WO2024204557A1

WO2024204557A1 - Composition, reactive diluent, curable composition, and method for producing composition

Info

Publication number: WO2024204557A1
Application number: PCT/JP2024/012686
Authority: WO
Inventors: 純金田; 祐樹安藤
Original assignee: Ｋｈネオケム株式会社
Priority date: 2023-03-31
Filing date: 2024-03-28
Publication date: 2024-10-03

Abstract

The present invention provides a composition which contains a specific diglycidyl ether, has a reduced total amount of chlorine, and has excellent insulation reliability. The present invention pertains to a composition which contains a chlorine-containing compound and a diglycidyl ether represented by formula (1), wherein the total amount of chlorine is 900 ppm or less. In formula (1), X represents an alkylene group having 9 to 11 carbon atoms.

Description

Composition, reactive diluent, curable composition and method for producing the composition

The present invention relates to a composition, a reactive diluent, a curable composition, and a method for producing the composition.

Curing compositions containing epoxy resins have excellent physical properties such as electrical insulation, heat resistance, moisture resistance, and dimensional stability, making them suitable for a wide range of applications.

In liquid molding such as casting molding, liquid epoxy resins such as bisphenol A type epoxy resins can be used. However, since such liquid epoxy resins often have high viscosity, a reactive diluent for epoxy resins may be used for the purpose of adjusting the viscosity of the curable composition and imparting physical properties to the curable composition.
For example, diglycidyl ether is one of the most commonly used reactive diluents.

For example, Patent Document 1 discloses a short-chain aliphatic compound having a glycidyloxymethyl group at a geminal position.

Patent Document 2 discloses a diglycidyl ether represented by a specific general formula.

Patent Document 3 discloses a method for producing high-purity fatty acid glycidyl ethers with low chlorine content, characterized in that when producing glycidyl ethers by reacting alcohols with epichlorohydrin in the presence of solid alkali metal hydroxide, the reaction is carried out in the presence of solid alkali metal hydroxide ground in the reaction mixture.

U.S. Patent No. 004481348 WO 98/39314 Japanese Patent Application Publication No. 1-151567

　Curable compositions containing epoxy resins are widely used in semiconductor encapsulants, LED encapsulants, printed circuit boards, build-up boards, electronic components such as resist inks, conductive adhesives such as conductive pastes and other adhesives, liquid encapsulants such as underfills, liquid crystal sealants, coverlays for flexible boards, adhesive films for build-up, die bonding films, non-conductive films, matrices for composite materials, paints, photopolymerization resins, photoresist materials, developer materials, etc. Among these, in electronic material applications such as semiconductors and printed wiring boards, there is an increasing demand for high performance encapsulants, board materials, etc., in line with technological innovations in these applications.

When epoxy resins are used for electronic materials, it is necessary to reduce the impurity content. For example, it is necessary to reduce the impurity content of reactive diluents for epoxy resins used for electronic materials. By reducing the impurity content, defects such as electrical short circuits in electronic components and migration between electronic circuit wiring can be avoided, and it is considered that the insulation reliability is excellent.
Furthermore, with regard to the diglycidyl ether contained in a reactive diluent used for electronic material applications, it is required to use a suitable diglycidyl ether from the viewpoint of reducing the viscosity of the epoxy resin without impairing the performance of the epoxy resin.

The problem that the present invention aims to solve is to provide a composition that contains a specific diglycidyl ether, has a reduced total chlorine content, and has excellent insulation reliability.

The present invention includes the following aspects.
[1] A composition comprising a chlorine-containing compound and a diglycidyl ether represented by the following formula (1):
A composition having a total chlorine content of 900 ppm or less.

(In formula (1), X represents an alkylene group having 9 to 11 carbon atoms.)
[2] The composition according to [1], wherein in the formula (1), the alkylene group is a branched alkylene group.
[3] The composition according to [1] or [2], wherein the diglycidyl ether is at least one of diglycidyl ethers represented by the following formula (1-1) and the following formula (1-2):

[4] A reactive diluent for epoxy resins, comprising the composition according to any one of [1] to [3].
[5] A curable composition comprising the reactive diluent according to [4].
[6] A method for producing a composition containing a chlorine-containing compound and a diglycidyl ether represented by the following formula (1),
The total chlorine content of the composition is 900 ppm or less,
a crude diglycidyl ether production step of reacting an alkanediol having 9 to 11 carbon atoms with epichlorohydrin to obtain a crude diglycidyl ether containing a diglycidyl ether represented by the following formula (1);
a purification step of purifying the obtained crude diglycidyl ether;
Including,
In the crude diglycidyl ether producing step, solid sodium hydroxide and water are added in portions to adjust the reaction temperature and the total chlorine content.

(In formula (1), X represents an alkylene group having 9 to 11 carbon atoms.)

The present invention provides a composition that contains a specific diglycidyl ether, has a reduced total chlorine content, and has excellent insulation reliability.

Hereinafter, an embodiment of the present invention (hereinafter, referred to as "the present embodiment") will be described in detail. The present invention is not limited to the following description, and can be practiced in various modifications within the scope of the gist thereof.
In this specification, ppm means ppm by mass.

<Composition>
The composition of the present embodiment is a composition containing a chlorine-containing compound and a diglycidyl ether represented by the following formula (1), and has a total chlorine content of 900 ppm or less.

(In formula (1), X represents an alkylene group having 9 to 11 carbon atoms.)
The composition of the present embodiment has the above-mentioned configuration and thus has excellent insulation reliability.
The composition of the present embodiment also tends to have an excellent balance of dielectric properties, coefficient of linear thermal expansion, and heat resistance. The above properties are required when the composition of the present embodiment is used for electronic material applications. Examples of electronic material applications include semiconductor encapsulation materials.

<Total chlorine content>
The total amount of chlorine refers to the amount of chlorine relative to the total amount of the composition. The total amount of chlorine is measured by a combustion type microcoulometric titration method (JIS K2170-2013 Appendix A).
The composition of the present embodiment contains a chlorine-containing compound and has a total chlorine content of 900 ppm or less.
A total chlorine content of 900 ppm or less provides excellent insulation reliability. From the above viewpoints, the total chlorine content is preferably 600 ppm or less, more preferably 500 ppm or less, and even more preferably 400 ppm or less.
For stable and low-cost production, the total chlorine content may be more than 0 ppm, may be 1 ppm or more, or may be 10 ppm or more.

The reason why the composition of the present embodiment contains a chlorine-containing compound is presumed to be as follows.
When diglycidyl ether is produced by the condensation reaction of alkanediol and epichlorohydrin, a compound having a terminal group containing a carbon-chlorine bond in the molecule is produced as a by-product. In particular, in the case of a diglycidyl ether having a branched alkylene group with a large number of carbon atoms, the reactivity and selectivity are lowered compared to linear compounds due to the steric bulkiness around the reaction point or the influence of electron donor, and by-products such as a compound having a terminal group containing a carbon-chlorine bond or a polymer condensation product of epichlorohydrin tend to be easily produced. It is presumed that these by-products containing chlorine are mixed into the composition of the present embodiment.

(Diglycidyl ether represented by formula (1))
The composition of the present embodiment contains a diglycidyl ether represented by formula (1).
When the diglycidyl ether represented by formula (1) is contained in a reactive diluent used in electronic material applications, it can reduce the viscosity of the epoxy resin without impairing the performance of the epoxy resin.

In the formula (1), the alkylene group may be linear or branched. From the viewpoint of reducing the viscosity of the epoxy resin without impairing its performance, the alkylene group is preferably a branched alkylene group.
In general, thermoplastic resins such as polyesters having branched alkylene groups tend to have low glass transition temperatures (Tg), and therefore have poor heat resistance. For this reason, it has been thought that reactive diluents having branched alkylene groups are difficult to use for applications such as semiconductor encapsulation materials. In contrast, in this embodiment, the diglycidyl ether represented by formula (1) in which X is a branched alkylene group having 9 to 11 carbon atoms has a high Tg in thermosetting resins such as epoxy resins. Therefore, the diglycidyl ether has excellent heat resistance and can be suitably used for applications such as semiconductor encapsulation materials that can withstand soldering when mounting electronic components on electronic boards.

In formula (1), X represents an alkylene group having 9 to 11 carbon atoms, preferably an alkylene group having 9 to 10 carbon atoms, and more preferably an alkylene group having 9 carbon atoms.

From the viewpoint of reducing the viscosity of the epoxy resin without impairing the performance of the epoxy resin, it is preferable that the diglycidyl ether is at least one of the diglycidyl ethers represented by the following formula (1-1) and the following formula (1-2).

In the composition of the present embodiment, the concentration of the diglycidyl ether represented by formula (A), calculated by the following calculation method using values measured under the following gas chromatographic analysis conditions, is preferably 94.5% or more, and more preferably 95.0% or more.
In the composition of the present embodiment, the concentration of the diglycidyl ether represented by formula (A) calculated by the following calculation method using values measured under the following gas chromatographic analysis conditions may be less than 100.0%.

[Gas chromatograph analysis conditions]
Analytical equipment: Agilent Technologies 7890A Gas Chromatography System
Analytical column: Agilent Technologies HP-5 (length 30 m × inner diameter 0.32 mm × film thickness 0.25 μm, packing: (5%-phenyl)-methylpolysiloxane)
Temperature increase conditions: After holding at 50° C. for 5 minutes, the temperature was increased from 50° C. to 320° C. at a rate of 10° C./min, and then held at 320° C. for 28 minutes. Sample introduction temperature: 320° C.
Carrier gas: nitrogen Column gas flow rate: 0.5 mL/min Detector and detection temperature: flame ionization detector (FID), 320° C.
Control mode: constant flow Split ratio: 50
Sample injection conditions: 1.0 μL

[Method of calculating diglycidyl ether concentration (DGE concentration)]
The diglycidyl ether concentration (DGE concentration) was calculated using the following formula (A) from the total area value of the diglycidyl ether peaks detected at retention times of 25.5 to 26.9 minutes (DGE detection peak area value) and the total area value of all peaks detected at retention times of 0.0 to 60.0 minutes (total detection peak area value) under the above measurement conditions.
DGE concentration (%) = (DGE detection peak area value / total detection peak area value) x 100 (A)

<Reactive diluent for epoxy resin>
The reactive diluent for the epoxy resin of this embodiment includes the composition of this embodiment.
The composition of the present embodiment can be suitably used as a reactive diluent for epoxy resins. By using the composition of the present embodiment as a reactive diluent for epoxy resins, a resin having excellent insulation reliability suitable for electronic components and the like can be obtained. The diglycidyl ether contained in the composition of the present embodiment can reduce the viscosity of the epoxy resin without impairing the performance of the epoxy resin. In addition, by using the composition of the present embodiment as a reactive diluent for epoxy resins, the obtained resin has excellent dielectric properties, thermal expansion coefficient, heat resistance, and the like.
The reactive diluent for the epoxy resin of the present embodiment may contain a known reactive diluent in addition to the composition of the present embodiment.

<Curable Composition>
The curable composition of the present embodiment includes a reactive diluent for the epoxy resin of the present embodiment.
The curable composition of the present embodiment can be prepared, for example, by mixing a curing agent, a curing accelerator, and the like with an epoxy resin composition containing an epoxy resin and a reactive diluent for the epoxy resin of the present embodiment.
The curable composition of the present embodiment contains a reactive diluent for the epoxy resin containing the composition of the present embodiment, and thereby a resin having excellent insulation reliability, dielectric properties, coefficient of linear thermal expansion, heat resistance, and the like, which is suitable for electronic components and the like, can be obtained.

<Production method of composition>
The method for producing the composition of the present embodiment is a method for producing the composition of the present embodiment.
The method for producing a composition according to the present embodiment is a method for producing a composition containing a chlorine-containing compound and a diglycidyl ether represented by the following formula (1), in which the total chlorine content of the composition is 900 ppm or less, and the method includes a crude diglycidyl ether production step of reacting an alkanediol having 9 to 11 carbon atoms with epichlorohydrin to obtain a crude diglycidyl ether containing the diglycidyl ether represented by the following formula (1), and a purification step of purifying the obtained crude diglycidyl ether, in which solid sodium hydroxide and water are added in portions in the crude diglycidyl ether production step to adjust the reaction temperature and the total chlorine content.

(In formula (1), X represents an alkylene group having 9 to 11 carbon atoms.)
In the formula (1), the alkylene group is preferably a branched alkylene group.

(Crude diglycidyl ether production process)
The crude diglycidyl ether production step is a step in which an alkanediol having 9 to 11 carbon atoms is reacted with epichlorohydrin to obtain a crude diglycidyl ether containing the diglycidyl ether represented by formula (1).
In the crude diglycidyl ether production step, the reaction temperature and the total amount of chlorine are adjusted by adding solid sodium hydroxide and water in portions.

In the crude diglycidyl ether production step, an alkanediol having 9 to 11 carbon atoms may be reacted with epichlorohydrin in the presence of solid sodium hydroxide, water, and a phase transfer catalyst to obtain a crude diglycidyl ether containing the diglycidyl ether represented by formula (1).

The phase transfer catalyst includes quaternary ammonium salts, quaternary phosphonium salts, etc. For example, tetraethylammonium chloride, tetra-n-butylammonium bromide, tetrabutylammonium sulfate, ethyltriphenylphosphonium bromide, etc., and tetra-n-butylammonium bromide is preferred.
The amount of the phase transfer catalyst used is preferably 0.5 mmol to 10.0 mmol, and more preferably 3.0 mmol to 7.0 mmol, per 1.0 mol of epichlorohydrin.

The amount of solid sodium hydroxide used is not particularly limited, but is preferably 1.0 mol to 12.0 mol in total, more preferably 1.5 mol to 10.0 mol, even more preferably 2.0 mol to 8.0 mol, and particularly preferably 3.0 mol to 6.0 mol per 1.0 mol of alkanediol having 9 to 11 carbon atoms.

The amount of water used is not particularly limited, but is preferably 0.5 mol to 1.0 mol in total, more preferably 0.6 mol to 0.95 mol, and even more preferably 0.7 mol to 0.90 mol per 1.0 mol of alkanediol having 9 to 11 carbon atoms.

In the crude diglycidyl ether production step, the reaction temperature, the hydroxide ion concentration in the reaction liquid, and the total chlorine content are adjusted by adding solid sodium hydroxide and water in portions.
This makes it possible to effectively suppress the total chlorine content in the resulting composition.
Therefore, the total chlorine content in the resulting composition can be easily controlled to 900 ppm or less.
When an aqueous sodium hydroxide solution is added instead of solid sodium hydroxide and water, it tends to be difficult to adjust the reaction temperature, the hydroxide ion concentration in the reaction liquid, and the total chlorine content.

The number of divided additions, for both the number of additions of solid sodium hydroxide and the number of additions of water, is preferably 3 to 10, and more preferably 4 to 8. The time required for all divided additions to be completed (hereinafter referred to as "time of divided addition") is preferably 1 to 5 hours, and more preferably 2 to 4 hours.
By adding solid sodium hydroxide three or more times and adding water three or more times, the hydroxide ion concentration in the reaction solution can be appropriately controlled, and the progress of side reactions can be suppressed.
By limiting the number of times that solid sodium hydroxide is added and the number of times that water is added to 10 or less, respectively, excessive addition work can be prevented.
By setting the time for divided addition to one hour or longer, the hydroxide ion concentration in the reaction solution can be appropriately controlled, and the progress of side reactions can be suppressed.
By limiting the time for divided addition to 5 hours or less, excessive addition can be prevented.
In the crude diglycidyl ether production step, it is preferable to add solid sodium hydroxide and water in amounts within the above-mentioned preferred ranges in multiple divided portions.
In the divided addition, the solid sodium hydroxide and water may be added simultaneously or separately, preferably separately.
In the divided addition, when solid sodium hydroxide and water are added separately, the order may be that solid sodium hydroxide is added first and then water is added, or the reverse order may be used. From the viewpoint of adjusting the reaction temperature, the hydroxide ion concentration in the reaction liquid, and the total amount of chlorine, the order of adding solid sodium hydroxide and then water is preferred. More preferably, divided addition of solid sodium hydroxide and then water is added as one cycle, and this cycle is repeated. When the cycle is repeated, it is preferable to repeat it 3 to 10 times, and more preferably 4 to 8 times.

The reaction temperature is preferably 35°C to 49°C.
By setting the reaction temperature at 35° C. or higher, the reaction can be promoted with good selectivity even in the case of an alkanediol having a branched alkylene group with a large carbon number. By setting the reaction temperature at 49° C. or lower, the progress of side reactions can be suppressed.
From the above viewpoints, the reaction temperature is more preferably 38°C to 48°C, and further preferably 40°C to 47°C.
By keeping the reaction temperature within the above range, the total chlorine content in the resulting composition can be effectively controlled. Furthermore, by carrying out the divided addition, it becomes easier to keep the reaction temperature within the above range.

By adding solid sodium hydroxide and water in separate portions, it is believed that it is possible to prevent the hydroxide ion concentration in the reaction solution from exceeding a certain level, and as a result, the reaction temperature can be controlled below a certain level.

It is preferable to further stir the reaction solution after the divided addition of the solid sodium hydroxide and water, which allows the reaction to proceed further.
The stirring time is preferably from 1 to 12 hours, more preferably from 2 to 10 hours, and further preferably from 4 to 8 hours.
The preferred temperature, more preferred temperature, and even more preferred temperature of the reaction liquid during stirring are the same as the reaction temperature described above.

In the raw material alkanediol having 9 to 11 carbon atoms, the alkane is preferably a branched alkane.
Examples of the alkanediol having 9 to 11 carbon atoms include 2,4-dialkyl-1,5-pentanediol and 2,2-dialkyl-1,3-propanediol.
Examples of 2,4-dialkyl-1,5-pentanediol include 2-methyl-4-propyl-1,5-pentanediol, 2-isopropyl-4-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 2-ethyl-4-propyl-1,5-pentanediol, 2-ethyl-4-isopropyl-1,5-pentanediol, 2,4-dipropyl-1,5-pentanediol, 2-isopropyl-4-propyl-1,5-pentanediol, 2,4-diisopropyl-1,5-pentanediol, etc. Among the above, 2,4-diethyl-1,5-pentanediol is preferred.

Examples of 2,2-dialkyl-1,3-propanediol include 2-methyl-2-pentyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 2-ethyl-2-(2-methylpropyl)-1,3-propanediol, 2,2-dipropyl-1,3-propanediol, 2-methyl-2-hexyl-1,3-propanediol, 2-ethyl-2-pentyl-1,3-propanediol, and 2-ethyl-2-(3-methylbutyl) 2-propyl-2-butyl-1,3-propanediol, 2-isopropyl-2-butyl-1,3-propanediol, 2-methyl-2-heptyl-1,3-propanediol, 2-ethyl-2-hexyl-1,3-propanediol, 2-propyl-2-pentyl-1,3-propanediol, 2-isopropyl-2-(3-methylbutyl)-1,3-propanediol, 2,2-dibutyl-1,3-propanediol, etc. Among the above, 2-butyl-2-ethyl-1,3-propanediol is preferred.

The alkanediol having 9 to 11 carbon atoms may be a commercially available product or may be produced according to a known method.
Examples of commercially available products include Kyowadiol PD-9 (manufactured by KH Neochem Co., Ltd.) and Butyl Ethyl Propanediol (manufactured by KH Neochem Co., Ltd.).
An example of the known method is the method described in International Publication No. WO 98/39314.

The amount of epichlorohydrin used is preferably 1.0 mol to 12.0 mol, more preferably 1.5 mol to 10.0 mol, even more preferably 2.0 mol to 8.0 mol, and particularly preferably 3.0 mol to 6.0 mol per 1.0 mol of alkanediol having 9 to 11 carbon atoms.

As an embodiment of the crude glycidyl ether producing step, the following (1) to (5) are shown.
(1) An alkanediol, 1.0 mol to 12.0 mol of epichlorohydrin per 1.0 mol of alkanediol, and 0.5 mmol to 10.0 mmol of a phase transfer catalyst per 1.0 mol of epichlorohydrin are charged into a reactor.
(2) 1.0 mol to 12.0 mol of solid sodium hydroxide per 1.0 mol of alkanediol is added to the reactor in 3 to 10 equal portions over a period of 1 to 5 hours, and simultaneously or separately, (3) 0.5 mol to 1.0 mol of water per 1 mol of alkanediol is added to the reactor in 3 to 10 equal portions over a period of 1 to 5 hours.
(4) After the addition of sodium hydroxide and water in portions is completed, the reaction solution is further stirred for 1 to 12 hours.
(5) During the steps (2) to (4) above, the temperature of the reaction solution is maintained at 35° C. to 49° C.
When each of the divided additions of (2) and (3) is considered as one step, the order of these steps is preferably such that the divided addition step of (2) comes after the divided addition step of (3) from the viewpoint of adjusting the reaction temperature, the hydroxide ion concentration in the reaction liquid, and the total amount of chlorine. The order of the divided addition step of (2) and the divided addition step of (3) is also preferably the same when these steps are repeated.

(Refining process)
The purification step is a step of purifying the obtained crude diglycidyl ether.
The crude diglycidyl ether may be purified by extracting the resulting crude diglycidyl ether and then distilling it.
The extraction may be carried out, for example, by filtering the crude diglycidyl ether and then adding chloroform to the filtrate.
The distillation may be carried out, for example, by vacuum distillation. The distillation conditions can be appropriately adjusted.

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples.
In the examples, the apparatus and conditions used for preparing samples and analyzing physical properties are as follows.

[GC (Gas Chromatography)]
Analytical equipment: Agilent Technologies 7890A Gas Chromatography System
Analytical column: Agilent Technologies HP-5 (length 30 m × inner diameter 0.32 mm × film thickness 0.25 μm, packing: (5%-phenyl)-methylpolysiloxane)
Temperature increase conditions: After holding at 50° C. for 5 minutes, the temperature was increased from 50° C. to 320° C. at a rate of 10° C./min, and then held at 320° C. for 28 minutes. Sample introduction temperature: 320° C.
Carrier gas: nitrogen Column gas flow rate: 0.5 mL/min Detector and detection temperature: flame ionization detector (FID), 320° C.
Control mode: constant flow Split ratio: 50
Sample injection conditions: 1.0 μL

[Calculation of diglycidyl ether concentration (DGE concentration)]
The following formula (A) was used to calculate the total area value of the peaks of diglycidyl ethers such as BEPG-DGE (DGE represented by formula (1-2)), an isomer of BEPG-DGE, and PD9-DGE (DGE represented by formula (1-1)) detected at a retention time of 25.5 to 26.9 minutes under the above measurement conditions (DGE detection peak area value) and the total area value of all peaks detected at a retention time of 0.0 to 60.0 minutes (total detection peak area value).
DGE concentration (%) = (DGE detection peak area value / total detection peak area value) x 100 (A)

[GC-MS (Gas Chromatography Mass Spectrometry)]
GC analyzer: Agilent Technologies 6890N
MS analysis device: JEOL Corporation Jms-K9 ultraQuad GC/MS
GC analytical column: Agilent Technologies HP-5 (length 30 m × inner diameter 0.32 mm × film thickness 0.25 μm, packing: (5%-phenyl)-methylpolysiloxane)
Temperature increase conditions: After holding at 50° C. for 5 minutes, the temperature was increased from 50° C. to 320° C. at a rate of 10° C./min, and then held at 320° C. for 28 minutes. Sample introduction temperature: 320° C.
Carrier gas: Helium Column gas flow rate: 0.5 mL/min Control mode: Constant flow Split ratio: 50
Sample injection conditions: 1.0 μL
MS measurement mode: CI
Interface temperature: 250°C
Ion source temperature: 150° C.
Ionization gas: isobutane The mass spectra of the peaks of BEPG-DGE and PD9-DGE detected at a retention time of 22.0 to 24.0 minutes under the above measurement conditions were confirmed.

[ ^1H NMR spectrum (500 MHz)]
Equipment: JEOL JNM-ECA500
Standard: tetramethylsilane (0.00 ppm)

[ ^13C NMR spectrum (126MHz)]
Equipment: JEOL JNM-ECA500
Standard: tetramethylsilane (0.00 ppm)

[Measurement of total chlorine content]
Apparatus: Mitsubishi Chemical Analytical NSX-2100
Argon gas flow rate: 100 ml/min Oxygen gas flow rate: 300 ml/min Heater temperature inlet: 900° C.
Heater temperature outlet: 1000℃
Chlorine measurement - Potentiometric titration End point: 290-315mV

[Epoxy equivalent, crosslink density]
Test method: ISO3001 (Tetraethylammonium bromide-perchloric acid method)
Crosslink density (calculated value): The reciprocal of the epoxy equivalent [g/eq] measured by the above method was taken as the crosslink density [eq/g].

[Dielectric tangent, relative dielectric constant]
Apparatus: Precision LCR meter E4980A manufactured by Agilent Technologies
Test method: Compliant with IEC 62631-2-1 Test dimensions: 60 x 60 x t3 (mm)
Frequency: 1MHz
Test temperature: 23°C

[Glass transition temperature, coefficient of linear thermal expansion]
Equipment: Rigaku TMA8311
Test method: JIS K 7197
Test dimensions: 10 x 5 x t3 (mm)
Heating rate: 5°C/min Measurement temperature range: room temperature to 300°C
Measurement mode: Compression (load 49 mN)
Atmosphere: Nitrogen flow (100 mL/min)

〔oven〕
Equipment: Yamato Scientific Co., Ltd. constant temperature incubator DKM600

The abbreviations have the following meanings:
PD-9: 2,4-diethyl-1,5-pentanediol BEPG: 2-butyl-2-ethyl-1,3-propanediol PD9-DGE: 2,4-diethyl-1,5-pentanediol diglycidyl ether BEPG-DGE: 2-butyl-2-ethyl-1,3-propanediol diglycidyl ether 16HD-DGE: 1,6-hexanediol diglycidyl ether [Epogose (registered trademark) HD (D), electronic material grade, manufactured by Yokkaichi Synthetic Co., Ltd.]
BPA: Bisphenol A epoxy resin [jER (registered trademark) 828, manufactured by Mitsubishi Chemical Corporation]
MH700: 4-methylhexahydrophthalic anhydride/hexahydrophthalic anhydride mixture (molar ratio 70:30) [manufactured by New Japan Chemical Co., Ltd., Rikacid (registered trademark) MH-700]
TBP-DEPS: Tetrabutylphosphonium O,O-diethyl phosphorodithioate [manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.]
EPH: epichlorohydrin [manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., purity 99%]
TBNB: Tetra-n-butylammonium bromide [manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.]
NaOH: Sodium hydroxide [manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., purity 97%, granular solid]
CDCl ₃ : deuterated chloroform [manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., containing 0.03% tetramethylsilane]

[Example 1]
<Preparation of a composition containing PD9-DGE (Composition A)>
As the alkanediol, Kyowadiol PD-9 manufactured by KH Neochem Co., Ltd. (a mixture of PD-9 and BEPG, with a GC area ratio of PD-9/BEPG of 95/5) was used.
Into the reaction flask, 305g (1.90mol) of alkanediol, 705g (7.62mol) of EPH, and 8.60g (26.7mmol) of TBNB were charged. Next, while stirring the charged liquid with a mechanical stirrer with stirring blades at a rotation speed of 250 rpm, the liquid temperature in the reaction flask was maintained at 45±1°C in a water bath, and 50.8g (1.25mol) of NaOH was added. Then, 5.08g (0.282mol) of water was added, and a cloudy heterogeneous mixture was obtained. At this time, no increase in the liquid temperature in the reaction flask was observed. While maintaining the heterogeneous mixture at 45±1°C, the mixture was stirred at 250 rpm for 30 minutes, and 50.8g (1.27mol) of NaOH was added again. Then, 5.08g (0.282mol) of water was added. The same operation was repeated six times in total, and 305 g (7.63 mol) of NaOH and 30.5 g (1.69 mol) of water were added to the reaction flask over a period of three hours. The mixture was stirred at 250 rpm for an additional six hours while maintaining the temperature at 45±1° C., to obtain a heterogeneous reaction liquid. The mixture was filtered to remove insoluble matter. 100 g of chloroform was added to the filtrate to extract the product, which was then washed with 1000 g of water. The product after washing with water was then purified by distillation under reduced pressure to obtain composition A. The boiling point of composition A was 145 to 150° C./0.9 kPa, and the isolated yield was 49% (based on alkanediol).
The DGE concentration, total chlorine content, epoxy equivalent, and crosslink density of the obtained composition A are shown in Table 1.

Then, GC-MS (CI), ¹ H-NMR and ¹³ C-NMR analyses were carried out, and the analytical results are shown below.
GC-MS (CI) m/z: 273 (GC-MS retention time; 22.5-22.7 minutes, BEPG-DGE, MH ⁺ ), 273 (GC-MS retention time; 23.0-23.5 minutes, PD9-DGE, MH ⁺ ).
¹ H NMR (CDCl ₃ , 500 MHz) δ 3.68 (m, 2H, glycidyl group), 3.40 (m, 2H, glycidyl group), 3.36 (m, 4H, CH ₂ CHCH ₂ O), 3.12 (m, 2H, glycidyl group), 2.78 (m, 2H, glycidyl group), 2.60 (m, 2H, glycidyl group), 1.60 (m, 2H, CH ₂ CHCH ₂ O), 1.46-1.28 (m, 4H, CH ₃ CH ₂ ), 1.25 (m, 2H, CH ₂ CHCH ₂ O), 0.88 (t, 6H, CH ₃ CH ₂ ).
^13C NMR ( _CDCl3 , 126MHz) δ74.6, 71.6, 51.0, 44.2, 37.4, 32.8, 24.3, 10.9.

[Example 2]
<Preparation of composition containing BEPG-DGE (composition B)>
Composition B was obtained in the same manner as in Example 1, except that the alkanediol was changed to BEPG manufactured by KH Neochem Co., Ltd.
The boiling point of composition B was 146 to 152° C./0.8 kPa, and the isolated yield was 29% (based on alkanediol).
The DGE concentration, total chlorine content, epoxy equivalent, and crosslink density of the obtained composition B are shown in Table 1.

Then, GC-MS (CI), ¹ H-NMR and ¹³ C-NMR analyses were carried out, and the analytical results are shown below.
GC-MS (CI) m/z: 273 (GC-MS retention time; 22.5-22.7 minutes, BEPG-DGE, MH ⁺ ), 273 (GC-MS retention time; 23.0-23.5 minutes, BEPG-DGE isomer MH ⁺ ).
¹ H NMR (CDCl ₃ , 500 MHz) δ 3.68 (m, 2H, glycidyl group), 3.40 (m, 2H, glycidyl group), 3.36 (m, 4H, CH ₂ CHCH ₂ O), 3.12 (m, 2H, glycidyl group), 2.78 (m, 2H, glycidyl group), 2.60 (m, 2H, glycidyl group), 1.60 (m, 2H, CH ₂ CHCH ₂ O), 1.46-1.28 (m, 4H, CH ₃ CH ₂ ), 1.25 (m, 2H, CH ₂ CHCH ₂ O), 0.88 (t, 6H, CH ₃ CH ₂ ).
^13C NMR ( _CDCl3 , 126MHz) δ74.6, 71.6, 51.0, 44.2, 37.4, 32.8, 24.3, 10.9.

[Comparative Example 1]
<Preparation of a composition containing PD9-DGE (Composition C)>
The same alkanediol as in Example 1 was used.
The reaction flask was charged with 305 g (1.90 mol) of alkanediol, 705 g (7.62 mol) of EPH, and 8.60 g (26.7 mmol) of TBNB. Next, the liquid temperature in the reaction flask was maintained at 45 ° C. in a water bath while stirring the charged liquid at a rotation speed of 250 rpm with a mechanical stirrer with a stirring blade, and 305 g (7.63 mol) of NaOH and 5.08 g (1.69 mol) of water were added simultaneously, and the liquid temperature in the reaction flask rapidly rose to 50 ° C. By cooling in a water bath for 1 hour and 15 minutes, a cloudy heterogeneous mixture with a liquid temperature of 45 ° C. in the reaction flask was obtained. The heterogeneous mixture was stirred at 250 rpm for 6 hours while maintaining it at 45 ± 1 ° C., and a heterogeneous reaction liquid was obtained. This was filtered to remove insoluble matter. 100 g of chloroform was added to the filtrate to extract the product, which was then washed with 1000 g of water. The product after washing with water was then purified by reduced pressure distillation to obtain composition C. Composition C had a boiling point of 145 to 150° C./0.9 kPa and an isolated yield of 49% (based on alkanediol).
The DGE concentration, total chlorine content, epoxy equivalent, and crosslink density of the obtained composition C are shown in Table 1.

[Comparative Example 2]
<Analysis of composition containing 16HD-DGE (composition D)>
Composition D, Epogosei (registered trademark) HD (D) manufactured by Yokkaichi Synthetic Co., Ltd., was analyzed.
The DGE concentration, total chlorine content, epoxy equivalent, and crosslink density of composition D are shown in Table 1.

[Examples 3 to 4, Comparative Examples 3 to 4]
<Preparation and Evaluation of Curable Compositions 1 to 4>
A mixture was obtained by adding MH700 as a curing agent in an equimolar amount to the epoxy groups in the epoxy resin composition and 1 part by mass of TBP-DEPS as a curing accelerator to 100 parts by mass of the epoxy resin composition shown in Table 2. This mixture was degassed by stirring under reduced pressure at room temperature (approximately 25° C.) for 30 minutes, to prepare curable compositions 1 to 4.
Each curable composition was sandwiched between two glass substrates that had been previously treated with a fine heat-resistant TFE coat (manufactured by Fine Chemical Japan Co., Ltd.) for release, together with a 3 mm thick U-shaped silicone rubber spacer. Then, each curable composition sandwiched between the two glass substrates was heated in an oven at 100° C. for 2 hours (pre-curing), and then heated to 150° C. for 5 hours (main curing). After gradual cooling, the glass substrates were removed to obtain each cured product with a thickness of 3 mm.
The obtained cured products were evaluated for dielectric constant, dielectric loss tangent, glass transition temperature (Tg), and coefficient of linear thermal expansion (CTE). Each physical property was measured by the following procedure. The results are shown in Table 2.

[Dielectric constant, dielectric loss tangent]
The dielectric loss tangent tan δ and the capacitance Cp were measured when a voltage of 1 V, 1 MHz was applied to the test piece sandwiched between the electrodes of the holder, and the relative dielectric constant _εr was calculated by dividing the measured values by the capacitance _C0 of air measured under the same conditions.
The lower the dielectric loss tangent tan δ or the relative dielectric constant _εr , the more excellent the dielectric properties.

[Glass transition temperature (Tg)]
The thermal properties of the test piece were measured by thermomechanical analysis (TMA), and tangents were drawn to the curves before and after the obtained TMA curve, and Tg was determined from the intersection of the tangents.
When the Tg is high, the glass state can be maintained even at high temperatures during soldering of electronic substrates, and the heat resistance is excellent, making the material suitable for use as a semiconductor encapsulant, for example.

[Coefficient of linear thermal expansion (CTE)]
The test piece was subjected to thermomechanical analysis (TMA), and the CTE was calculated from the slope of the obtained TMA curve in the section from 50° C. to 100° C.
The lower the CTE, the better the dimensional stability.

As shown in Table 1, Composition A and Composition B, which are compositions containing a chlorine-containing compound and a diglycidyl ether represented by formula (1) and have a total chlorine content of 900 ppm or less, have a total chlorine content sufficiently lower than the threshold value (900 ppm or less) of the halogen-free grade desired in the electronic materials field, and are therefore excellent in insulation reliability.
On the other hand, the composition C of Comparative Example 1, which was produced by a conventionally known production method (WO98/39314) and in which the total chlorine content was not 900 ppm or less, has a total chlorine content higher than the threshold value (900 ppm or less), and is considered to have a significantly low insulation reliability. Therefore, it is considered difficult to use it for, for example, semiconductor encapsulation applications.

As shown in Table 2, curable composition 1 (Example 3) to which composition A obtained in Example 1 was added as a reactive diluent had a lower relative dielectric constant and CTE than curable composition 3 (Comparative Example 3) to which composition C obtained in Comparative Example 1, which was made by the conventionally known manufacturing method (WO98/39314), was added as a reactive diluent.

As shown in Table 2, curable composition 1 (Example 3) to which composition A obtained in Example 1 was added as a reactive diluent had a lower relative dielectric constant, dielectric loss tangent, and CTE than curable composition 4 (Comparative Example 4) to which composition D of the conventionally known Comparative Example 2 was added as a reactive diluent.

As shown in Table 2, curable composition 2 (Example 4) to which composition B obtained in Example 2 was added as a reactive diluent had a lower relative dielectric constant, dielectric loss tangent, and CTE than curable composition 4 (Comparative Example 4) to which composition D of the conventionally known Comparative Example 2 was added as a reactive diluent.

Furthermore, as shown in Table 1, the crosslink density of the reactive diluent (Example 1: composition A) was 0.86 times that of the conventionally known reactive diluent (Comparative Example 2: composition D), and the crosslink density was low in Example 1. In contrast, as shown in Table 2, the difference in Tg between the curable composition 4 (Comparative Example 4) to which the conventionally known reactive diluent (Comparative Example 2: composition D) was added and the curable composition 1 (Example 3) to which the reactive diluent (Example 1: composition A) was added was 2° C., and they were equivalent.
Furthermore, as shown in Table 1, the crosslink density of the reactive diluent (Example 2: composition B) was 0.86 times that of the conventionally known reactive diluent (Comparative Example 2: composition D), and the crosslink density was low in Example 2. In contrast, as shown in Table 2, the Tg of curable composition 2 (Example 4) to which a reactive diluent (Example 2: composition B) was added was improved by 6° C. compared to the Tg of curable composition 4 (Comparative Example 4) to which a conventionally known reactive diluent (Comparative Example 2: composition D) was added.

This application is based on a Japanese patent application (Patent Application No. 2023-058088) filed with the Japan Patent Office on March 31, 2023, the contents of which are incorporated herein by reference.

The composition of the present invention has industrial applicability as a reactive diluent for epoxy resins, a curable composition, a method for producing a composition, etc.

Claims

A composition comprising a chlorine-containing compound and a diglycidyl ether represented by the following formula (1):
A composition having a total chlorine content of 900 ppm or less.

(In formula (1), X represents an alkylene group having 9 to 11 carbon atoms.)
The composition according to claim 1, wherein the alkylene group in X of formula (1) is a branched alkylene group.
The composition according to claim 1, wherein the diglycidyl ether is at least one of diglycidyl ethers represented by the following formula (1-1) and the following formula (1-2):
A reactive diluent for epoxy resins comprising the composition according to claim 1.
A curable composition comprising the reactive diluent according to claim 4.
A method for producing a composition containing a chlorine-containing compound and a diglycidyl ether represented by the following formula (1),
The total chlorine content of the composition is 900 ppm or less,
a crude diglycidyl ether production step of reacting an alkanediol having 9 to 11 carbon atoms with epichlorohydrin to obtain a crude diglycidyl ether containing a diglycidyl ether represented by the following formula (1);
a purification step of purifying the obtained crude diglycidyl ether;
Including,
In the crude diglycidyl ether producing step, the reaction temperature and the total chlorine content are adjusted by adding solid sodium hydroxide and water in portions.

(In formula (1), X represents an alkylene group having 9 to 11 carbon atoms.)