commercially available acrylic acid or methacrylic acid can be used.

In the step of reacting the polyfunctional epoxy resin with the (meth) acrylic acid, the (meth) acrylic acid to be reacted with respect to 1 equivalent of the epoxy group of the polyfunctional epoxy resin is preferably 10 to 90 equivalent%, more preferably 20 to 80 equivalent%, More preferably, it is 30-70 equivalent%, Especially preferably, it is 40-60 equivalent%.

When (meth) acrylic acid is reacted within the above range with respect to 1 equivalent of the epoxy group of the polyfunctional epoxy resin, resin properties favorable for temporary fixing are obtained during the first polymerization in which only unsaturated groups are reacted, and phase separation is carried out during the secondary polymerization. It is possible to obtain a partially esterified epoxy resin capable of forming a homogeneous polymer without generating such a material.

A polymer supported basic catalyst means what carried the basic catalyst used at the process of making a polyfunctional epoxy resin and (meth) acrylic acid react on a polymer.

As a basic catalyst, it is preferable that they are a trivalent organophosphorus compound and / or an amine compound. The basic atom of a basic catalyst is phosphorus and / or nitrogen.

Examples of the trivalent organophosphorus compound include alkylphosphines such as triethylphosphine, tri-n-propylphosphine and tri-n-butylphosphine and salts thereof, triphenylphosphine, tri-m-tolylphosphine and tris Aryl phosphines such as-(2,6-dimethoxyphenyl) phosphine and salts thereof; phosphorous acid triesters such as triphenyl phosphite, triethyl phosphite, tris (nonylphenyl) phosphite and salts thereof; Can be. As a salt of a trivalent organophosphorus compound, a triphenyl phosphine ethyl bromide, a triphenyl phosphine butyl bromide, a triphenyl phosphine octyl bromide, a triphenyl phosphine decyl bromide, a triphenyl phosphine isobutyl bromide, Triphenyl phosphine propyl chloride, triphenyl phosphine pentyl chloride, triphenyl phosphine hexyl bromide and the like. Especially, triphenylphosphine is preferable.

As the amine compound, tertiary amines such as secondary amines such as diethanolamine, triethanolamine, dimethylbenzylamine, trisdimethylaminomethylphenol, trisdiethylaminomethylphenol, and 1,5,7-triazabicyclo [ 4.4.0] Deca-5-ene (TBD), 7-methyl-1,5,7-triazabicyclo [4.4.0] deca-5-ene (Me-TBD), 1,8-diazabicyclo [ 5.4.0] undec-7-ene (DBU), 6-dibutylamino-1,8-diazabicyclo [5.4.0] undec-7-ene, 1,5-diazabicyclo [4.3.0 ] Strong base amines, such as nona-5-ene (DBN) and 1,1,3,3- tetramethylguanidine, and its salt are mentioned. Especially, 1,5,7-triazabicyclo [4.4.0] deca-5-ene (TBD) is preferable. As a salt of an amine compound, benzyl trimethyl ammonium chloride and benzyl triethyl ammonium chloride are mentioned.

As a polymer which carries a basic catalyst, it does not specifically limit, The polymer which crosslinked polystyrene by divinylbenzene, the polymer which crosslinked the acrylic resin with divinylbenzene, etc. are used. Such a polymer is insoluble in the solvent (for example, methyl ethyl ketone, methyl isobutyl ketone, toluene, etc.), a raw material, and a product which are used for reaction of a polyfunctional epoxy resin and (meth) acrylic acid.

The polymer-supported basic catalyst is methylethyl by chemically bonding the basic catalyst to the insoluble polymer or introducing the basic catalyst into the monomer, polymerizing the monomer, and then crosslinking three-dimensionally with a crosslinking monomer such as divinylbenzene. A polymer supported basic catalyst insoluble in a solvent such as ketone, methyl isobutyl ketone, toluene, or the like can be produced.

Specific examples of the polymer-supported basic catalyst include diphenylphosphinopolystyrene, 1,5,7-triazabicyclo [4.4.0] deca-5-ene polystyrene, N, N- (diisopropyl) aminomethylpolystyrene, N- (methyl polystyrene) -4- (methyl amino) pyridine, etc. are mentioned. These polymer-supported basic catalysts may be used alone or in combination of two or more.

A commercially available polymer-supported basic catalyst may be used. Commercially available polymer-supported basic catalysts include, for example, PS-PPh ₃ (diphenylphosphinopolystyrene, manufactured by Biotage), PS-TBD (1,5,7-triazabicyclo [4.4.0] deca-5- N polystyrene and the Biotage company make) are mentioned.

It is preferable that the basic catalyst of a polymer supported basic catalyst is 0.5-5.0 milliliter equivalents, and, as for the usage ratio of a polymer supported basic catalyst, it is more preferable that it is 1.0-3.0 milliliter equivalents with respect to 1 equivalent of epoxy of a polyfunctional epoxy resin. It is preferable from a viewpoint of reaction rate, reaction time, and a catalyst cost, if the use ratio of a polymer carrying basic catalyst is in the said range.

In the manufacturing method of this invention, the temperature in the reaction process of a polyfunctional epoxy resin and (meth) acrylic acid becomes like this. Preferably it is 60-120 degreeC, More preferably, it is 80-120 degreeC, More preferably, it is 90-110 degreeC to be.

When the polyfunctional epoxy resin is reacted with (meth) acrylic acid in the presence of a catalyst, it is necessary to appropriately maintain the oxygen concentration in the gas phase in the reaction system and on the reaction system in order to prevent gelation. For example, if air is actively blown into the reaction system, the catalyst may be oxidized and the activity may be lowered, so care must be taken.

The reaction of the polyfunctional epoxy resin with the (meth) acrylic acid is preferably performed in a container that shields ultraviolet rays since the partially esterified epoxy resin obtained by this reaction is cured by active energy rays such as ultraviolet rays. Do. The reaction between the polyfunctional epoxy resin and (meth) acrylic acid may be performed in the presence of a reflux solvent that exhibits good solvent resistance to the epoxy resin in order to prevent gas phase polymerization. In this case, the solvent may be removed after completion of the reaction. Since it is necessary, it is preferable to carry out by a solvent. Acetone, methyl ethyl ketone, etc. are mentioned as a reflux solvent.

In the production method of the present invention, the polymer-supported basic catalyst is removed after the polyfunctional epoxy resin is reacted with (meth) acrylic acid. As a method of removing a polymer supported basic catalyst, it is preferable to use filtration or centrifugation.

As a method of filtering a polymer supported basic catalyst, the method of filtering a polymer supported basic catalyst using 10 micrometers of nylon mesh NY-10HC (made by Sefar, Switzerland) is mentioned, for example.

As a method of centrifuging a polymer carrying basic catalyst, the method of removing a polymer carrying basic catalyst by solid-liquid separation using a centrifugal separator is mentioned.

According to the production method of the present invention, by removing the polymer-supported basic catalyst by a relatively simple method such as filtration or centrifugation, it is possible to obtain a high-purity partially esterified epoxy resin containing almost no polymer-supported basic catalyst.

According to the production method of the present invention, since the polymer-supported basic catalyst is removed by a relatively simple physical method such as filtration or centrifugation, the production method is compared with a method using a conventional cleaning solvent or a polymerization inhibitor for inactivating the catalyst. The cost can be reduced.

The partial esterified epoxy resin of the present invention is made by reacting a polyfunctional epoxy resin with (meth) acrylic acid in the presence of a polymer supported basic catalyst to remove a polymer supported basic catalyst, and a basic atom derived from a polymer supported basic catalyst. The content of is 50 ppm or less.

The partial esterified epoxy resin of the present invention has a low content of basic atoms derived from the polymer-supported basic catalyst at 50 ppm or less, and is excellent in electrical characteristics as compared with the partially esterified epoxy resin obtained by a conventional method. In addition, the partially esterified epoxy resin of the present invention has a low content of basic atoms derived from the polymer-supported basic catalyst, which is 50 ppm or less, and does not require the addition of a polymerization inhibitor in the reaction step. It is excellent in storage stability compared with the partially esterified epoxy resin which added the polymerization inhibitor in order to activate.

The partial esterified epoxy resin preferably has few impurities, and the content of the basic atoms derived from the polymer-supported basic catalyst is preferably 40 ppm or less, more preferably 30 ppm or less, still more preferably 20 ppm or less, particularly preferably Is 10 ppm or less.

The basic atom derived from a polymer carrying basic catalyst is phosphorus, nitrogen, etc. specifically ,. By measuring the content of such basic atoms contained in the partially esterified epoxy resin, the residual amount of the polymer-supported basic catalyst residue in the partially esterified epoxy resin can be estimated. The basic atom of the polymer-supported basic catalyst can be measured by inductively coupled plasma emission spectrometry (ICP / AES).

The curable composition of the present invention is made by reacting (meth) acrylic acid with a polyfunctional epoxy resin in the presence of a polymer supported basic catalyst and removing a polymer supported basic catalyst, and the content of basic atoms derived from the polymer supported basic catalyst is 50 ppm. The partial esterified epoxy resin which is the following is included.

The said hardening composition can superpose | polymerize by energy rays or heat, such as an ultraviolet-ray, and can obtain hardened | cured material.

The curable composition of the present invention has a low content of the basic atoms of the polymer-supported basic catalyst to 50 ppm or less, and includes a partially esterified epoxy resin containing almost no polymer-supported basic catalyst residue and a polymerization inhibitor, and thus the catalyst residue and polymerization. It does not generate oxidation products by inhibitors, and is excellent in electrical properties and storage stability. Therefore, the curable composition of this invention can be used suitably as a dripping sealing material for liquid crystal panels, the coating material of an electrical component, etc. which an electric characteristic and a pollution become a problem.

Example

Next, although the specific form of this invention is demonstrated in detail by an Example, this invention is not limited by these examples.

Example 1

A 500 ml glass sand dune flask equipped with a stirrer, a thermometer, and a reflux condenser was prepared, and 340 g (2.0 equivalents / epoxy group) of bisphenol A epoxy resin; , PS-PPh ₃ (diphenylphosphinopolystyrene, 2.0 mmol / g) [manufactured by Biotaji Co., Ltd.] 750 mg (1.5 mmol equivalent / TPP (triphenylphosphine) catalyst amount (g)) were mixed, and the acid value was 1.0 at 100 ° C. The reaction was stirred until the KOHmg / g or less. Cooling the reaction solution to 60 ℃, and the scale of 10μm nylon mesh to remove the NY-10HC (Switzerland three Parr Co.) catalyst, PS-PPh ₃ to obtain a partially esterified epoxy resin (PR-1). The epoxy equivalent of obtained resin was 468g / eq. After the wet decomposition of the resin (PR-1), the content of phosphorus atoms in the resin (PR-1) measured by inductively coupled plasma emission spectrometry (ICP / AES) was 2 ppm or less.

[Example 2]

A partially esterified epoxy resin (PR-2) was obtained in the same manner as in Example 1 except that 326 g (2.0 equivalents / epoxy group) of bisphenol AD type epoxy resin; EPOMIK R1710 [manufactured by Purin Tech Co., Ltd.] was used. The epoxy equivalent of obtained resin (PR-2) was 450 g / eq. Content of the phosphorus atom in resin (PR-2) measured similarly to Example 1 was 2 ppm or less.

[Example 3]

Stirrer, thermometer, reflux prepare a four-necked glass flask of 500ml equipped with a cooling tube, and a bisphenol A type epoxy resin; epi clones EXA850CRP [DIC Co., Ltd.] to 340g (2.0 equivalent / epoxy _{group), PS-PPh 3 (2.0mmol} / g ) [Biotaji company] 750 mg (1.5 milliliter equivalents of / TPP [triphenylphosphine] catalyst amount (g)), PS-TBD (1,5,7-triazabicyclo [4.4.0] deca-5-ene polystyrene, 1.40 mmol / g) (manufactured by Biotaji Co., Ltd.) 1.07 g (1.5 mmol equivalent / amine catalyst amount (g)) were mixed and reacted while slowly adding 76.0 g (1.0 equivalent) of acrylic acid over 6 hours while stirring at 100 ° C. . The addition of acrylic acid was completed, and the reaction was further stirred at 100 ° C until the acid value became 1.0 KOHmg / g or less. Cooling the reaction solution to 60 ℃ and scale 10μm nylon mesh NY-10HC (Switzerland three Parr Corp.) to remove the PS-PPh ₃ and PS-TBD of catalytic partial esters screen to give the epoxy resin (PR-3). The epoxy equivalent of obtained resin (PR-3) was 461g / eq. Content of the phosphorus atom in resin (PR-3) measured similarly to Example 1 was 2 ppm or less.

Comparative Example 1

A 500 ml glass sand dune flask equipped with a stirrer, an air inlet tube, a thermometer, and a reflux cooling tube was prepared, and 340 g (2.0 equiv / epoxy) of bisphenol A epoxy resin; Epiclon EXA850CRP [DIC Corporation], 90.4 g of methacrylic acid (1.0 equiv), TPP (triphenylphosphine) [manufactured by Tokyo Kasei Co., Ltd.] 0.5 g (1.9 mmol equivalent), 25 mg of hydroquinone and 100 mg of p-methoxy phenol as a polymerization inhibitor were mixed, and the acid value was 1.0 KOHmg at 100 ° C. It was made to react by stirring until it became / g or less. After completion | finish of reaction, it oxidized at 80 degreeC for 2 hours, blowing air into a liquid, and obtained partially esterified epoxy resin (KR-1). The epoxy equivalent of obtained resin (KR-1) was 465g / eq. Content of phosphorus atom in resin (KR-1) measured in the same manner as in Example 1 was 290 ppm.

Comparative Example 2

The reaction was carried out in the same manner as in Comparative Example 1 except that 25 mg of hydroquinone and 100 mg of p-methoxy phenol were not added, but gelated in the middle of the reaction.

About the partially esterified epoxy resin of Examples 1-4 and Comparative Example 1, the heat stability test and the reduced pressure heating promotion test were done as follows.

[Heating Stability Test]

50 g of each partially esterified epoxy resin was put in a 100 ml brown polyethylene container, plugged, left to stand in an oven at 60 ° C., and taken out after 20 hours, 200 hours, and 500 hours. The viscosity was measured at 2.5 rpm of the rotation speed of a cone rotor using (RE105U by the Tokko Sangyo Co., Ltd.). The change rate at the time of making the viscosity immediately after manufacture 100 is calculated | required according to following formula (1). The results are shown in Table 1.

Viscosity Change Rate = (Measured Viscosity after Viscosity Period / Viscosity Immediately After Production)... (One)

[Decompression heating promotion test]

50 g of each partially esterified epoxy resin was placed in a 100 ml brown polyethylene container, without being capped, and stored in a container oven, 50 ° C. and a vacuum oven reduced to 100 Pa, and taken out after 20 hours, 200 hours, and 500 hours. The viscosity was measured at 2.5 rpm of the rotation speed of a cone rotor using the E-type viscosity meter (RE105U by the AX KK). The change rate at the time of making the viscosity immediately after manufacture 100 is calculated | required according to said Formula (1). The results are shown in Table 1.

As shown in Table 1, the partial esterified epoxy resin of Examples 1-3 has little change in viscosity even if it passes 500 hours under the temperature of 60 degreeC, and it can confirm that it is excellent in storage stability also under a heating test. there was.

On the other hand, after 500 hours, the partial esterification epoxy resin of the comparative example 1 changed the viscosity nearly twice, and the heat stability fell.

In addition, as shown in Table 1, the partial esterification epoxy resin of Examples 1-3 has little change in viscosity even if it passes 500 hours under reduced pressure of 50 degreeC and 100 Pa, and also the storage stability also under the reduced pressure heating test. It was confirmed that it is excellent.

On the other hand, the partially esterified epoxy resin of Comparative Example 1 gelled after 500 hours.

Subsequently, the dielectric properties of the partially esterified epoxy resins of Example 1 and Comparative Example 1 were measured by the following method.

[Measurement of dielectric properties]

As a reference, bisphenol A epoxy resin as a raw material; Epiclone EXA850CRP (manufactured by DIC Corporation) was used. Using a dielectric measuring system 126096W [Solatron Co., Ltd.] and liquid electrode SR-C1R (cell capacity: 2 pF, distance between electrodes: 1 mm) [Toyo Technica Co., Ltd.], using a raw material resin (reference), Example Dielectric properties (impedance, capacitance, phase angle at 25 ° C., 50 ° C., and 80 ° C. when the frequency of 1.0 × 10 ⁻² Hz to 1.0 × 10 ⁶ Hz of the partially esterified epoxy resin of 1 and Comparative Example 1 were changed) θ) was measured. By evaluating the dielectric properties of the resin in the uncured state, the influence of impurities in the resin can be semi-quantified. The results are shown in FIGS. 1 to 9. In addition, in drawing, the notation, such as "1.0E-02", shows the meaning of 1.0x10 <^-2> .

As shown in Figs. 1 to 3, at 25 ° C, the dielectric properties (impedance, capacitance, and phase angle θ) of the partially esterified epoxy resin of Example 1 are almost the same as those of the raw material resin as a reference, There was no influence by impurities in the partially esterified epoxy resin, and it was confirmed that it had excellent electrical properties.

On the other hand, as shown in FIGS. 1-3, the dielectric properties of the partially esterified epoxy resin of the comparative example 1 changed with respect to the dielectric properties of raw material resin. That is, as shown in FIG. 1, the impedance of the comparative example 1 fell with respect to the impedance of raw material resin, and from this, it was confirmed that the voltage retention of the partially esterified epoxy resin of the comparative example 1 fell. 2, the capacitance of the comparative example 1 was changed with respect to the capacitance of the raw material resin, and from this, it was confirmed that the holding capacity of the partially esterified epoxy resin of the comparative example 1 was varied. In addition, as shown in FIG. 3, with respect to the phase angle (theta) of raw material resin, the phase angle (theta) of the comparative example 1 shift | deviates in the direction of -90 degree to 0 degree, From this, the partial esterified epoxy resin of the comparative example 1 The energy loss occurred, and it was confirmed that the delay such as the response speed occurred. As described above, the partial esterified epoxy resin of Comparative Example 1 was degraded in dielectric properties, and the lowering of the dielectric properties was caused by the influence of impurities contained in the partially esterified epoxy resin of Comparative Example 1.

As shown in FIGS. 4-9, when the measurement temperature rises to 50 degreeC and 80 degreeC, the dielectric properties (impedance, capacitance, and phase angle (theta)) of the partially esterified epoxy resin of Example 1 become a reference resin The dielectric properties of, although slightly changed, it was assumed that this is due to the influence of the intermolecular interaction by the vinyl group, ester structure, hydroxyl group and the like contained in the partially esterified epoxy resin due to the temperature rise. On the other hand, as shown in FIGS. 4-9, the dielectric properties of the partially esterified epoxy resin of the comparative example 1 changed largely from the dielectric properties of raw material resin, and the electrical property fell as temperature increased.

From the results shown in Figs. 1 to 9, the dielectric properties (impedance, capacitance, and phase angle θ) of the partially esterified epoxy resin of Example 1 were about the same as those of the raw material resin, and contained almost no impurities. Therefore, there was no change in dielectric properties due to the influence of impurities, and it was confirmed that it was a partially esterified epoxy resin having excellent electrical properties.

Example 4

As a catalyst, PS-PPh ₃ (diphenylphosphinopolystyrene, 2.0 mmol / g) [manufactured by Biota Co., Ltd.] 500 mg (1.33 mmol equivalent / TPP (triphenylphosphine) catalyst amount (g)) and TPP (triphenylphosphine) ) A partially esterified epoxy resin (PR-4) was obtained in the same manner as in Example 1 except that 160 mg (manufactured by Kanto Chemical Co., Ltd.) (0.61 mmol equivalent / TPP (triphenylphosphine) catalyst amount (g)) was used. . The epoxy equivalent of obtained resin was 458g / eq. Content of the phosphorus atom in resin (PR-4) measured similarly to Example 1 was 100 ppm.

[Example 5]

As a catalyst, PS-PPh ₃ (diphenylphosphinopolystyrene, 2.0 mmol / g) [manufactured by Biota Co., Ltd.] 650 mg (1.73 milliequivalents / TPP (triphenylphosphine) catalyst amount (g)) and TPP (triphenylphosphine) ) A partially esterified epoxy resin (PR-5) was obtained in the same manner as in Example 1 except that 80 mg (manufactured by Kanto Chemical Co., Ltd.) (0.31 mmol equivalent / TPP (triphenylphosphine) catalyst amount (g)) was used. . The epoxy equivalent of obtained resin was 466g / eq. Content of the phosphorus atom in resin (PR-5) measured similarly to Example 1 was 48 ppm.

[Example 6]

As a catalyst, PS-PPh ₃ (diphenylphosphinopolystyrene, 2.0 mmol / g) [manufactured by Biota Co., Ltd.] 700 mg (1.87 mmol equivalent / TPP (triphenylphosphine) catalyst amount (g)) and TPP (triphenylphosphine) ) A partially esterified epoxy resin (PR-6) was obtained in the same manner as in Example 1 except that 40 mg (manufactured by Kanto Chemical Co., Ltd.) (0.15 mmol equivalent / TPP (triphenylphosphine) catalyst amount (g)) was used. . The epoxy equivalent of obtained resin was 456g / eq. Content of phosphorus atom in resin (PR-6) measured in the same manner as in Example 1 was 26 ppm.

[Comparative Example 3]

After the completion of the reaction, a partial esterified epoxy resin (KR-2) was obtained in the same manner as in Comparative Example 1 except that the oxidation treatment was not performed at 80 ° C for 2 hours. The epoxy equivalent of obtained resin (KR-2) was 465g / eq. To 300 parts of this resin, 15 parts of ion exchange resin (umber list 15DRY (ion exchange resin with benzenesulfonic acid attached to the main chain, manufactured by Organo)) was added and stirred at 80 ° C for 3 hours. The reaction liquid was cooled to 60 degreeC, ion-exchange resin was removed by nylon mesh NY-10HC (Switzerland Separ company) of scale 10micrometer, and the partial esterification epoxy resin (KR-3) was obtained. Content of the phosphorus atom in resin (KR-2 and KR-3) measured similarly to Example 1 was 300 ppm and 250 ppm, respectively. From this result, even when a strongly acidic ion exchange resin was used, the obtained partial ester epoxy resin contained relatively many impurities (phosphorus atoms) derived from the catalyst, and it was confirmed that the effect of reducing impurities derived from the catalyst was small. there was.

Partial esterified epoxy resin of Example 1 (content of phosphorus atom: 2 ppm or less), partial esterified epoxy resin of Example 4 (content of phosphorus atom: 100 ppm), part of Example 5 Esterified epoxy resin (PR-5: content of phosphorus atom: 48 ppm), partial esterified epoxy resin of Example 6 (PR-6: content of phosphorus atom: 26 ppm) and partially esterified epoxy resin of Comparative Example 3 (KR -2: Content of phosphorus atom: 300 ppm) By the measurement of said dielectric characteristic, the capacitance of the frequency of 10mHz-100Hz, and the phase angle of the frequency of 50Hz-10KHz were measured at the measurement temperature of 50 degreeC. The relationship between the content of phosphorus atoms and the capacitance contained in each resin at each frequency is shown in FIG. 10, and the relationship between the content of the phosphorus atoms contained in each resin at each frequency and the phase angle θ is shown in FIG. 11.

As shown in FIG. 10, it can be seen that the change in capacitance (holding capacity) is significantly reduced when the impurity contained in the partially esterified epoxy resin, that is, the phosphorus atom content is 50 ppm or less, which is the inflection point. In particular, when the measurement is performed at a low frequency of 200 mHz or less, the change in capacitance (holding capacity) is remarkable because the low frequency has a slower voltage change than when measured at a high frequency. Therefore, as shown in FIG. 10, when measured by the low frequency of 200 mHz or less, the partial esterified epoxy resin whose content of phosphorus atom is 50 ppm or less is more capacitance than the partial esterified epoxy resin whose content of phosphorus atom exceeds 50 ppm. It can be confirmed that the change in the (holding capacity) is remarkably small, and the dielectric properties do not change.

As shown in FIG. 11, in 50 ppm or less partially esterified epoxy resin whose content of phosphorus atom is an inflection point, the change of phase angle (theta) shifted from -90 degrees to 0 degrees is small, and voltage fall rate and response speed are small. It is confirmed that the delay is small and has excellent dielectric properties. In particular, when measured in the direct current range (0 Hz) to the low frequency region (for example, the region of 50 Hz to 200 Hz, as shown in FIG. 11) applied to the recent liquid crystal panel, the content of phosphorus atoms is 50 ppm or less. Partially esterified epoxy resins are markedly smaller in change in phase angle θ than partial esterified epoxy resins having a phosphorus atom content of more than 50 ppm, and thus, energy loss does not occur and it can be confirmed that they have excellent dielectric properties. have.

 Industrial Applicability

The partially esterified epoxy resin obtained by the production method of the present invention is stable and can be stored for a long time, and has excellent stability and electrical properties under reduced pressure conditions, and can be polymerized by any of active energy rays such as ultraviolet rays and heat. Since it can use as a raw material, it is useful as raw materials, such as a sealing material of liquid crystal panels, an electrical component paint, etc.

Claims (6)

Reacting the polyfunctional epoxy resin with (meth) acrylic acid in the presence of a polymer-supported basic catalyst, and
A process of removing the polymer-supported basic catalyst to obtain a partially esterified epoxy resin
Method for producing a partially esterified epoxy resin, characterized in that it comprises a. The method for producing a partially esterified epoxy resin according to claim 1, wherein the basic catalyst of the polymer-supported basic catalyst is a trivalent organophosphorus compound and / or an amine compound. The process for reacting a polyfunctional epoxy resin with (meth) acrylic acid according to claim 1 or 2, wherein 10 to 90 equivalent% of (meth) acrylic acid is reacted with respect to 1 equivalent of the epoxy group of the polyfunctional epoxy resin. , Method for producing partially esterified epoxy resin. The method for producing a partially esterified epoxy resin according to any one of claims 1 to 3, wherein filtration or centrifugation is used in the step of removing the polymer-supported basic catalyst. Partial esterification, obtained by reacting (meth) acrylic acid with a polyfunctional epoxy resin in the presence of a polymer supported basic catalyst and removing the polymer supported basic catalyst, wherein the content of basic atoms derived from the polymer supported basic catalyst is 50 ppm or less. Epoxy resin. Curable composition containing the partially esterified epoxy resin of Claim 5.

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