WO2021131768A1 - Epoxy resin and method for manufacturing same - Google Patents
Epoxy resin and method for manufacturing same Download PDFInfo
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- WO2021131768A1 WO2021131768A1 PCT/JP2020/046179 JP2020046179W WO2021131768A1 WO 2021131768 A1 WO2021131768 A1 WO 2021131768A1 JP 2020046179 W JP2020046179 W JP 2020046179W WO 2021131768 A1 WO2021131768 A1 WO 2021131768A1
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- tetramethylbisphenol
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- JNKNWEGSCDBNLV-UHFFFAOYSA-N C=Nc(cc1N)cc(N)c1O[N]#C Chemical compound C=Nc(cc1N)cc(N)c1O[N]#C JNKNWEGSCDBNLV-UHFFFAOYSA-N 0.000 description 1
- 0 CC(C)(N)Oc(c(N)cc(N)c1)c1*#C Chemical compound CC(C)(N)Oc(c(N)cc(N)c1)c1*#C 0.000 description 1
- NKTALNATFMAEJR-UHFFFAOYSA-N CCC(C)(N)Oc(c(N)cc(N)c1)c1N Chemical compound CCC(C)(N)Oc(c(N)cc(N)c1)c1N NKTALNATFMAEJR-UHFFFAOYSA-N 0.000 description 1
- VHWHISLSSKROOL-UHFFFAOYSA-N Cc1cccc(C)c1OCC1OC1 Chemical compound Cc1cccc(C)c1OCC1OC1 VHWHISLSSKROOL-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
- C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
Definitions
- the present invention relates to an epoxy resin. More specifically, the present invention relates to a tetramethylbisphenol F type epoxy resin which is liquid at room temperature and has excellent handleability, and a method for producing the same.
- Epoxy resin is widely used in civil engineering / construction, adhesives, casting materials, etc. because it has excellent corrosion resistance, adhesion, chemical resistance, and flexibility when combined with various curing agents.
- the bisphenol A type liquid epoxy resin undergoes a modification reaction and a polymerization reaction with various phenols, carboxylic acids and the like, and is widely used as a raw material for heavy-duty anticorrosion paints, PCM paints, powder paints and can paints.
- Epoxy resins are widely used in civil engineering / construction, adhesives, raw materials for paints, etc. because they are excellent in corrosion resistance, adhesion, chemical resistance, and flexibility when combined with various curing agents. Conventionally, bisphenol A type liquid epoxy resin and bisphenol F type liquid epoxy have been used in these fields, and there is currently no other type.
- the present invention provides a tetramethylbisphenol F-type epoxy resin that has low crystallinity and remains liquid at room temperature.
- the present inventor has found that an epoxy resin derived by reacting tetramethylbisphenol F containing a certain amount of polynuclear body with epichlorohydrin under specific conditions remains liquid at room temperature, and has reached the present invention. ..
- the present invention contains 0.1 to 2.5 area% of the epoxy resin (a) represented by the following formula (1) in high performance liquid chromatography (HPLC) measurement, and gel permeation chromatography (GPC) measurement.
- the tetramethylbisphenol F type epoxy resin of the present invention can be obtained by reacting a raw material phenol compound represented by the following formula (3) with epichlorohydrin in the presence of an alkali metal hydroxide.
- n is the number of repetitions, and the average value thereof is 1.005 to 3.
- m is the number of repetitions.
- the tetramethylbisphenol F type epoxy resin has an epoxy equivalent of 200 to 220 g / eq. , Hydrolyzable chlorine is less than 5,000 ppm, ⁇ -diol content is 1 to 20 meq. / 100 g, phenolic hydroxyl group content 1 to 20 meq.
- the viscosity at / 100 g and 25 ° C. is preferably 50,000 to 200,000 mPa ⁇ s.
- a phenol compound containing 0.5 to 2.5 area% of components having n 2 or more in the following formula (3) and 2.0 to 3 with respect to 1 mol of the phenolic hydroxyl group thereof.
- the tetramethylbisphenol F-type epoxy resin which comprises reacting 0.0 mol of epichlorohydrin with 1 mol of its phenolic hydroxyl group in the presence of 0.9 to 1.1 mol of an alkali metal hydroxide. It is a manufacturing method of. (Here, n is the number of repetitions, and the average value thereof is 1.005 to 3.)
- the tetramethylbisphenol F-type epoxy resin of the present invention does not form crystals for 100 days or more at room temperature, remains liquid, and has excellent handleability.
- the HPLC measurement conditions are according to the method described in Examples.
- the tetramethylbisphenol F type epoxy resin of the present invention can be obtained by reacting a specific tetramethylbisphenol F with a specific amount of epichlorohydrin in the presence of a specific amount of alkali metal hydroxide. At this time, it is preferable to evaporate epichlorohydrin and water by azeotrope, return epichlorohydrin to the system, and remove water from the system.
- the GPC measurement conditions are based on the method described in the examples.
- the raw material phenol compound has a tetramethylbisphenol F represented by the following formula (3a) of 96 to 96 in GPC measurement. It is preferably contained in an area% of 99.
- the epoxy equivalent of the tetramethylbisphenol F-type epoxy resin of the present invention is 200 to 220 g / eq. Is preferable, and 202 g to 215 g / eq. Is more preferable. 200 g / eq. If it is less than, the crystallinity becomes high, and 220 g / eq. If it exceeds, the viscosity may increase.
- the hydrolyzable chlorine is preferably less than 5,000 ppm, more preferably 1000 ppm or less. If it exceeds 5,000 ppm, the reactivity with the curing agent is deteriorated, and the physical properties of the obtained cured product may be deteriorated.
- the ⁇ -diol content is 1 to 20 meq. / 100 g is preferable, and 3 to 12 meq. / 100g is more preferable. 1meq. If it is less than / 100 g, the crystallinity becomes high, and 20 meq. If it exceeds / 100 g, the reactivity with the curing agent is deteriorated, and the physical properties of the obtained cured product may be deteriorated.
- the viscosity at 25 ° C. is preferably 50,000 to 200,000 mPa ⁇ s, more preferably 70,000 to 150,000 mPa ⁇ s. If it is less than 50,000 mPa ⁇ s, the crystallinity becomes high, and if it is 200,000 mPa ⁇ s or more, it is difficult to handle at room temperature, which is not preferable.
- a raw material phenol compound containing 0.5 to 2.5 area% of components of n 2 or more in the formula (3) in GPC measurement and 2.0 to 3.0 with respect to 1 mol of the phenolic hydroxyl group thereof.
- Mol epichlorohydrin is reacted with 1 mol of its phenolic hydroxyl group in the presence of 0.9-1.1 mol of alkali metal hydroxide.
- the amount of alkali metal hydroxide is less than 0.9 mol with respect to 1 mol of phenolic hydroxyl group, the ⁇ -diol content, hydrolyzable chlorine, and phenolic hydroxyl group content will be high and the reactivity with the curing agent will be inferior. There is a risk that the physical properties of the cured product will deteriorate. Further, if it exceeds 1.1 mol, the content of ⁇ -diol, hydrolyzable chlorine, and phenolic hydroxyl group becomes low, and the crystallinity may become high.
- the alkali metal hydroxide that can be used include potassium hydroxide, sodium hydroxide, lithium hydroxide and the like. These alkali metal hydroxides may be used alone or in combination of two or more. These alkali metal hydroxides are usually used in the form of a 20-50% by weight aqueous solution.
- Epoxy equivalent Measured in accordance with JIS K 7236 standard, unit is g / eq. Is.
- Hydrolyzable chlorine Measured in accordance with ASTM D-1726 standard, and the unit is ppm in terms of weight of chlorine atom.
- ⁇ -diol content After dissolving the sample in chloroform and adding an excess ammonium benzyltrimethylperiodic acid solution for reaction, add a 10% sulfuric acid aqueous solution and a 20% potassium iodide aqueous solution, and add 1 / of the generated iodine. It was determined by potential differential titration with a 5N sodium thiosulfate solution. The unit is meq. / 100g.
- Phenolic hydroxyl group content In a mixture of tetrahydrofuran and methanol 4%, tetramethylammonium hydroxyside was allowed to act on the phenolic hydroxyl group to develop a color, and the absorbance at 305 nm was measured using a spectrophotometer. The phenolic hydroxyl group content was determined in advance using a calibration curve prepared in the same manner using tetramethylbisphenol F as a standard. The unit is meq. / 100g.
- Viscosity The viscosity at 25 ° C was measured using a Brookfield type viscometer. The unit is mPa ⁇ s.
- Body content Determined by GPC measurement, the unit is area%. The GPC measurement conditions are shown below.
- HPLC measurement conditions are shown below.
- TMBPF-1 Tetramethylbisphenol F
- TMBPF-2 Tetramethylbisphenol F
- n 1 body: 97.5 area%
- n 2 body: 0.94 area%
- n 3 body: 1.2 area%
- n 2 body: 0.18 area%
- n 3 body: 0 area%.
- Example 1 TMBPF-1: 128.0 parts, epichlorohydrin: 231.3 parts (TMBPF-1) in a glass separable flask equipped with a stirrer, thermometer, nitrogen introduction pipe, reflux condenser with oil-water separator and decompression device.
- Epichlorohydrin 2.5 mol was charged with respect to 1 mol of the phenolic hydroxyl group, and the temperature was raised to 60 ° C. with stirring under a nitrogen atmosphere. Next, while maintaining the temperature in the reaction system at 60 ° C., the pressure was gradually reduced to reflux epichlorohydrin.
- the reaction system was returned to normal pressure, 300 parts of toluene was added to dissolve the reaction system, and 500 parts of water was added to separate and remove the by-produced salt. Then, washing was repeated with 300 parts of water until the washing water became neutral. Toluene was removed from this solution by heating to 150 ° C. under a reduced pressure of 5 mmHg to obtain a tetramethylbisphenol type liquid epoxy resin.
- Viscosity 98,000 mPa ⁇ s
- Hydrolyzable chlorine 300 ppm
- ⁇ -diol content 9 meq. / 100 g
- phenolic hydroxyl group content 7 meq. It was / 100 g.
- the resin was allowed to stand at 25 ° C. for 100 days, but no crystals were formed and the resin remained liquid.
- Example 3 Using the same equipment as in Example 1, the amount charged was TMBPF-1: 128.0 parts, epichlorohydrin: 268.3 parts (epichlorohydrin was 2.9 mol with respect to 1 mol of phenolic hydroxyl group of TMBPF-1). The same operation as in Example 1 was performed except that the above was performed.
- the resin was allowed to stand at 25 ° C. for 100 days, but no crystals were formed and the resin remained liquid.
- Comparative Example 1 The same operation was carried out except that the raw material was TMBPF-2 in the same apparatus as in Example 1 to obtain a tetramethylbisphenol F type liquid resin.
- the epoxy resin (a) could not be detected. When this resin was allowed to stand at 25 ° C., crystals were formed on the 23rd day.
- the tetramethylbisphenol F type epoxy resin of the present invention is useful for flooring materials, adhesives, etc., especially for applications used in an outdoor environment. It is also useful as an industrial raw material such as a raw material for paints.
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- Epoxy Resins (AREA)
Abstract
Provided is a tetramethyl bisphenol F-type epoxy resin that provides an excellent handling ability and that is liquid at an ordinary temperature. This tetramethyl bisphenol F-type epoxy resin contains, in an HPLC assay, 0.1-2.5 area% of an epoxy resin represented by formula (1), and, in a GPC assay, 75-85 area％ of an m=0 body of an epoxy resin represented by formula (2), and is liquid at an ordinary temperature. (Here, k represents 2 or 3, and m represents the number of repeats.)
Description
本発明はエポキシ樹脂に関する。詳しくは、ハンドリング性に優れた常温で液状のテトラメチルビスフェノールＦ型エポキシ樹脂及びその製造方法に関する。
The present invention relates to an epoxy resin. More specifically, the present invention relates to a tetramethylbisphenol F type epoxy resin which is liquid at room temperature and has excellent handleability, and a method for producing the same.
エポキシ樹脂は種々の硬化剤と組み合わせることにより、耐食性、密着性、耐薬品性、可撓性に優れるため、土木・建築、接着剤、注型材などの用途で幅広く使用されている。特にビスフェノールＡ型液状エポキシ樹脂は、様々なフェノール類、カルボン酸類等と変性反応、重合反応を行い重防食塗料、ＰＣＭ塗料、粉体塗料、缶塗料の原料として多用に使用されている。
Epoxy resin is widely used in civil engineering / construction, adhesives, casting materials, etc. because it has excellent corrosion resistance, adhesion, chemical resistance, and flexibility when combined with various curing agents. In particular, the bisphenol A type liquid epoxy resin undergoes a modification reaction and a polymerization reaction with various phenols, carboxylic acids and the like, and is widely used as a raw material for heavy-duty anticorrosion paints, PCM paints, powder paints and can paints.
土木・建築、接着剤用途では製品形態、使用形態からエポキシ樹脂は常温で液状であることが必須とされる。また、重防食塗料、ＰＣＭ塗料、粉体塗料、缶塗料用原料に変性、重合する場合、原料となるエポキシ樹脂は原料貯蔵、搬送、仕込み等の操作の際、液状であることが重要である。
エポキシ樹脂は種々の硬化剤と組み合わせることにより、耐食性、密着性、耐薬品性、可撓性に優れるため、土木・建築、接着剤、塗料用原料などの用途で幅広く使用されている。これらの分野では従来ビスフェノールＡ型液状エポキシ樹脂及びビスフェノールＦ型液状エポキシが使用され、これ以外には存在しないのが現状である。
常温で液状を保つエポキシ樹脂を提供するものとして、テトラメチルビスフェノールＦを用い、少なくとも８５％以上がそのｎ＝０体及びｎ＝１体を含む組成物が提案されているが、結晶性や粘度、さらには不純物の観点等から十分に検証されているとは言えないものである（特許文献１）。 For civil engineering / construction and adhesive applications, it is essential that the epoxy resin is liquid at room temperature due to the product form and usage form. Further, when modifying or polymerizing into a raw material for heavy-duty anticorrosion paint, PCM paint, powder paint, or can paint, it is important that the epoxy resin as the raw material is in a liquid state during operations such as raw material storage, transportation, and preparation. ..
Epoxy resins are widely used in civil engineering / construction, adhesives, raw materials for paints, etc. because they are excellent in corrosion resistance, adhesion, chemical resistance, and flexibility when combined with various curing agents. Conventionally, bisphenol A type liquid epoxy resin and bisphenol F type liquid epoxy have been used in these fields, and there is currently no other type.
As an epoxy resin that remains liquid at room temperature, a composition using tetramethylbisphenol F and containing at least 85% or more of the n = 0 and n = 1 has been proposed, but the crystallinity and viscosity have been proposed. Furthermore, it cannot be said that it has been sufficiently verified from the viewpoint of impurities (Patent Document 1).
エポキシ樹脂は種々の硬化剤と組み合わせることにより、耐食性、密着性、耐薬品性、可撓性に優れるため、土木・建築、接着剤、塗料用原料などの用途で幅広く使用されている。これらの分野では従来ビスフェノールＡ型液状エポキシ樹脂及びビスフェノールＦ型液状エポキシが使用され、これ以外には存在しないのが現状である。
常温で液状を保つエポキシ樹脂を提供するものとして、テトラメチルビスフェノールＦを用い、少なくとも８５％以上がそのｎ＝０体及びｎ＝１体を含む組成物が提案されているが、結晶性や粘度、さらには不純物の観点等から十分に検証されているとは言えないものである（特許文献１）。 For civil engineering / construction and adhesive applications, it is essential that the epoxy resin is liquid at room temperature due to the product form and usage form. Further, when modifying or polymerizing into a raw material for heavy-duty anticorrosion paint, PCM paint, powder paint, or can paint, it is important that the epoxy resin as the raw material is in a liquid state during operations such as raw material storage, transportation, and preparation. ..
Epoxy resins are widely used in civil engineering / construction, adhesives, raw materials for paints, etc. because they are excellent in corrosion resistance, adhesion, chemical resistance, and flexibility when combined with various curing agents. Conventionally, bisphenol A type liquid epoxy resin and bisphenol F type liquid epoxy have been used in these fields, and there is currently no other type.
As an epoxy resin that remains liquid at room temperature, a composition using tetramethylbisphenol F and containing at least 85% or more of the n = 0 and n = 1 has been proposed, but the crystallinity and viscosity have been proposed. Furthermore, it cannot be said that it has been sufficiently verified from the viewpoint of impurities (Patent Document 1).
本発明は、結晶性が低く、常温で液状を保つテトラメチルビスフェノールＦ型エポキシ樹脂を提供するものである。
The present invention provides a tetramethylbisphenol F-type epoxy resin that has low crystallinity and remains liquid at room temperature.
本発明者は、多核体を一定量含有するテトラメチルビスフェノールＦとエピクロルヒドリンとを特定条件下で反応させることにより誘導されるエポキシ樹脂が、常温で液状を保つことを見出して、本発明に至った。
The present inventor has found that an epoxy resin derived by reacting tetramethylbisphenol F containing a certain amount of polynuclear body with epichlorohydrin under specific conditions remains liquid at room temperature, and has reached the present invention. ..
即ち本発明は、高速液体クロマトグラフィー（ＨＰＬＣ）測定において、下記式（１）で表されるエポキシ樹脂（ａ）を０．１～２．５面積％含み、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）測定において、下記式（２）で表されるエポキシ樹脂（ｂ）のｍ＝０体を７５～８５面積％含み、常温で液状であることを特徴とするテトラメチルビスフェノールＦ型エポキシ樹脂である。
（ここで、ｋは２又は３である。）
（ここで、ｍは繰り返し数である。） That is, the present invention contains 0.1 to 2.5 area% of the epoxy resin (a) represented by the following formula (1) in high performance liquid chromatography (HPLC) measurement, and gel permeation chromatography (GPC) measurement. The tetramethylbisphenol F type epoxy resin is characterized in that it contains 75 to 85 area% of m = 0 of the epoxy resin (b) represented by the following formula (2) and is liquid at room temperature.
(Here, k is 2 or 3.)
(Here, m is the number of repetitions.)
（ここで、ｋは２又は３である。）
（ここで、ｍは繰り返し数である。） That is, the present invention contains 0.1 to 2.5 area% of the epoxy resin (a) represented by the following formula (1) in high performance liquid chromatography (HPLC) measurement, and gel permeation chromatography (GPC) measurement. The tetramethylbisphenol F type epoxy resin is characterized in that it contains 75 to 85 area% of m = 0 of the epoxy resin (b) represented by the following formula (2) and is liquid at room temperature.
(Here, k is 2 or 3.)
(Here, m is the number of repetitions.)
また、本発明のテトラメチルビスフェノールＦ型エポキシ樹脂は、下記式（３）で表される原料フェノール化合物とエピクロルヒドリンとを、アルカリ金属水酸化物の存在下で反応させることにより得られるが、ここで、原料フェノール化合物はＧＰＣ測定においてｎ＝２以上の成分を０．５～２．５面積％含む。そして、下記式（２）で表されるエポキシ樹脂のｍ＝０体を７５～８５面積％含み、常温で液状であることを特徴とするテトラメチルビスフェノールＦ型エポキシ樹脂が得られる。
（ここで、ｎは繰り返し数であり、その平均値は１．００５～３である。）
（ここで、ｍは繰り返し数である。） Further, the tetramethylbisphenol F type epoxy resin of the present invention can be obtained by reacting a raw material phenol compound represented by the following formula (3) with epichlorohydrin in the presence of an alkali metal hydroxide. , The raw material phenol compound contains 0.5 to 2.5 area% of components having n = 2 or more in GPC measurement. Then, a tetramethylbisphenol F type epoxy resin containing 75 to 85 area% of m = 0 of the epoxy resin represented by the following formula (2) and being liquid at room temperature can be obtained.
(Here, n is the number of repetitions, and the average value thereof is 1.005 to 3.)
(Here, m is the number of repetitions.)
（ここで、ｎは繰り返し数であり、その平均値は１．００５～３である。）
（ここで、ｍは繰り返し数である。） Further, the tetramethylbisphenol F type epoxy resin of the present invention can be obtained by reacting a raw material phenol compound represented by the following formula (3) with epichlorohydrin in the presence of an alkali metal hydroxide. , The raw material phenol compound contains 0.5 to 2.5 area% of components having n = 2 or more in GPC measurement. Then, a tetramethylbisphenol F type epoxy resin containing 75 to 85 area% of m = 0 of the epoxy resin represented by the following formula (2) and being liquid at room temperature can be obtained.
(Here, n is the number of repetitions, and the average value thereof is 1.005 to 3.)
(Here, m is the number of repetitions.)
上記テトラメチルビスフェノールＦ型エポキシ樹脂は、エポキシ当量が２００～２２０ｇ／ｅｑ．、加水分解性塩素が５，０００ｐｐｍ未満、αジオール含有量が１～２０ｍｅｑ．／１００ｇ、フェノール性水酸基含有量が１～２０ｍｅｑ．／１００ｇ、２５℃における粘度が５０，０００～２００，０００ｍＰａ・ｓであることが好ましい。
The tetramethylbisphenol F type epoxy resin has an epoxy equivalent of 200 to 220 g / eq. , Hydrolyzable chlorine is less than 5,000 ppm, α-diol content is 1 to 20 meq. / 100 g, phenolic hydroxyl group content 1 to 20 meq. The viscosity at / 100 g and 25 ° C. is preferably 50,000 to 200,000 mPa · s.
また本発明は、ＧＰＣ測定において、下記式（３）におけるｎ＝２以上の成分を０．５～２．５面積％含むフェノール化合物と、そのフェノール性水酸基１モルに対して２．０～３．０モルのエピクロルヒドリンとを、そのフェノール性水酸基１モルに対して０．９～１．１モルのアルカリ金属水酸化物の存在下で反応させることを特徴とする上記テトラメチルビスフェノールＦ型エポキシ樹脂の製造方法である。
（ここで、ｎは繰り返し数であり、その平均値は１．００５～３である。） Further, according to the present invention, in GPC measurement, a phenol compound containing 0.5 to 2.5 area% of components having n = 2 or more in the following formula (3) and 2.0 to 3 with respect to 1 mol of the phenolic hydroxyl group thereof. The tetramethylbisphenol F-type epoxy resin, which comprises reacting 0.0 mol of epichlorohydrin with 1 mol of its phenolic hydroxyl group in the presence of 0.9 to 1.1 mol of an alkali metal hydroxide. It is a manufacturing method of.
(Here, n is the number of repetitions, and the average value thereof is 1.005 to 3.)
（ここで、ｎは繰り返し数であり、その平均値は１．００５～３である。） Further, according to the present invention, in GPC measurement, a phenol compound containing 0.5 to 2.5 area% of components having n = 2 or more in the following formula (3) and 2.0 to 3 with respect to 1 mol of the phenolic hydroxyl group thereof. The tetramethylbisphenol F-type epoxy resin, which comprises reacting 0.0 mol of epichlorohydrin with 1 mol of its phenolic hydroxyl group in the presence of 0.9 to 1.1 mol of an alkali metal hydroxide. It is a manufacturing method of.
(Here, n is the number of repetitions, and the average value thereof is 1.005 to 3.)
本発明のテトラメチルビスフェノールＦ型エポキシ樹脂は、常温で１００日以上結晶の生成がなく、液状を保て、ハンドリング性に優れたものである。
The tetramethylbisphenol F-type epoxy resin of the present invention does not form crystals for 100 days or more at room temperature, remains liquid, and has excellent handleability.
本発明のテトラメチルビスフェノールＦ型エポキシ樹脂は、上記式（１）で表される多核体成分のエポキシ樹脂（ａ）と、上記式（２）で表される２官能のエポキシ樹脂（ｂ）の混合物であり、エポキシ樹脂（ａ）とエポキシ樹脂（ｂ）のｍ＝０体とを特定量含有することで、常温で１００日以上結晶の生成がなく、液状を保てる特性を有するものである。
The tetramethylbisphenol F type epoxy resin of the present invention comprises a polynuclear component epoxy resin (a) represented by the above formula (1) and a bifunctional epoxy resin (b) represented by the above formula (2). It is a mixture, and by containing a specific amount of m = 0 of the epoxy resin (a) and the epoxy resin (b), it has the property of not forming crystals for 100 days or more at room temperature and maintaining a liquid state.
エポキシ樹脂（ａ）は、結合位置により種々の多核体が考えられるが、非常に少ない成分は検出や分離が困難であることから、下記式（１ａ）～（１ｃ）で表される３種類のエポキシ樹脂の混合物が主な成分と推察される。
Various polynuclear bodies can be considered for the epoxy resin (a) depending on the bonding position, but since it is difficult to detect and separate very few components, there are three types represented by the following formulas (1a) to (1c). A mixture of epoxy resins is presumed to be the main component.
上記エポキシ樹脂（ａ）の含有量は、ＨＰＬＣ測定において、０．１～２．５面積％であり、０．５～２．３面積％が好ましい。０．１面積％未満ではエポキシ樹脂（ｂ）のｍ＝０体の含有量に関係なく結晶性が高くなり好ましくなく、２．５面積％を超えると粘度が高くなり好ましくない。
なお、このようなエポキシ樹脂（ａ）については、ＧＰＣによる測定では他の検出ピークとの関係で検出が困難であることから、ＨＰＬＣによる測定から求められる。ＨＰＬＣ測定条件は実施例に記載の方法による。 The content of the epoxy resin (a) is 0.1 to 2.5 area%, preferably 0.5 to 2.3 area% in the HPLC measurement. If it is less than 0.1 area%, the crystallinity becomes high regardless of the content of m = 0 of the epoxy resin (b), which is not preferable, and if it exceeds 2.5 area%, the viscosity becomes high, which is not preferable.
Since it is difficult to detect such an epoxy resin (a) in relation to other detection peaks by GPC measurement, it can be obtained by HPLC measurement. The HPLC measurement conditions are according to the method described in Examples.
なお、このようなエポキシ樹脂（ａ）については、ＧＰＣによる測定では他の検出ピークとの関係で検出が困難であることから、ＨＰＬＣによる測定から求められる。ＨＰＬＣ測定条件は実施例に記載の方法による。 The content of the epoxy resin (a) is 0.1 to 2.5 area%, preferably 0.5 to 2.3 area% in the HPLC measurement. If it is less than 0.1 area%, the crystallinity becomes high regardless of the content of m = 0 of the epoxy resin (b), which is not preferable, and if it exceeds 2.5 area%, the viscosity becomes high, which is not preferable.
Since it is difficult to detect such an epoxy resin (a) in relation to other detection peaks by GPC measurement, it can be obtained by HPLC measurement. The HPLC measurement conditions are according to the method described in Examples.
上記エポキシ樹脂（ｂ）はＧＰＣ測定において、ｍ＝０体含有量が７５～８５面積％であり、７６～８２面積％が好ましい。７５面積％未満では粘度が高く、常温でのハンドリング性が困難となり、８５面積％を超えると、エポキシ樹脂（ａ）が存在していても結晶性が著しく高くなる恐れがある。また、ｍ＝１体やｍ＝２体の含有量は特に限定する必要はないが、ｍ＝１体含有量は１０～２０面積％が好ましく、ｍ＝２体含有量は１～４面積％が好ましい。ｍ＝１体やｍ＝２体が多すぎると、本発明のテトラメチルビスフェノールＦ型エポキシ樹脂の粘度が高くなり好ましくない。
The epoxy resin (b) has a m = 0 body content of 75 to 85 area%, preferably 76 to 82 area% in GPC measurement. If it is less than 75 area%, the viscosity is high and it becomes difficult to handle at room temperature, and if it exceeds 85 area%, the crystallinity may be remarkably increased even in the presence of the epoxy resin (a). Further, the content of m = 1 body or m = 2 body is not particularly limited, but the content of m = 1 body is preferably 10 to 20 area%, and the content of m = 2 body is 1 to 4 area%. Is preferable. If there are too many m = 1 or m = 2, the viscosity of the tetramethylbisphenol F type epoxy resin of the present invention becomes high, which is not preferable.
また、本発明のテトラメチルビスフェノールＦ型エポキシ樹脂は、特定のテトラメチルビスフェノールＦを特定量のエピクロルヒドリンと、特定量のアルカリ金属水酸化物の存在下で反応させることにより得ることができる。この時、エピクロルヒドリンと水を共沸により蒸発させ、エピクロルヒドリンを系内に戻し、水を系内から除去することが好ましい。
Further, the tetramethylbisphenol F type epoxy resin of the present invention can be obtained by reacting a specific tetramethylbisphenol F with a specific amount of epichlorohydrin in the presence of a specific amount of alkali metal hydroxide. At this time, it is preferable to evaporate epichlorohydrin and water by azeotrope, return epichlorohydrin to the system, and remove water from the system.
本発明のテトラメチルビスフェノールＦ型エポキシ樹脂の原料である上記式（３）で表されるフェノール化合物は、ＧＰＣ測定におけるｎ＝２以上の成分の含有量の合計は０．５～２．５面積％であり、０．５５～２．２面積％が好ましく、０．６～２．０面積％がより好ましい。０．５面積％未満ではエポキシ樹脂とした場合、エポキシ樹脂（ａ）の生成量が少ないため、結晶性が高くなり好ましくなく、２．５面積％以上ではエポキシ樹脂（ａ）の生成量が多くなりすぎるため、粘度が高くなり好ましくない。また、ｎ＝２以上の成分の構造は、主に上記式（１ａ）～式（１ｃ）で表されるエポキシ樹脂のグリシジル基が水素原子に置換された構造である。
なお、ＧＰＣ測定条件は実施例に記載の方法による。
ここで、前記エポキシ樹脂（ｂ）のｍ＝０体含有量を所定の範囲とする観点では、当該原料フェノール化合物は、ＧＰＣ測定において下記式（３ａ）で表されるテトラメチルビスフェノールＦが９６～９９面積％含有されていることが好ましい。なお、式（３）におけるｎ＝１体の異性体としては、ｐ－ｐ体、ｏ－ｐ体、ｏ－ｏ体が考えられるが、下記式（３ａ）で表されるｐ－ｐ体がほとんどであり、ｏ－ｐ及びｏ－ｏ体は含有されていたとしても非常に微量なため無視してよい。また、テトラメチルビスフェノールＦとしては様々な微量成分が不純物として含まれている。例えば、２，６－キシレノールの水酸基と別の２，６－キシレノールのパラ位が付加重合した構造物等がある。そのため精製してこれらの不純物を除去することが好ましいが、その時、上記式（３）のｎ＝２以上の成分を除去しすぎないように調整することが重要である。 The phenol compound represented by the above formula (3), which is the raw material of the tetramethylbisphenol F-type epoxy resin of the present invention, has a total content of n = 2 or more in the GPC measurement of 0.5 to 2.5 areas. %, More preferably 0.55 to 2.2 area%, more preferably 0.6 to 2.0 area%. If the area is less than 0.5 area%, the amount of epoxy resin (a) produced is small, which is not preferable because the amount of epoxy resin (a) produced is small. If the area is 2.5 area% or more, the amount of epoxy resin (a) produced is large. Since it becomes too much, the viscosity becomes high, which is not preferable. The structure of the component having n = 2 or more is a structure in which the glycidyl group of the epoxy resin represented by the above formulas (1a) to (1c) is mainly substituted with a hydrogen atom.
The GPC measurement conditions are based on the method described in the examples.
Here, from the viewpoint that the m = 0 body content of the epoxy resin (b) is within a predetermined range, the raw material phenol compound has a tetramethylbisphenol F represented by the following formula (3a) of 96 to 96 in GPC measurement. It is preferably contained in an area% of 99. As the n = 1 isomer in the formula (3), a pp isomer, an opp isomer, and an oo isomer can be considered, and the pp isomer represented by the following formula (3a) is used. Most of them, and even if they are contained in op and o-o, they are very small and can be ignored. In addition, various trace components of tetramethylbisphenol F are contained as impurities. For example, there is a structure in which the hydroxyl group of 2,6-xylenol and another para-position of 2,6-xylenol are addition-polymerized. Therefore, it is preferable to purify to remove these impurities, but at that time, it is important to adjust so as not to remove too much the component of n = 2 or more in the above formula (3).
なお、ＧＰＣ測定条件は実施例に記載の方法による。
ここで、前記エポキシ樹脂（ｂ）のｍ＝０体含有量を所定の範囲とする観点では、当該原料フェノール化合物は、ＧＰＣ測定において下記式（３ａ）で表されるテトラメチルビスフェノールＦが９６～９９面積％含有されていることが好ましい。なお、式（３）におけるｎ＝１体の異性体としては、ｐ－ｐ体、ｏ－ｐ体、ｏ－ｏ体が考えられるが、下記式（３ａ）で表されるｐ－ｐ体がほとんどであり、ｏ－ｐ及びｏ－ｏ体は含有されていたとしても非常に微量なため無視してよい。また、テトラメチルビスフェノールＦとしては様々な微量成分が不純物として含まれている。例えば、２，６－キシレノールの水酸基と別の２，６－キシレノールのパラ位が付加重合した構造物等がある。そのため精製してこれらの不純物を除去することが好ましいが、その時、上記式（３）のｎ＝２以上の成分を除去しすぎないように調整することが重要である。 The phenol compound represented by the above formula (3), which is the raw material of the tetramethylbisphenol F-type epoxy resin of the present invention, has a total content of n = 2 or more in the GPC measurement of 0.5 to 2.5 areas. %, More preferably 0.55 to 2.2 area%, more preferably 0.6 to 2.0 area%. If the area is less than 0.5 area%, the amount of epoxy resin (a) produced is small, which is not preferable because the amount of epoxy resin (a) produced is small. If the area is 2.5 area% or more, the amount of epoxy resin (a) produced is large. Since it becomes too much, the viscosity becomes high, which is not preferable. The structure of the component having n = 2 or more is a structure in which the glycidyl group of the epoxy resin represented by the above formulas (1a) to (1c) is mainly substituted with a hydrogen atom.
The GPC measurement conditions are based on the method described in the examples.
Here, from the viewpoint that the m = 0 body content of the epoxy resin (b) is within a predetermined range, the raw material phenol compound has a tetramethylbisphenol F represented by the following formula (3a) of 96 to 96 in GPC measurement. It is preferably contained in an area% of 99. As the n = 1 isomer in the formula (3), a pp isomer, an opp isomer, and an oo isomer can be considered, and the pp isomer represented by the following formula (3a) is used. Most of them, and even if they are contained in op and o-o, they are very small and can be ignored. In addition, various trace components of tetramethylbisphenol F are contained as impurities. For example, there is a structure in which the hydroxyl group of 2,6-xylenol and another para-position of 2,6-xylenol are addition-polymerized. Therefore, it is preferable to purify to remove these impurities, but at that time, it is important to adjust so as not to remove too much the component of n = 2 or more in the above formula (3).
また、本発明のテトラメチルビスフェノールＦ型エポキシ樹脂のエポキシ当量は２００～２２０ｇ／ｅｑ．が好ましく、２０２ｇ～２１５ｇ／ｅｑ．がより好ましい。２００ｇ／ｅｑ．未満では結晶性が高くなり、２２０ｇ／ｅｑ．を超えると粘度が高くなる恐れがある。
The epoxy equivalent of the tetramethylbisphenol F-type epoxy resin of the present invention is 200 to 220 g / eq. Is preferable, and 202 g to 215 g / eq. Is more preferable. 200 g / eq. If it is less than, the crystallinity becomes high, and 220 g / eq. If it exceeds, the viscosity may increase.
加水分解性塩素は５，０００ｐｐｍ未満が好ましく、１０００ｐｐｍ以下がより好ましい。５，０００ｐｐｍを超えると硬化剤との反応性が悪くなり、得られる硬化物の物性が低下する恐れがある。
The hydrolyzable chlorine is preferably less than 5,000 ppm, more preferably 1000 ppm or less. If it exceeds 5,000 ppm, the reactivity with the curing agent is deteriorated, and the physical properties of the obtained cured product may be deteriorated.
αジオール含有量は１～２０ｍｅｑ．／１００ｇが好ましく、３～１２ｍｅｑ．／１００ｇがより好ましい。１ｍｅｑ．／１００ｇ未満では結晶性が高くなり、２０ｍｅｑ．／１００ｇを超えると硬化剤との反応性が悪くなり、得られる硬化物の物性が低下する恐れがある。
The α-diol content is 1 to 20 meq. / 100 g is preferable, and 3 to 12 meq. / 100g is more preferable. 1meq. If it is less than / 100 g, the crystallinity becomes high, and 20 meq. If it exceeds / 100 g, the reactivity with the curing agent is deteriorated, and the physical properties of the obtained cured product may be deteriorated.
フェノール性水酸基含有量は１～２０ｍｅｑ．／１００ｇが好ましく、３～１２ｍｅｑ．／１００ｇがより好ましい。１ｍｅｑ．／１００ｇ未満では結晶性が高くなり、２０ｍｅｑ／１００ｇを超えると硬化剤との反応性が悪くなり、得られる硬化物の物性が低下する恐れがある。
The phenolic hydroxyl group content is 1 to 20 meq. / 100 g is preferable, and 3 to 12 meq. / 100g is more preferable. 1meq. If it is less than / 100 g, the crystallinity becomes high, and if it exceeds 20 meq / 100 g, the reactivity with the curing agent deteriorates, and the physical properties of the obtained cured product may deteriorate.
２５℃における粘度は５０，０００～２００，０００ｍＰａ・ｓが好ましく、７０，０００～１５０，０００ｍＰａ・ｓがより好ましい。５０，０００ｍＰａ・ｓ未満では結晶性が高くなり、２００，０００ｍＰａ・ｓ以上では常温でのハンドリングが困難であり好ましくない。
The viscosity at 25 ° C. is preferably 50,000 to 200,000 mPa · s, more preferably 70,000 to 150,000 mPa · s. If it is less than 50,000 mPa · s, the crystallinity becomes high, and if it is 200,000 mPa · s or more, it is difficult to handle at room temperature, which is not preferable.
次に、本発明の製造方法について説明する。本発明は、ＧＰＣ測定における式（３）におけるｎ＝２以上の成分を０．５～２．５面積％含む原料フェノール化合物と、そのフェノール性水酸基１モルに対して２．０～３．０モルのエピクロルヒドリンとを、そのフェノール性水酸基１モルに対して０．９～１．１モルのアルカリ金属水酸化物の存在下で反応させる。
Next, the manufacturing method of the present invention will be described. In the present invention, a raw material phenol compound containing 0.5 to 2.5 area% of components of n = 2 or more in the formula (3) in GPC measurement and 2.0 to 3.0 with respect to 1 mol of the phenolic hydroxyl group thereof. Mol epichlorohydrin is reacted with 1 mol of its phenolic hydroxyl group in the presence of 0.9-1.1 mol of alkali metal hydroxide.
エピクロルヒドリンの量がフェノール性水酸基１モルに対して２．０モル未満では上記式（２）におけるｍ＝０体の含有量が７５面積％未満となり、得られるテトラメチルビスフェノールＦ型エポキシ樹脂の粘度及びエポキシ当量が高くなり、常温でのハンドリング性が悪くなる恐れがある。また、３．０モルを超えると、ｍ＝０体の含有量が８５面積％を超えるため、エポキシ樹脂（ａ）が存在していても、結晶性が高くなる恐れがある。
When the amount of epichlorohydrin is less than 2.0 mol with respect to 1 mol of phenolic hydroxyl group, the content of m = 0 in the above formula (2) is less than 75 area%, and the viscosity of the obtained tetramethylbisphenol F type epoxy resin and The epoxy equivalent becomes high, and the handleability at room temperature may deteriorate. Further, if it exceeds 3.0 mol, the content of m = 0 body exceeds 85 area%, so that even if the epoxy resin (a) is present, the crystallinity may be increased.
アルカリ金属水酸化物の量がフェノール性水酸基１モルに対して０．９モル未満ではαジオール含有量、加水分解性塩素、フェノール性水酸基含有量が高くなり硬化剤との反応性が劣り、得られる硬化物の物性が悪くなる恐れがある。また、１．１モルを超えるとαジオール、加水分解性塩素、フェノール性水酸基含有量が低くなり、結晶性が高くなる恐れがある。使用できるアルカリ金属水酸化物としては、水酸化カリウム、水酸化ナトリウム、水酸化リチウム等が挙げられる。これらのアルカリ金属水酸化物は、単独で使用してもよいし、２種類以上を併用してもよい。これらアルカリ金属水酸化物は通常２０～５０重量％の水溶液の形として使用される。
If the amount of alkali metal hydroxide is less than 0.9 mol with respect to 1 mol of phenolic hydroxyl group, the α-diol content, hydrolyzable chlorine, and phenolic hydroxyl group content will be high and the reactivity with the curing agent will be inferior. There is a risk that the physical properties of the cured product will deteriorate. Further, if it exceeds 1.1 mol, the content of α-diol, hydrolyzable chlorine, and phenolic hydroxyl group becomes low, and the crystallinity may become high. Examples of the alkali metal hydroxide that can be used include potassium hydroxide, sodium hydroxide, lithium hydroxide and the like. These alkali metal hydroxides may be used alone or in combination of two or more. These alkali metal hydroxides are usually used in the form of a 20-50% by weight aqueous solution.
また、上記モル比のアルカリ金属水酸化物の存在下で、エピクロルヒドリンと水を共沸により蒸発させ、エピクロルヒドリンを系内に戻し、生成水及び持込水を系内から除去しながら反応させることが好ましい。
Further, in the presence of the alkali metal hydroxide having the above molar ratio, epichlorohydrin and water can be evaporated by azeotrope, epichlorohydrin can be returned to the system, and the reaction can be carried out while removing the produced water and the brought-in water from the system. preferable.
なお、この反応では、原料フェノール化合物のｎ＝２以上の成分とエポキシ樹脂（ｂ）が反応したエポキシ樹脂（ｃ）も得られるが、非常に微量なため、エポキシ樹脂（ｂ）と分離することは難しい。そのため本発明ではこのエポキシ樹脂（ｃ）もエポキシ樹脂（ｂ）としてみなしている。
In this reaction, the epoxy resin (c) obtained by reacting the n = 2 or more component of the raw material phenol compound with the epoxy resin (b) can also be obtained, but since the amount is very small, it should be separated from the epoxy resin (b). Is difficult. Therefore, in the present invention, this epoxy resin (c) is also regarded as the epoxy resin (b).
実施例及び比較例を挙げて本発明を具体的に説明するが、本発明はその要旨を超えない限り、これらに限定されるものではない。特に断りがない限り、部は重量部を表し、％は重量％を表す。また、分析方法、測定方法は以下に示す。
The present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited thereto as long as the gist thereof is not exceeded. Unless otherwise specified, parts represent parts by weight and% represents% by weight. The analysis method and measurement method are shown below.
エポキシ当量：ＪＩＳ Ｋ ７２３６規格に準拠して測定を行い、単位はｇ／ｅｑ．である。
Epoxy equivalent: Measured in accordance with JIS K 7236 standard, unit is g / eq. Is.
加水分解性塩素：ＡＳＴＭ Ｄ－１７２６規格に準拠して測定を行い、単位は塩素原子の重量換算のｐｐｍである。
Hydrolyzable chlorine: Measured in accordance with ASTM D-1726 standard, and the unit is ppm in terms of weight of chlorine atom.
αジオール含有量：試料をクロロホルムに溶解後し、過剰のベンジルトリメチル過ヨウ素酸アンモニウム溶液を加えて反応させた後、１０％硫酸水溶液、２０％ヨウ化カリウム水溶液を加え、発生したヨウ素を１／５規定チオ硫酸ナトリウム溶液で電位差滴定することにより求めた。単位はｍｅｑ．／１００ｇである。
α-diol content: After dissolving the sample in chloroform and adding an excess ammonium benzyltrimethylperiodic acid solution for reaction, add a 10% sulfuric acid aqueous solution and a 20% potassium iodide aqueous solution, and add 1 / of the generated iodine. It was determined by potential differential titration with a 5N sodium thiosulfate solution. The unit is meq. / 100g.
フェノール性水酸基含有量：テトラヒドロフランとメタノール４％の混合物中でフェノール性水酸基にテトラメチルアンモニウムヒドロキサイドを作用し、発色させ、分光光度計を用いて３０５ｎｍにおける吸光度を測定した。予め、テトラメチルビスフェノールＦを標準として、同様の操作にて作成した検量線を用いて、フェノール性水酸基含有量を求めた。単位はｍｅｑ．／１００ｇである。
Phenolic hydroxyl group content: In a mixture of tetrahydrofuran and methanol 4%, tetramethylammonium hydroxyside was allowed to act on the phenolic hydroxyl group to develop a color, and the absorbance at 305 nm was measured using a spectrophotometer. The phenolic hydroxyl group content was determined in advance using a calibration curve prepared in the same manner using tetramethylbisphenol F as a standard. The unit is meq. / 100g.
粘度：ブルックフィールド型粘度計を用い、２５℃の粘度を測定した。単位はｍＰａ・ｓである。
Viscosity: The viscosity at 25 ° C was measured using a Brookfield type viscometer. The unit is mPa · s.
上記式（３）で表される原料フェノール化合物であるテトラメチルビスフェノールＦのｎ＝１体～ｎ＝３体の含有量、上記式（２）で表されるエポキシ樹脂（ｂ）のｍ＝０体の含有量：ＧＰＣ測定により求め、単位は面積％である。ＧＰＣ測定条件を次に示す。
装置：ＧＰＣ－８２２０システム（東ソー社製）
カラム：ＴＳＫ－ＧＥＬ（東ソー社製）
Ｇ２０００ＨＸＬ×２本＋Ｇ１０００ＨＸＬ
温度：４０℃
溶離液：テトラヒドロフラン
流量：１．０ｍＬ／分
検出器：ＲＩ
試料濃度：０．１ｇ／１０ｍＬ（テトラヒドロフラン）
試料注入量：２５μＬ The content of n = 1 to n = 3 of tetramethylbisphenol F, which is a raw material phenol compound represented by the above formula (3), and m = 0 of the epoxy resin (b) represented by the above formula (2). Body content: Determined by GPC measurement, the unit is area%. The GPC measurement conditions are shown below.
Equipment: GPC-8220 system (manufactured by Tosoh)
Column: TSK-GEL (manufactured by Tosoh)
G2000H XL x 2 + G1000H XL
Temperature: 40 ° C
Eluent: tetrahydrofuran Flow rate: 1.0 mL / min Detector: RI
Sample concentration: 0.1 g / 10 mL (tetrahydrofuran)
Sample injection volume: 25 μL
装置：ＧＰＣ－８２２０システム（東ソー社製）
カラム：ＴＳＫ－ＧＥＬ（東ソー社製）
Ｇ２０００ＨＸＬ×２本＋Ｇ１０００ＨＸＬ
温度：４０℃
溶離液：テトラヒドロフラン
流量：１．０ｍＬ／分
検出器：ＲＩ
試料濃度：０．１ｇ／１０ｍＬ（テトラヒドロフラン）
試料注入量：２５μＬ The content of n = 1 to n = 3 of tetramethylbisphenol F, which is a raw material phenol compound represented by the above formula (3), and m = 0 of the epoxy resin (b) represented by the above formula (2). Body content: Determined by GPC measurement, the unit is area%. The GPC measurement conditions are shown below.
Equipment: GPC-8220 system (manufactured by Tosoh)
Column: TSK-GEL (manufactured by Tosoh)
G2000H XL x 2 + G1000H XL
Temperature: 40 ° C
Eluent: tetrahydrofuran Flow rate: 1.0 mL / min Detector: RI
Sample concentration: 0.1 g / 10 mL (tetrahydrofuran)
Sample injection volume: 25 μL
上記式（１）で表されるエポキシ樹脂（ａ）の含有量：ＨＰＬＣ測定により求め、単位は面積％である。ＨＰＬＣ測定条件を次に示す。
装置：ＨＰＬＣ １２００Ｓｅｒｉｅｓ
（Ａｇｉｌｅｎｔ Ｔｅｃｈｎｏｌｏｇｉｅｓ社製）
カラム：Ｃａｄｅｒｎｚａ ＣＤ－Ｃ１８
（Ｉｎｔａｋｔ社製、粒径５μｍ、内径４．６ｍｍ、長さ１００ｍｍ）
温度：４０℃
溶離液：（Ａ液）蒸留水 、（Ｂ液）アセトニトリル
グラジェント条件：時間 Ａ液 Ｂ液
０分 ４０％ ６０％
５分 ４０％ ６０％
２０分 ０％ １００％
３０分 ０％ １００％
流量：１．０ｍＬ／分
検出器：ＵＶ（２４５ｎｍ）
試料濃度：０．０５ｇ／１０ｍＬ（アセトニトリル）
試料注入量：１０μＬ The content of the epoxy resin (a) represented by the above formula (1): determined by HPLC measurement, and the unit is area%. The HPLC measurement conditions are shown below.
Equipment: HPLC 1200 Series
(Manufactured by Agilent Technologies)
Column: Cadernza CD-C18
(Made by Intak, particle size 5 μm, inner diameter 4.6 mm, length 100 mm)
Temperature: 40 ° C
Eluent: (Liquid A) Distilled water, (Liquid B) Acetonitrile Granant Conditions: Time Liquid A Liquid B 0 minutes 40% 60%
5 minutes 40% 60%
20 minutes 0% 100%
30 minutes 0% 100%
Flow rate: 1.0 mL / min Detector: UV (245 nm)
Sample concentration: 0.05g / 10mL (acetonitrile)
Sample injection volume: 10 μL
装置：ＨＰＬＣ １２００Ｓｅｒｉｅｓ
（Ａｇｉｌｅｎｔ Ｔｅｃｈｎｏｌｏｇｉｅｓ社製）
カラム：Ｃａｄｅｒｎｚａ ＣＤ－Ｃ１８
（Ｉｎｔａｋｔ社製、粒径５μｍ、内径４．６ｍｍ、長さ１００ｍｍ）
温度：４０℃
溶離液：（Ａ液）蒸留水 、（Ｂ液）アセトニトリル
グラジェント条件：時間 Ａ液 Ｂ液
０分 ４０％ ６０％
５分 ４０％ ６０％
２０分 ０％ １００％
３０分 ０％ １００％
流量：１．０ｍＬ／分
検出器：ＵＶ（２４５ｎｍ）
試料濃度：０．０５ｇ／１０ｍＬ（アセトニトリル）
試料注入量：１０μＬ The content of the epoxy resin (a) represented by the above formula (1): determined by HPLC measurement, and the unit is area%. The HPLC measurement conditions are shown below.
Equipment: HPLC 1200 Series
(Manufactured by Agilent Technologies)
Column: Cadernza CD-C18
(Made by Intak, particle size 5 μm, inner diameter 4.6 mm, length 100 mm)
Temperature: 40 ° C
Eluent: (Liquid A) Distilled water, (Liquid B) Acetonitrile Granant Conditions: Time Liquid A Liquid B 0 minutes 40% 60%
5 minutes 40% 60%
20 minutes 0% 100%
30 minutes 0% 100%
Flow rate: 1.0 mL / min Detector: UV (245 nm)
Sample concentration: 0.05g / 10mL (acetonitrile)
Sample injection volume: 10 μL
実施例、比較例で使用した上記式（３）で表される原料フェノール化合物であるテトラメチルビスフェノールＦ（ＴＭＢＰＦ－１、ＴＭＢＰＦ－２）は以下のものである。
（ＴＭＢＰＦ－１）
ｎ＝１体：９７．５面積％、ｎ＝２体：０．９４面積％、ｎ＝３体：１．２面積％。
（ＴＭＢＰＦ－２）
ｎ＝１体：９９．７面積％、ｎ＝２体：０．１８面積％、ｎ＝３体：０面積％。 Tetramethylbisphenol F (TMBPF-1, TMBPF-2), which is a raw material phenol compound represented by the above formula (3) used in Examples and Comparative Examples, is as follows.
(TMBPF-1)
n = 1 body: 97.5 area%, n = 2 body: 0.94 area%, n = 3 body: 1.2 area%.
(TMBPF-2)
n = 1 body: 99.7 area%, n = 2 body: 0.18 area%, n = 3 body: 0 area%.
（ＴＭＢＰＦ－１）
ｎ＝１体：９７．５面積％、ｎ＝２体：０．９４面積％、ｎ＝３体：１．２面積％。
（ＴＭＢＰＦ－２）
ｎ＝１体：９９．７面積％、ｎ＝２体：０．１８面積％、ｎ＝３体：０面積％。 Tetramethylbisphenol F (TMBPF-1, TMBPF-2), which is a raw material phenol compound represented by the above formula (3) used in Examples and Comparative Examples, is as follows.
(TMBPF-1)
n = 1 body: 97.5 area%, n = 2 body: 0.94 area%, n = 3 body: 1.2 area%.
(TMBPF-2)
n = 1 body: 99.7 area%, n = 2 body: 0.18 area%, n = 3 body: 0 area%.
実施例１
撹拌機、温度計、窒素導入管、油水分離器付き還流冷却管及び減圧装置を装備したガラス製セパラブルフラスコに、ＴＭＢＰＦ－１：１２８．０部、エピクロルヒドリン：２３１．３部（ＴＭＢＰＦ－１のフェノール性水酸基１モルに対してエピクロルヒドリンは２．５モル）を仕込み、窒素雰囲気下、６０℃まで撹拌しながら昇温した。次に反応系内の温度を６０℃に維持しながら、徐々に減圧してエピクロルヒドリンを還流させた。４９％水酸化ナトリウム水溶液７７．６部（ＴＭＢＰＦ－１のフェノール性水酸基１モルに対して水酸化ナトリウムは０．９５モル）を１５０分かけて連続的に滴下した。この間、温度は６０～６５℃、減圧度は１００～１４０ｍｍＨｇで水とエピクロルヒドリンの共沸物を油水分離管で二層に分離し、下層のエピクロルヒドリンは系内に戻し、上層の水は系外に除去した。反応後、徐々に減圧度、温度を上げて、最終的に１５０℃、５ｍｍＨｇになるまでエピクロルヒドリンを蒸留、除去した。その後、反応系を常圧に戻し、トルエン３００部を加え溶解し、水を５００部加えて副生した食塩を分離、除去した。その後、３００部の水で、洗浄水が中性になるまで洗浄を繰り返した。この溶液から５ｍｍＨｇの減圧下、１５０℃に加熱してトルエンを除去し、テトラメチルビスフェノール型液状エポキシ樹脂を得た。得られたテトラメチルビスフェノールＦ型液状樹脂は、エポキシ樹脂（ａ）：２．３面積％、エポキシ樹脂（ｂ）のｍ＝０体：７８．２面積％、エポキシ当量：２０８ｇ／ｅｑ．、粘度：９８，０００ｍＰａ・ｓ、加水分解性塩素：２１０ｐｐｍ、αジオール含有量：９ｍｅｑ．／１００ｇ、フェノール性水酸基含有量：８ｍｅｑ．／１００ｇであった。この樹脂を２５℃で１００日間静置したが結晶が生成せず、液状を保った。 Example 1
TMBPF-1: 128.0 parts, epichlorohydrin: 231.3 parts (TMBPF-1) in a glass separable flask equipped with a stirrer, thermometer, nitrogen introduction pipe, reflux condenser with oil-water separator and decompression device. Epichlorohydrin (2.5 mol) was charged with respect to 1 mol of the phenolic hydroxyl group, and the temperature was raised to 60 ° C. with stirring under a nitrogen atmosphere. Next, while maintaining the temperature in the reaction system at 60 ° C., the pressure was gradually reduced to reflux epichlorohydrin. 77.6 parts of a 49% aqueous sodium hydroxide solution (0.95 mol of sodium hydroxide with respect to 1 mol of phenolic hydroxyl group of TMBPF-1) was continuously added dropwise over 150 minutes. During this period, the temperature was 60 to 65 ° C. and the decompression degree was 100 to 140 mmHg. The azeotropic product of water and epichlorohydrin was separated into two layers by an oil-water separation pipe, the lower epichlorohydrin was returned to the inside of the system, and the upper layer of water was removed from the system. Removed. After the reaction, the temperature was gradually increased to 150 ° C., and epichlorohydrin was distilled and removed until the temperature reached 150 ° C. and 5 mmHg. Then, the reaction system was returned to normal pressure, 300 parts of toluene was added to dissolve the reaction system, and 500 parts of water was added to separate and remove the by-produced salt. Then, washing was repeated with 300 parts of water until the washing water became neutral. Toluene was removed from this solution by heating to 150 ° C. under a reduced pressure of 5 mmHg to obtain a tetramethylbisphenol type liquid epoxy resin. The obtained tetramethylbisphenol F type liquid resin had an epoxy resin (a): 2.3 area%, m = 0 body of the epoxy resin (b): 78.2 area%, and an epoxy equivalent: 208 g / eq. , Viscosity: 98,000 mPa · s, Hydrolyzable chlorine: 210 ppm, α-diol content: 9 meq. / 100 g, phenolic hydroxyl group content: 8 meq. It was / 100 g. The resin was allowed to stand at 25 ° C. for 100 days, but no crystals were formed and the resin remained liquid.
撹拌機、温度計、窒素導入管、油水分離器付き還流冷却管及び減圧装置を装備したガラス製セパラブルフラスコに、ＴＭＢＰＦ－１：１２８．０部、エピクロルヒドリン：２３１．３部（ＴＭＢＰＦ－１のフェノール性水酸基１モルに対してエピクロルヒドリンは２．５モル）を仕込み、窒素雰囲気下、６０℃まで撹拌しながら昇温した。次に反応系内の温度を６０℃に維持しながら、徐々に減圧してエピクロルヒドリンを還流させた。４９％水酸化ナトリウム水溶液７７．６部（ＴＭＢＰＦ－１のフェノール性水酸基１モルに対して水酸化ナトリウムは０．９５モル）を１５０分かけて連続的に滴下した。この間、温度は６０～６５℃、減圧度は１００～１４０ｍｍＨｇで水とエピクロルヒドリンの共沸物を油水分離管で二層に分離し、下層のエピクロルヒドリンは系内に戻し、上層の水は系外に除去した。反応後、徐々に減圧度、温度を上げて、最終的に１５０℃、５ｍｍＨｇになるまでエピクロルヒドリンを蒸留、除去した。その後、反応系を常圧に戻し、トルエン３００部を加え溶解し、水を５００部加えて副生した食塩を分離、除去した。その後、３００部の水で、洗浄水が中性になるまで洗浄を繰り返した。この溶液から５ｍｍＨｇの減圧下、１５０℃に加熱してトルエンを除去し、テトラメチルビスフェノール型液状エポキシ樹脂を得た。得られたテトラメチルビスフェノールＦ型液状樹脂は、エポキシ樹脂（ａ）：２．３面積％、エポキシ樹脂（ｂ）のｍ＝０体：７８．２面積％、エポキシ当量：２０８ｇ／ｅｑ．、粘度：９８，０００ｍＰａ・ｓ、加水分解性塩素：２１０ｐｐｍ、αジオール含有量：９ｍｅｑ．／１００ｇ、フェノール性水酸基含有量：８ｍｅｑ．／１００ｇであった。この樹脂を２５℃で１００日間静置したが結晶が生成せず、液状を保った。 Example 1
TMBPF-1: 128.0 parts, epichlorohydrin: 231.3 parts (TMBPF-1) in a glass separable flask equipped with a stirrer, thermometer, nitrogen introduction pipe, reflux condenser with oil-water separator and decompression device. Epichlorohydrin (2.5 mol) was charged with respect to 1 mol of the phenolic hydroxyl group, and the temperature was raised to 60 ° C. with stirring under a nitrogen atmosphere. Next, while maintaining the temperature in the reaction system at 60 ° C., the pressure was gradually reduced to reflux epichlorohydrin. 77.6 parts of a 49% aqueous sodium hydroxide solution (0.95 mol of sodium hydroxide with respect to 1 mol of phenolic hydroxyl group of TMBPF-1) was continuously added dropwise over 150 minutes. During this period, the temperature was 60 to 65 ° C. and the decompression degree was 100 to 140 mmHg. The azeotropic product of water and epichlorohydrin was separated into two layers by an oil-water separation pipe, the lower epichlorohydrin was returned to the inside of the system, and the upper layer of water was removed from the system. Removed. After the reaction, the temperature was gradually increased to 150 ° C., and epichlorohydrin was distilled and removed until the temperature reached 150 ° C. and 5 mmHg. Then, the reaction system was returned to normal pressure, 300 parts of toluene was added to dissolve the reaction system, and 500 parts of water was added to separate and remove the by-produced salt. Then, washing was repeated with 300 parts of water until the washing water became neutral. Toluene was removed from this solution by heating to 150 ° C. under a reduced pressure of 5 mmHg to obtain a tetramethylbisphenol type liquid epoxy resin. The obtained tetramethylbisphenol F type liquid resin had an epoxy resin (a): 2.3 area%, m = 0 body of the epoxy resin (b): 78.2 area%, and an epoxy equivalent: 208 g / eq. , Viscosity: 98,000 mPa · s, Hydrolyzable chlorine: 210 ppm, α-diol content: 9 meq. / 100 g, phenolic hydroxyl group content: 8 meq. It was / 100 g. The resin was allowed to stand at 25 ° C. for 100 days, but no crystals were formed and the resin remained liquid.
実施例２
実施例１と同様の装置で原料をＴＭＢＰＦ－１：２５．６部とＴＭＢＰＦ－２：１０２．４部の混合物とした以外は同様の操作を行って、テトラメチルビスフェノールＦ型液状樹脂を得た。この原料混合物はｎ＝１体：９９．２３面積％、ｎ＝２体：０．３３面積％、ｎ＝３体：０．２４面積％であった。得られたテトラメチルビスフェノールＦ型液状樹脂は、エポキシ樹脂（ａ）：０．６０面積％、エポキシ樹脂（ｂ）のｍ＝０体：７８．０面積％、エポキシ当量：２０５ｇ／ｅｑ．、粘度：９８，０００ｍＰａ・ｓ、加水分解性塩素：３００ｐｐｍ、αジオール含有量：９ｍｅｑ．／１００ｇ、フェノール性水酸基含有量：７ｍｅｑ．／１００ｇであった。この樹脂を２５℃で１００日間静置したが結晶が生成せず、液状を保った。 Example 2
The same operation was carried out except that the raw material was a mixture of TMBPF-1: 25.6 parts and TMBPF-2: 102.4 parts in the same apparatus as in Example 1 to obtain a tetramethylbisphenol F type liquid resin. .. This raw material mixture had n = 1 body: 99.23 area%, n = 2 bodies: 0.33 area%, and n = 3 bodies: 0.24 area%. The obtained tetramethylbisphenol F type liquid resin had an epoxy resin (a): 0.60 area%, an m = 0 body of the epoxy resin (b): 78.0 area%, and an epoxy equivalent: 205 g / eq. , Viscosity: 98,000 mPa · s, Hydrolyzable chlorine: 300 ppm, α-diol content: 9 meq. / 100 g, phenolic hydroxyl group content: 7 meq. It was / 100 g. The resin was allowed to stand at 25 ° C. for 100 days, but no crystals were formed and the resin remained liquid.
実施例１と同様の装置で原料をＴＭＢＰＦ－１：２５．６部とＴＭＢＰＦ－２：１０２．４部の混合物とした以外は同様の操作を行って、テトラメチルビスフェノールＦ型液状樹脂を得た。この原料混合物はｎ＝１体：９９．２３面積％、ｎ＝２体：０．３３面積％、ｎ＝３体：０．２４面積％であった。得られたテトラメチルビスフェノールＦ型液状樹脂は、エポキシ樹脂（ａ）：０．６０面積％、エポキシ樹脂（ｂ）のｍ＝０体：７８．０面積％、エポキシ当量：２０５ｇ／ｅｑ．、粘度：９８，０００ｍＰａ・ｓ、加水分解性塩素：３００ｐｐｍ、αジオール含有量：９ｍｅｑ．／１００ｇ、フェノール性水酸基含有量：７ｍｅｑ．／１００ｇであった。この樹脂を２５℃で１００日間静置したが結晶が生成せず、液状を保った。 Example 2
The same operation was carried out except that the raw material was a mixture of TMBPF-1: 25.6 parts and TMBPF-2: 102.4 parts in the same apparatus as in Example 1 to obtain a tetramethylbisphenol F type liquid resin. .. This raw material mixture had n = 1 body: 99.23 area%, n = 2 bodies: 0.33 area%, and n = 3 bodies: 0.24 area%. The obtained tetramethylbisphenol F type liquid resin had an epoxy resin (a): 0.60 area%, an m = 0 body of the epoxy resin (b): 78.0 area%, and an epoxy equivalent: 205 g / eq. , Viscosity: 98,000 mPa · s, Hydrolyzable chlorine: 300 ppm, α-diol content: 9 meq. / 100 g, phenolic hydroxyl group content: 7 meq. It was / 100 g. The resin was allowed to stand at 25 ° C. for 100 days, but no crystals were formed and the resin remained liquid.
実施例３
実施例１と同様の装置を使用し、仕込量をＴＭＢＰＦ－１：１２８．０部、エピクロルヒドリン：２６８．３部（ＴＭＢＰＦ－１のフェノール性水酸基１モルに対してエピクロルヒドリンは２．９モル）とした以外は実施例１と同様の操作を行った。得られたテトラメチルビスフェノールＦ型液状樹脂は、エポキシ樹脂（ａ）：２．３面積％、エポキシ樹脂（ｂ）のｍ＝０体：８４．２面積％、エポキシ当量：２０２ｇ／ｅｑ．、粘度：７９，０００ｍＰａ・ｓ、加水分解性塩素：２００ｐｐｍ、αジオール含有量：７ｍｅｑ．／１００ｇ、フェノール性水酸基含有量：７ｍｅｑ．／１００ｇであった。この樹脂を２５℃で１００日間静置したが結晶が生成せず、液状を保った。 Example 3
Using the same equipment as in Example 1, the amount charged was TMBPF-1: 128.0 parts, epichlorohydrin: 268.3 parts (epichlorohydrin was 2.9 mol with respect to 1 mol of phenolic hydroxyl group of TMBPF-1). The same operation as in Example 1 was performed except that the above was performed. The obtained tetramethylbisphenol F type liquid resin had an epoxy resin (a): 2.3 area%, an m = 0 body of the epoxy resin (b): 84.2 area%, and an epoxy equivalent: 202 g / eq. , Viscosity: 79,000 mPa · s, Hydrolyzable chlorine: 200 ppm, α-diol content: 7 meq. / 100 g, phenolic hydroxyl group content: 7 meq. It was / 100 g. The resin was allowed to stand at 25 ° C. for 100 days, but no crystals were formed and the resin remained liquid.
実施例１と同様の装置を使用し、仕込量をＴＭＢＰＦ－１：１２８．０部、エピクロルヒドリン：２６８．３部（ＴＭＢＰＦ－１のフェノール性水酸基１モルに対してエピクロルヒドリンは２．９モル）とした以外は実施例１と同様の操作を行った。得られたテトラメチルビスフェノールＦ型液状樹脂は、エポキシ樹脂（ａ）：２．３面積％、エポキシ樹脂（ｂ）のｍ＝０体：８４．２面積％、エポキシ当量：２０２ｇ／ｅｑ．、粘度：７９，０００ｍＰａ・ｓ、加水分解性塩素：２００ｐｐｍ、αジオール含有量：７ｍｅｑ．／１００ｇ、フェノール性水酸基含有量：７ｍｅｑ．／１００ｇであった。この樹脂を２５℃で１００日間静置したが結晶が生成せず、液状を保った。 Example 3
Using the same equipment as in Example 1, the amount charged was TMBPF-1: 128.0 parts, epichlorohydrin: 268.3 parts (epichlorohydrin was 2.9 mol with respect to 1 mol of phenolic hydroxyl group of TMBPF-1). The same operation as in Example 1 was performed except that the above was performed. The obtained tetramethylbisphenol F type liquid resin had an epoxy resin (a): 2.3 area%, an m = 0 body of the epoxy resin (b): 84.2 area%, and an epoxy equivalent: 202 g / eq. , Viscosity: 79,000 mPa · s, Hydrolyzable chlorine: 200 ppm, α-diol content: 7 meq. / 100 g, phenolic hydroxyl group content: 7 meq. It was / 100 g. The resin was allowed to stand at 25 ° C. for 100 days, but no crystals were formed and the resin remained liquid.
比較例１
実施例１と同様の装置で原料をＴＭＢＰＦ－２とした以外は同様の操作を行い、テトラメチルビスフェノールＦ型液状樹脂を得た。得られたテトラメチルビスフェノールＦ型液状樹脂は、エポキシ樹脂（ｂ）のｍ＝０体：７７．５面積％、エポキシ当量：２０７ｇ／ｅｑ．、粘度：９５，０００ｍＰａ・ｓ、加水分解性塩素：２２０ｐｐｍ、αジオール含有量：８ｍｅｑ．／１００ｇ、フェノール性水酸基含有量：８ｍｅｑ．／１００ｇであった。なお、エポキシ樹脂（ａ）は検出できなかった。この樹脂を２５℃で静置したところ２３日目で結晶が生成した。 Comparative Example 1
The same operation was carried out except that the raw material was TMBPF-2 in the same apparatus as in Example 1 to obtain a tetramethylbisphenol F type liquid resin. The obtained tetramethylbisphenol F type liquid resin had m = 0 body of epoxy resin (b): 77.5 area%, epoxy equivalent: 207 g / eq. , Viscosity: 95,000 mPa · s, Hydrolyzable chlorine: 220 ppm, α-diol content: 8 meq. / 100 g, phenolic hydroxyl group content: 8 meq. It was / 100 g. The epoxy resin (a) could not be detected. When this resin was allowed to stand at 25 ° C., crystals were formed on the 23rd day.
実施例１と同様の装置で原料をＴＭＢＰＦ－２とした以外は同様の操作を行い、テトラメチルビスフェノールＦ型液状樹脂を得た。得られたテトラメチルビスフェノールＦ型液状樹脂は、エポキシ樹脂（ｂ）のｍ＝０体：７７．５面積％、エポキシ当量：２０７ｇ／ｅｑ．、粘度：９５，０００ｍＰａ・ｓ、加水分解性塩素：２２０ｐｐｍ、αジオール含有量：８ｍｅｑ．／１００ｇ、フェノール性水酸基含有量：８ｍｅｑ．／１００ｇであった。なお、エポキシ樹脂（ａ）は検出できなかった。この樹脂を２５℃で静置したところ２３日目で結晶が生成した。 Comparative Example 1
The same operation was carried out except that the raw material was TMBPF-2 in the same apparatus as in Example 1 to obtain a tetramethylbisphenol F type liquid resin. The obtained tetramethylbisphenol F type liquid resin had m = 0 body of epoxy resin (b): 77.5 area%, epoxy equivalent: 207 g / eq. , Viscosity: 95,000 mPa · s, Hydrolyzable chlorine: 220 ppm, α-diol content: 8 meq. / 100 g, phenolic hydroxyl group content: 8 meq. It was / 100 g. The epoxy resin (a) could not be detected. When this resin was allowed to stand at 25 ° C., crystals were formed on the 23rd day.
比較例２
実施例１と同様の装置を使用し、仕込量をＴＭＢＰＦ－１：１２８．０部、エピクロルヒドリン：５５５．０部（ＴＭＢＰＦ－１のフェノール性水酸基１モルに対してエピクロルヒドリンは６．０モル）とした以外は実施例１と同様の操作を行った。得られたテトラメチルビスフェノールＦ型液状樹脂は、エポキシ樹脂（ａ）：２．３面積％、エポキシ樹脂（ｂ）のｍ＝０体：８８．８面積％、エポキシ当量：２００ｇ／ｅｑ．、粘度：７２，０００ｍＰａ・ｓ、加水分解性塩素：２００ｐｐｍ、αジオール含有量：６ｍｅｑ．／１００ｇ、フェノール性水酸基含有量：７ｍｅｑ．／１００ｇであった。この樹脂を２５℃で静置したところ１５日目で結晶が生成した。 Comparative Example 2
Using the same equipment as in Example 1, the amount charged was TMBPF-1: 128.0 parts and epichlorohydrin: 555.0 parts (epichlorohydrin was 6.0 mol with respect to 1 mol of phenolic hydroxyl group of TMBPF-1). The same operation as in Example 1 was performed except that the above was performed. The obtained tetramethylbisphenol F type liquid resin had an epoxy resin (a): 2.3 area%, an m = 0 body of the epoxy resin (b): 88.8 area%, and an epoxy equivalent: 200 g / eq. , Viscosity: 72,000 mPa · s, Hydrolyzable chlorine: 200 ppm, α-diol content: 6 meq. / 100 g, phenolic hydroxyl group content: 7 meq. It was / 100 g. When this resin was allowed to stand at 25 ° C., crystals were formed on the 15th day.
実施例１と同様の装置を使用し、仕込量をＴＭＢＰＦ－１：１２８．０部、エピクロルヒドリン：５５５．０部（ＴＭＢＰＦ－１のフェノール性水酸基１モルに対してエピクロルヒドリンは６．０モル）とした以外は実施例１と同様の操作を行った。得られたテトラメチルビスフェノールＦ型液状樹脂は、エポキシ樹脂（ａ）：２．３面積％、エポキシ樹脂（ｂ）のｍ＝０体：８８．８面積％、エポキシ当量：２００ｇ／ｅｑ．、粘度：７２，０００ｍＰａ・ｓ、加水分解性塩素：２００ｐｐｍ、αジオール含有量：６ｍｅｑ．／１００ｇ、フェノール性水酸基含有量：７ｍｅｑ．／１００ｇであった。この樹脂を２５℃で静置したところ１５日目で結晶が生成した。 Comparative Example 2
Using the same equipment as in Example 1, the amount charged was TMBPF-1: 128.0 parts and epichlorohydrin: 555.0 parts (epichlorohydrin was 6.0 mol with respect to 1 mol of phenolic hydroxyl group of TMBPF-1). The same operation as in Example 1 was performed except that the above was performed. The obtained tetramethylbisphenol F type liquid resin had an epoxy resin (a): 2.3 area%, an m = 0 body of the epoxy resin (b): 88.8 area%, and an epoxy equivalent: 200 g / eq. , Viscosity: 72,000 mPa · s, Hydrolyzable chlorine: 200 ppm, α-diol content: 6 meq. / 100 g, phenolic hydroxyl group content: 7 meq. It was / 100 g. When this resin was allowed to stand at 25 ° C., crystals were formed on the 15th day.
比較例３
実施例１と同様の装置を使用し、仕込量をＴＭＢＰＦ－２：１２８．０部、エピクロルヒドリン：１８０．０部（ＴＭＢＰＦ－１のフェノール性水酸基１モルに対してエピクロルヒドリンは１．９４モル）とした以外は実施例１と同様の操作を行った。得られたテトラメチルビスフェノールＦ型液状樹脂は、エポキシ樹脂（ａ）：０面積％、エポキシ樹脂（ｂ）のｍ＝０体：７３．２面積％、エポキシ当量：２１９ｇ／ｅｑ．、粘度：１８７，０００ｍＰａ・ｓ、加水分解性塩素：５０ｐｐｍ、αジオール含有量：８ｍｅｑ．／１００ｇ、フェノール性水酸基含有量：４ｍｅｑ．／１００ｇであった。この樹脂を２５℃で静置したところ９６日目で結晶が生成した。 Comparative Example 3
Using the same equipment as in Example 1, the amount charged was TMBPF-2: 128.0 parts, epichlorohydrin: 180.0 parts (1 mol of phenolic hydroxyl group of TMBPF-1 and 1.94 mol of epichlorohydrin). The same operation as in Example 1 was performed except that the above was performed. The obtained tetramethylbisphenol F type liquid resin had an epoxy resin (a): 0 area%, an m = 0 body of the epoxy resin (b): 73.2 area%, and an epoxy equivalent: 219 g / eq. , Viscosity: 187,000 mPa · s, Hydrolyzable chlorine: 50 ppm, α-diol content: 8 meq. / 100 g, phenolic hydroxyl group content: 4 meq. It was / 100 g. When this resin was allowed to stand at 25 ° C., crystals were formed on the 96th day.
実施例１と同様の装置を使用し、仕込量をＴＭＢＰＦ－２：１２８．０部、エピクロルヒドリン：１８０．０部（ＴＭＢＰＦ－１のフェノール性水酸基１モルに対してエピクロルヒドリンは１．９４モル）とした以外は実施例１と同様の操作を行った。得られたテトラメチルビスフェノールＦ型液状樹脂は、エポキシ樹脂（ａ）：０面積％、エポキシ樹脂（ｂ）のｍ＝０体：７３．２面積％、エポキシ当量：２１９ｇ／ｅｑ．、粘度：１８７，０００ｍＰａ・ｓ、加水分解性塩素：５０ｐｐｍ、αジオール含有量：８ｍｅｑ．／１００ｇ、フェノール性水酸基含有量：４ｍｅｑ．／１００ｇであった。この樹脂を２５℃で静置したところ９６日目で結晶が生成した。 Comparative Example 3
Using the same equipment as in Example 1, the amount charged was TMBPF-2: 128.0 parts, epichlorohydrin: 180.0 parts (1 mol of phenolic hydroxyl group of TMBPF-1 and 1.94 mol of epichlorohydrin). The same operation as in Example 1 was performed except that the above was performed. The obtained tetramethylbisphenol F type liquid resin had an epoxy resin (a): 0 area%, an m = 0 body of the epoxy resin (b): 73.2 area%, and an epoxy equivalent: 219 g / eq. , Viscosity: 187,000 mPa · s, Hydrolyzable chlorine: 50 ppm, α-diol content: 8 meq. / 100 g, phenolic hydroxyl group content: 4 meq. It was / 100 g. When this resin was allowed to stand at 25 ° C., crystals were formed on the 96th day.
本発明のテトラメチルビスフェノールＦ型エポキシ樹脂は、床材、接着剤等、特に屋外環境下で使用される用途に有用である。また、塗料用原料等工業原料としても有用である。
The tetramethylbisphenol F type epoxy resin of the present invention is useful for flooring materials, adhesives, etc., especially for applications used in an outdoor environment. It is also useful as an industrial raw material such as a raw material for paints.
Claims (4)
- 高速液体クロマトグラフィー測定において、下記式（１）で表されるエポキシ樹脂を０．１～２．５面積％含み、ゲルパーミエーションクロマトグラフィー測定において、下記式（２）で表されるエポキシ樹脂のｍ＝０体を７５～８５面積％含み、常温で液状であることを特徴とするテトラメチルビスフェノールＦ型エポキシ樹脂。
（ここで、ｋは２又は３である。）
（ここで、ｍは繰り返し数である。） In the high performance liquid chromatography measurement, the epoxy resin represented by the following formula (1) is contained in an area% of 0.1 to 2.5 area%, and in the gel permeation chromatography measurement, the epoxy resin represented by the following formula (2) is contained. A tetramethylbisphenol F-type epoxy resin containing 75 to 85 area% of m = 0 and liquid at room temperature.
(Here, k is 2 or 3.)
(Here, m is the number of repetitions.) - 下記式（３）で表されるフェノール化合物とエピクロルヒドリンとをアルカリ金属水酸化物の存在下で反応させることにより得られ、ゲルパーミエーションクロマトグラフィー測定において、下記式（２）で表されるエポキシ樹脂のｍ＝０体を７５～８５面積％含み、常温で液状であることを特徴とするテトラメチルビスフェノールＦ型エポキシ樹脂。
（ここで、ｎは繰り返し数であり、その平均値は１．００５～３である。ゲルパーミエーションクロマトグラフィー測定において、ｎ＝２以上の成分を０．５～２．５面積％含む。）
（ここで、ｍは繰り返し数である。） It is obtained by reacting a phenol compound represented by the following formula (3) with epichlorohydrin in the presence of an alkali metal hydroxide, and in gel permeation chromatography measurement, an epoxy resin represented by the following formula (2). A tetramethylbisphenol F-type epoxy resin containing 75 to 85 area% of m = 0 and liquid at room temperature.
(Here, n is the number of repetitions, and the average value thereof is 1.005 to 3. In the gel permeation chromatography measurement, 0.5 to 2.5 area% of components having n = 2 or more are contained.)
(Here, m is the number of repetitions.) - エポキシ当量が２００～２２０ｇ／ｅｑ．、加水分解性塩素が５，０００ｐｐｍ未満、αジオール含有量が１～２０ｍｅｑ．／１００ｇ、フェノール性水酸基含有量が１～２０ｍｅｑ．／１００ｇ、２５℃における粘度が５０，０００～２００，０００ｍＰａ・ｓである請求項１又は２に記載のテトラメチルビスフェノールＦ型エポキシ樹脂。 Epoxy equivalent is 200-220 g / eq. , Hydrolyzable chlorine is less than 5,000 ppm, α-diol content is 1 to 20 meq. / 100 g, phenolic hydroxyl group content 1 to 20 meq. The tetramethylbisphenol F type epoxy resin according to claim 1 or 2, which has a viscosity of 50,000 to 200,000 mPa · s at / 100 g and 25 ° C.
- 請求項１～３のいずれか１項に記載のテトラメチルビスフェノールＦ型エポキシ樹脂を製造する方法であって、
ゲルパーミエーションクロマトグラフィー測定において、下記式（３）におけるｎ＝２以上の成分を０．５～２．５面積％含むフェノール化合物と、該フェノール化合物のフェノール性水酸基１モルに対して２．０～３．０モルのエピクロルヒドリンとを、該フェノール化合物のフェノール性水酸基１モルに対して０．９～１．１モルのアルカリ金属水酸化物の存在下で反応させることを特徴とするテトラメチルビスフェノールＦ型エポキシ樹脂の製造方法。
（ここで、ｎは繰り返し数であり、その平均値は１．００５～３である。）
The method for producing a tetramethylbisphenol F type epoxy resin according to any one of claims 1 to 3.
In the gel permeation chromatography measurement, a phenol compound containing 0.5 to 2.5 area% of n = 2 or more components in the following formula (3) and 2.0 per 1 mol of phenolic hydroxyl group of the phenol compound. Tetramethylbisphenol characterized by reacting with ~ 3.0 mol of epichlorohydrin with 1 mol of phenolic hydroxyl group of the phenol compound in the presence of 0.9 to 1.1 mol of alkali metal hydroxide. A method for producing an F-type epoxy resin.
(Here, n is the number of repetitions, and the average value thereof is 1.005 to 3.)
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| JPH07109328A (en) * | 1993-10-15 | 1995-04-25 | Nippon Steel Chem Co Ltd | High-purity and low-viscosity solid epoxy resin and production thereof |
| JPH07126574A (en) * | 1993-10-29 | 1995-05-16 | Nippon Steel Chem Co Ltd | Epoxy resin composition for powder coating |
| JPH07179564A (en) * | 1993-12-24 | 1995-07-18 | Nippon Steel Chem Co Ltd | Production of low viscosity crystalline epoxy resin |
| JPH1060088A (en) * | 1996-08-22 | 1998-03-03 | Nippon Steel Chem Co Ltd | Epoxy resin composition for sealing electronic part and its cured substance |
| JP2000345008A (en) * | 1999-06-09 | 2000-12-12 | Sumitomo Chem Co Ltd | Epoxy resin composition and molded article thereof |
| JP2003012763A (en) * | 2001-06-27 | 2003-01-15 | Toto Kasei Co Ltd | Epoxy resin, epoxy resin composition including the same, and cured product of the composition |
| JP2017155080A (en) * | 2016-02-29 | 2017-09-07 | 新日鉄住金化学株式会社 | Bisphenol f type epoxy resin and manufacturing method thereof |
| JP2018536754A (en) * | 2015-11-03 | 2018-12-13 | エスダブリューアイエムシー・エルエルシー | Liquid epoxy resin composition useful for polymer production |
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| JPH06345850A (en) * | 1993-06-08 | 1994-12-20 | Nippon Steel Chem Co Ltd | Epoxy resin composition |
| JPH07109328A (en) * | 1993-10-15 | 1995-04-25 | Nippon Steel Chem Co Ltd | High-purity and low-viscosity solid epoxy resin and production thereof |
| JPH07126574A (en) * | 1993-10-29 | 1995-05-16 | Nippon Steel Chem Co Ltd | Epoxy resin composition for powder coating |
| JPH07179564A (en) * | 1993-12-24 | 1995-07-18 | Nippon Steel Chem Co Ltd | Production of low viscosity crystalline epoxy resin |
| JPH1060088A (en) * | 1996-08-22 | 1998-03-03 | Nippon Steel Chem Co Ltd | Epoxy resin composition for sealing electronic part and its cured substance |
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| JP2018536754A (en) * | 2015-11-03 | 2018-12-13 | エスダブリューアイエムシー・エルエルシー | Liquid epoxy resin composition useful for polymer production |
| JP2017155080A (en) * | 2016-02-29 | 2017-09-07 | 新日鉄住金化学株式会社 | Bisphenol f type epoxy resin and manufacturing method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114929773A (en) * | 2019-11-21 | 2022-08-19 | Swimc有限公司 | Two-part epoxy composition for adhesive coating of storage articles |
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