JP2017114947A - Fluorene condensate composition and epoxidation composition and manufacturing method thereof - Google Patents
Fluorene condensate composition and epoxidation composition and manufacturing method thereof Download PDFInfo
- Publication number
- JP2017114947A JP2017114947A JP2015248877A JP2015248877A JP2017114947A JP 2017114947 A JP2017114947 A JP 2017114947A JP 2015248877 A JP2015248877 A JP 2015248877A JP 2015248877 A JP2015248877 A JP 2015248877A JP 2017114947 A JP2017114947 A JP 2017114947A
- Authority
- JP
- Japan
- Prior art keywords
- group
- compound represented
- fluorene
- formula
- integer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Phenolic Resins Or Amino Resins (AREA)
- Epoxy Resins (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
本発明は、機能性樹脂の原料、半導体製造工程で用いられるレジストや下層膜の原料として有用なフルオレン縮合体組成物およびエポキシ化組成物ならびにそれらの製造方法に関する。 The present invention relates to a functional resin raw material, a fluorene condensate composition and an epoxidized composition useful as a raw material for a resist and an underlayer film used in a semiconductor manufacturing process, and a method for producing them.
フルオレノン類とフェノール類および／またはナフトール類とを反応させて得られるビスフェノールフルオレン類は、ポリエステル、ポリカーボネート、エポキシ樹脂等の機能性樹脂の原料として有用である。また、ビスフェノールフルオレン類は、半導体製造工程で用いられるレジストや下層膜等の原料またはブレンド物としても用いられる。ビスフェノールフルオレン類を原料に用いた樹脂は、光学特性、耐熱性、強度などに優れている。 Bisphenolfluorenes obtained by reacting fluorenones with phenols and / or naphthols are useful as raw materials for functional resins such as polyesters, polycarbonates, and epoxy resins. Bisphenolfluorenes are also used as raw materials or blends for resists and underlayer films used in semiconductor manufacturing processes. Resins using bisphenol fluorenes as raw materials are excellent in optical properties, heat resistance, strength, and the like.
このようなビスフェノールフルオレン類の製造に関しては、特許文献１〜３に開示されている。また、特許文献４には、ビスフェノールフルオレン類の製造時に、２量体以上の縮合体も同時に生成することが記載されている。 The production of such bisphenol fluorenes is disclosed in Patent Documents 1 to 3. Further, Patent Document 4 describes that a condensate of a dimer or higher is simultaneously generated during the production of bisphenol fluorenes.
しかしながら、従来の公知文献は、２量体以上の縮合体は、反応生成物に対して１０％以下の含有量であるか、または、縮合体含有量に関する開示がなされていないものがほとんどである。また、縮合体含有量が１０％以上組成物の特性は従来の公知文献では明らかにされていなかった。 However, in the conventional publicly known literature, most of the condensates having a dimer or more have a content of 10% or less with respect to the reaction product, or most of the condensates are not disclosed. . Further, the properties of the composition having a condensate content of 10% or more have not been clarified in the conventional known literature.
一方、従来の、ビスフェノールフルオレン類単量体を高純度で含む化合物は、２５０℃以上の高温で昇華しやすく、そのため、高温で揮発分が問題となる用途、例えば、半導体製造工程で使用するレジストや下層膜に、ブレンドして用いる場合は、その使用が制限される問題があった。 On the other hand, conventional compounds containing bisphenolfluorene monomers with high purity are likely to sublime at a high temperature of 250 ° C. or higher. Therefore, resists used in semiconductor manufacturing processes, for example, where volatile matter becomes a problem at high temperatures. In the case of blending with a lower layer film, there is a problem that its use is limited.
また、高純度ビスフェノールフルオレン類は、結晶が飛散しやすく、飛散して人体に付着すると、一時的なかゆみや長期的な健康障害を起こす可能性があるため、その製造工程では、高度の防御服の使用や粉塵対策設備が必要である問題があった。 High-purity bisphenol fluorenes can easily disperse crystals, which can cause temporary itchiness and long-term health problems when scattered. There was a problem that the use of dust and equipment for dust prevention were necessary.
そこで、本発明は、熱重量減少率が小さく、合成作業の際のかゆみの問題もない、フルオレン縮合体組成物およびその製造方法、ならびにエポキシ樹脂の原料として有用なエポキシ化組成物およびその製造方法を提供することを課題とする。 Therefore, the present invention provides a fluorene condensate composition having a small thermogravimetric reduction rate and no problem of itching during the synthesis work, and a method for producing the same, and an epoxidized composition useful as a raw material for the epoxy resin and a method for producing the same. It is an issue to provide.
本発明者は、上記課題を解決すべく鋭意検討を重ねた結果、下記（１）式で示される化合物（フルオレン縮合体）を１２〜９０質量％、および下記（２）式で示される化合物（フルオレン誘導体）を８８〜１０質量％含有し、これらの合計含有量が８５質量％であるフルオレン縮合体組成物は、熱重量減少率が小さく、その合成作業の際のかゆみの問題もないこと、さらに、このフルオレン縮合体組成物をエポキシ化して得られるエポキシ化組成物がエポキシ樹脂の原料として有用であることを知得し、本発明を完成させた。 As a result of intensive studies to solve the above problems, the present inventor has obtained 12 to 90% by mass of a compound (fluorene condensate) represented by the following formula (1) and a compound represented by the following formula (2) ( The fluorene condensate composition containing 88 to 10% by mass of the fluorene derivative) and the total content thereof is 85% by mass has a small thermal weight reduction rate, and there is no problem of itching during the synthesis work. Furthermore, the inventors have learned that an epoxidized composition obtained by epoxidizing this fluorene condensate composition is useful as a raw material for an epoxy resin, and completed the present invention.
すなわち、本発明は以下の［１］〜［１０］である。
［１］下記（１）式で示される化合物を１２〜９０質量％、および
下記（２）式で示される化合物を８８〜１０質量％含有し、
下記（１）式で示される化合物および下記（２）式で示される化合物の合計含有量が８５質量％以上である、フルオレン縮合体組成物。
［２］ｎが０以上５以下の整数である、上記［１］に記載のフルオレン縮合体組成物。
［３］Ａｒがベンゼン環またはナフタレン環である、上記［１］または［２］に記載のフルオレン縮合体組成物。
［４］ｑ＝０である、またはｑ＝１であり、かつ、Ｒ１がメチル基である、上記［１］〜［３］のいずれか１つに記載のフルオレン縮合体組成物。
［５］Ｘがヒドロキシ基であり、かつ、ｐ＝１である、上記［１］〜［４］のいずれか１つに記載のフルオレン縮合体組成物。
［６］下記（３）式で示される化合物を１２〜９０質量％、および
下記（４）式で示される化合物を８８〜１０質量％含有し、
下記（３）式で示される化合物および下記（４）式で示される化合物の合計含有量が８５質量％以上である、エポキシ化組成物。
［７］下記（Ａ）式で示される化合物と下記（Ｂ）式で示される化合物とを酸性触媒下で反応させる縮合工程を含み、
（Ａ）式で示される化合物と（Ｂ）式で示される化合物の混合比「（Ａ）式で示される化合物の合計モル数／（Ｂ）式で示される化合物の合計モル数」が１．０以上６．０以下であり、かつ、反応温度が１００℃超である、フルオレン縮合体組成物の製造方法。
［８］縮合工程において、混合比が１．０超、２．０未満であり、かつ、反応温度が１００℃超、１５０℃以下である、上記［７］に記載のフルオレン縮合体組成物の製造方法。
［９］下記（Ａ）式で示される化合物と下記（Ｂ）式で示される化合物とを酸性触媒下で反応させる縮合工程、および
縮合工程で得られたフルオレン縮合体組成物をエポキシ化するエポキシ化工程を含み、
（Ａ）式で示される化合物と（Ｂ）式で示される化合物の混合比「（Ａ）式で示される化合物の合計モル数／（Ｂ）式で示される化合物の合計モル数」が１．０以上６．０以下であり、かつ、反応温度が１００℃超である、エポキシ化組成物の製造方法。
［１０］縮合工程において、混合比が１．０超、２．０未満であり、かつ、反応温度が１００℃超、１５０℃以下である、上記［９］に記載のエポキシ化組成物の製造方法。
That is, the present invention includes the following [1] to [10].
[1] 12 to 90% by mass of a compound represented by the following formula (1), and 88 to 10% by mass of a compound represented by the following formula (2),
A fluorene condensate composition in which the total content of the compound represented by the following formula (1) and the compound represented by the following formula (2) is 85% by mass or more.
[2] The fluorene condensate composition according to the above [1], wherein n is an integer of 0 or more and 5 or less.
[3] The fluorene condensate composition according to [1] or [2] above, wherein Ar is a benzene ring or a naphthalene ring.
[4] The fluorene condensate composition according to any one of the above [1] to [3], wherein q = 0, q = 1, and R 1 is a methyl group.
[5] The fluorene condensate composition according to any one of [1] to [4], wherein X is a hydroxy group and p = 1.
[6] 12 to 90% by mass of a compound represented by the following formula (3), and 88 to 10% by mass of a compound represented by the following formula (4),
An epoxidized composition having a total content of a compound represented by the following formula (3) and a compound represented by the following formula (4) of 85% by mass or more.
[7] including a condensation step of reacting a compound represented by the following formula (A) with a compound represented by the following formula (B) under an acidic catalyst;
The mixing ratio of the compound represented by the formula (A) and the compound represented by the formula (B) “total number of moles of the compound represented by formula (A) / total number of moles of the compound represented by formula (B)” is 1. The manufacturing method of the fluorene condensate composition which is 0 or more and 6.0 or less, and reaction temperature is over 100 degreeC.
[8] The fluorene condensate composition according to [7] above, wherein in the condensation step, the mixing ratio is more than 1.0 and less than 2.0, and the reaction temperature is more than 100 ° C. and not more than 150 ° C. Production method.
[9] A condensation step in which a compound represented by the following formula (A) and a compound represented by the following formula (B) are reacted in an acidic catalyst, and an epoxy that epoxidizes the fluorene condensate composition obtained in the condensation step Including
The mixing ratio of the compound represented by the formula (A) and the compound represented by the formula (B) “total number of moles of the compound represented by formula (A) / total number of moles of the compound represented by formula (B)” is 1. A method for producing an epoxidized composition, which is 0 or more and 6.0 or less and the reaction temperature is higher than 100 ° C.
[10] Production of epoxidized composition according to [9] above, wherein in the condensation step, the mixing ratio is more than 1.0 and less than 2.0, and the reaction temperature is more than 100 ° C. and not more than 150 ° C. Method.
本発明によれば、熱重量減少率が小さく、合成作業の際のかゆみの問題もない、フルオレン縮合体組成物およびその製造方法、ならびにエポキシ樹脂の原料として有用なエポキシ化組成物およびその製造方法が提供される。 According to the present invention, a fluorene condensate composition having a small thermogravimetric reduction rate and no problem of itchiness during synthesis work, a method for producing the same, and an epoxidized composition useful as a raw material for an epoxy resin and a method for producing the same Is provided.
本発明の特徴的な点は、フルオレン縮合体を合成する際の反応温度を従来よりも高い１００℃超とし、かつ、原料の混合比（仕込比）を特定範囲内とした点にある。これにより、フルオレン縮合体組成物中のフルオレン縮合体の含量を１２質量％以上として、熱重量減少率を小さく、かつ、飛散し難くすることができた。これは、本発明のフルオレン縮合体組成物中のフルオレン縮合体（（１）式で示される化合物）の含量を従来に比べて大きくすることによって、フルオレン縮合体組成物に含まれる揮発分の含量を従来に比べて小さくすることができ、その結果として熱重量減少率を小さくすることができたこと、および、フルオレン縮合体組成物に含まれるフルオレン縮合体の平均分子量が従来に比べて大きくなって、フルオレン縮合体組成物の微細結晶が生成しにくくなり、その結果として、フルオレン縮合体組成物を飛散し難くすることができたことによるものであると考えられる。
以下、本発明についてさらに詳しく説明する。
The characteristic point of the present invention is that the reaction temperature at the time of synthesizing the fluorene condensate is higher than 100 ° C., and the mixing ratio (feeding ratio) of raw materials is within a specific range. Thereby, the content of the fluorene condensate in the fluorene condensate composition was set to 12% by mass or more, and the thermal weight reduction rate was made small and it was difficult to scatter. This is because the content of volatile components contained in the fluorene condensate composition is increased by increasing the content of the fluorene condensate (compound represented by the formula (1)) in the fluorene condensate composition of the present invention. As a result, the thermal weight loss rate could be reduced, and the average molecular weight of the fluorene condensate contained in the fluorene condensate composition was larger than before. Thus, it is considered that it is difficult to produce fine crystals of the fluorene condensate composition, and as a result, the fluorene condensate composition can be hardly scattered.
Hereinafter, the present invention will be described in more detail.
［フルオレン縮合体組成物］
本発明のフルオレン縮合体組成物は、下記（１）式で示される化合物を１２〜９０質量％、および下記（２）式で示される化合物を８８〜１０質量％含有し、下記（１）式で示される化合物および下記（２）式で示される化合物の合計含有量が８５質量％以上である。
[Fluorene condensate composition]
The fluorene condensate composition of the present invention contains 12 to 90% by mass of a compound represented by the following formula (1), and 88 to 10% by mass of a compound represented by the following formula (2). And the total content of the compound represented by the following formula (2) is 85% by mass or more.
本発明のフルオレン縮合体組成物は、好ましくは、下記（１）式で示される化合物を２０〜９０質量％、および下記（２）式で示される化合物を８０〜１０質量％含有し、より好ましくは、下記（１）式で示される化合物を３０〜８０質量％、および下記（２）式で示される化合物を７０〜２０質量％含有する。 The fluorene condensate composition of the present invention preferably contains 20 to 90% by mass of a compound represented by the following formula (1) and 80 to 10% by mass of a compound represented by the following formula (2). Contains 30 to 80% by mass of a compound represented by the following formula (1) and 70 to 20% by mass of a compound represented by the following formula (2).
下記（１）式で示される化合物の含有量がこの範囲内であると、本発明のフルオレン縮合体組成物は、揮発分が少なく、高温時の重量減少率（熱重量減少率）が小さい。熱重量減少率が小さいことで、本発明のフルオレンン縮合体組成物をエポキシ樹脂の原料として用いた際にも熱重量減少率が小さく、耐熱性に優れたエポキシ樹脂とすることができる。 When the content of the compound represented by the following formula (1) is within this range, the fluorene condensate composition of the present invention has a small volatile content and a small weight loss rate (thermal weight loss rate) at high temperatures. Since the thermal weight reduction rate is small, even when the fluorene condensate composition of the present invention is used as a raw material for the epoxy resin, the thermal weight reduction rate is small and an epoxy resin excellent in heat resistance can be obtained.
また、下記（１）式で示される化合物の含有量がこの範囲内であると、結晶の飛散が少なく、使用者の人体に付着しにくい。そのため、本発明のフルオレン縮合体組成物を合成する際のかゆみの問題も無い。これは、本発明のフルオレン縮合体組成物中の下記（１）式で示される化合物の含量が多いと、本発明のフルオレン縮合体組成物に含まれるフルオレン縮合体の平均分子量が大きくなって、フルオレン縮合体組成物の微細結晶が生成しにくく、飛散し難いことによるものであると考えられる。 In addition, when the content of the compound represented by the following formula (1) is within this range, there is little scattering of crystals and it is difficult to adhere to the user's human body. Therefore, there is no itching problem when the fluorene condensate composition of the present invention is synthesized. When the content of the compound represented by the following formula (1) in the fluorene condensate composition of the present invention is large, the average molecular weight of the fluorene condensate contained in the fluorene condensate composition of the present invention is increased. It is thought that this is because fine crystals of the fluorene condensate composition are not easily generated and are not easily scattered.
（１）式および（２）式中、Ａｒは芳香環を示す。
Ａｒは分子間および／または分子内で互いに同じであっても異なっていてもよく、好ましくは分子間および分子内で同じ種類である。Ａｒが分子間および分子内で同じ種類であると、製造の際に（１）式で示される化合物が合成されやすくなり、工業的に製造する際に有利である。
In the formulas (1) and (2), Ar represents an aromatic ring.
Ar may be the same as or different from each other within a molecule and / or within a molecule, and is preferably the same type between molecules and within a molecule. When Ar is the same type between molecules and within a molecule, the compound represented by the formula (1) is easily synthesized during production, which is advantageous for industrial production.
（１）式および（２）式中、Ａｒで示される芳香環としては、ヒュッケル則を満たす不飽和炭化水素環であれば特に限定されないが、例えば、下記（ａ）式から（ｇ）式までに示された芳香環を挙げることができる。Ａｒは、原料の入手の容易さおよび取扱いの容易さから、好ましくはベンゼン環（下記（ａ）式で示される）またはナフタレン環（下記（ｂ）式で示される。）であり、より好ましくはベンゼン環である。 In the formulas (1) and (2), the aromatic ring represented by Ar is not particularly limited as long as it is an unsaturated hydrocarbon ring that satisfies the Hückel rule. For example, from the following formulas (a) to (g) An aromatic ring shown in the above can be mentioned. Ar is preferably a benzene ring (shown by the following formula (a)) or a naphthalene ring (shown by the following formula (b)), more preferably from the viewpoint of easy availability and handling of the raw material. Benzene ring.
Ａｒの置換可能な位置の数ｔは、芳香環Ａｒを構成する炭素原子に結合可能な水素原子の数と一致し、例えば、上記（ａ）式で示されるベンゼン環では６、上記（ｂ）式で示されるナフタレン環では８、上記（ｃ）式で示されるアントラセン環では１０、上記（ｄ）式で示されるフェナントレン環では１０、上記（ｅ）式で示されるテトラセン環では１２、上記（ｆ）式で示されるクリセン環では１２、上記（ｇ）式で示されるアズレン環では８である。 The number t of substitutable positions of Ar is the same as the number of hydrogen atoms that can be bonded to the carbon atoms constituting the aromatic ring Ar. For example, in the benzene ring represented by the above formula (a), 6 8 for the naphthalene ring represented by formula, 10 for the anthracene ring represented by formula (c), 10 for the phenanthrene ring represented by formula (d), 12 for the tetracene ring represented by formula (e), ( f) 12 for the chrysene ring represented by the formula, and 8 for the azulene ring represented by the formula (g).
なお、ヒュッケル則を満たすとは、環を構成するすべての原子がｓｐ２混成軌道をとっていること、π電子系に含まれる電子の数が４ｋ＋２（ここで、ｋは０以上の整数である。）個であること、および、環全体が平面構造をとっていることをいう。 Satisfying the Hückel rule means that all atoms constituting the ring have sp 2 hybrid orbitals, and the number of electrons contained in the π-electron system is 4k + 2 (where k is an integer of 0 or more). .) It is individual and the entire ring has a planar structure.
（１）式および（２）式中、Ｘはヒドロキシ基および一般式−［Ｏ−（Ｒ３Ｏ）ｍ−Ｈ］によって示される基（ただし、Ｒ３はアルキレン基を示し、ｍは１以上の整数である。）からなる群から選択される置換基を示し、Ａｒに結合するＸの個数ｐは１以上の整数である。Ｘ、Ｒ３、ｍおよびｐは、それぞれ、分子間および／または分子内で互いに同じであっても異なっていてもよい。 In the formulas (1) and (2), X represents a hydroxy group and a group represented by the general formula — [O— (R 3 O) m —H] (wherein R 3 represents an alkylene group, and m is 1 or more. And the number p of X bonded to Ar is an integer of 1 or more. X, R 3 , m, and p may be the same as or different from each other and / or within the molecule.
Ｘにおいて、Ｒ３によって示されるアルキレン基は、特に限定されないが、原料化合物の入手の容易さから、好ましくはＣ１−１０アルキレン基、より好ましくはＣ１−４アルキレン基、さらに好ましくはＣ２−３アルキレン基、いっそう好ましくはエチレン基またはトリメチレン基、よりいっそう好ましくはエチレン基である。Ｒ３としては、具体的には、例えば、メチレン基（−ＣＨ２−）、エチレン基（−ＣＨ２ＣＨ２−）、トリメチレン基（−ＣＨ２ＣＨ２ＣＨ２−）、プロピレン基（−ＣＨ（ＣＨ３）ＣＨ２−）、プロピリデン基（＞ＣＨＣＨ２ＣＨ３）、イソプロピリデン基（＞Ｃ（ＣＨ３）２）、およびブタン−１，２−ジイル基（−ＣＨ２ＣＨ２（ＣＨ２ＣＨ３）−）等が挙げられる。なお、Ｒ３は、同一の、または異なるアルキレン基であってもよい。すなわち、ｍが２以上の整数である場合、Ｒ３は同一であってもよいし、異なっていてもよい。すなわち、ｍが２以上の整数である場合、ポリオキシアルキレン単位（Ｒ３Ｏ）は同一種類のオキシアルキレン単位から構成されてもよいし、異なる種類のオキシアルキレン単位、例えば、オキシエチレン単位およびオキシプロピレン単位等から構成されてもよい。 In X, the alkylene group represented by R 3 is not particularly limited, but is preferably a C 1-10 alkylene group, more preferably a C 1-4 alkylene group, and still more preferably C 2 because of the availability of raw material compounds. -3 alkylene group, more preferably ethylene group or trimethylene group, and still more preferably ethylene group. Specific examples of R 3 include a methylene group (—CH 2 —), an ethylene group (—CH 2 CH 2 —), a trimethylene group (—CH 2 CH 2 CH 2 —), and a propylene group (—CH 2 ). (CH 3 ) CH 2 —), propylidene group (> CHCH 2 CH 3 ), isopropylidene group (> C (CH 3 ) 2 ), and butane-1,2-diyl group (—CH 2 CH 2 (CH 2 CH 3) -) and the like. R 3 may be the same or different alkylene groups. That is, when m is an integer of 2 or more, R 3 may be the same or different. That is, when m is an integer of 2 or more, the polyoxyalkylene units (R 3 O) may be composed of the same type of oxyalkylene units, or different types of oxyalkylene units such as oxyethylene units and oxyethylene units. You may be comprised from a propylene unit etc.
Ｘにおいて、オキシアルキレン単位（Ｒ３Ｏ）の繰返し数（付加モル数）ｍは、特に限定されないが、原料化合物の入手の容易さから、好ましくは１〜１５、より好ましくは１〜１０、さらに好ましくは１〜８、いっそう好ましくは１〜６、よりいっそう好ましくは１〜４、特に好ましくは１〜２である。 In X, the number of repeating oxyalkylene units (R 3 O) (number of added moles) m is not particularly limited, but is preferably 1 to 15, more preferably 1 to 10, more preferably from the viewpoint of availability of raw material compounds. Preferably it is 1-8, More preferably, it is 1-6, More preferably, it is 1-4, Most preferably, it is 1-2.
Ｘは、原料化合物の入手の容易さから、好ましくはヒドロキシ基、２−ヒドロキシエチル基および３−ヒドロキシプロピル基からなる群から選択される少なくとも１種類以上であり、より好ましくはヒドロキシ基および２−ヒドロキシエチル基からなる群から選択される少なくとも１種類以上であり、さらに好ましくはヒドロキシ基である。 X is preferably at least one selected from the group consisting of a hydroxy group, a 2-hydroxyethyl group, and a 3-hydroxypropyl group, more preferably a hydroxy group and 2- At least one selected from the group consisting of hydroxyethyl groups, more preferably a hydroxy group.
ｐは、ｐ＋ｑ≦ｔ−２を満たせば特に限定されないが、好ましくは１または２であり、原料化合物の入手の容易さから、より好ましくは１である。ここで、ｔは芳香環Ａｒの置換可能な位置の数であり、ｑはＡｒに結合するＲ１の数である。 Although p will not be specifically limited if p + q <= t-2 is satisfy | filled, Preferably it is 1 or 2, More preferably, it is 1 from the ease of acquisition of a raw material compound. Here, t is the number of substitutable positions of the aromatic ring Ar, and q is the number of R 1 bonded to Ar.
（１）式および（２）式中、Ｒ１は脂肪族基を示し、Ａｒに結合するＲ１の個数ｑは０以上の整数である。Ｒ１およびｑは、それぞれ、分子間および／または分子内で互いに同じであっても異なっていてもよい。
脂肪族基は、特に限定されないが、好ましくは飽和脂肪族基または不飽和脂肪族基であり、より好ましくは飽和脂肪族基である。飽和脂肪族基は、好ましくはアルキル基であり、より好ましくは炭素数１〜１０個のアルキル基であり、さらに好ましくは炭素数１〜４個のアルキル基である。
炭素数１〜４個のアルキル基としては、メチル基、エチル基、プロピル基、プロパン−２−イル基（イソプロピル基）、ブチル基、２−メチルプロピル基（イソブチル基）等が挙げられる。
Ｒ１は、原料化合物の入手の容易さから、特に好ましくはメチル基である。
Ａｒに置換するＲ１の個数ｑは、０以上の整数であり、ｐ＋ｑ≦ｔ−２を満たせば特に限定されないが、好ましくは０または１であり、原料化合物の入手の容易さから、より好ましくは０である。ここで、ｔは芳香環Ａｒの置換可能な位置の数であり、ｐはＡｒに置換するＸの数である。ｑ＝１であるとき、Ｒ１は好ましくはメチル基である。
In the formulas (1) and (2), R 1 represents an aliphatic group, and the number q of R 1 bonded to Ar is an integer of 0 or more. R 1 and q may be the same or different from each other between molecules and / or within a molecule.
The aliphatic group is not particularly limited, but is preferably a saturated aliphatic group or an unsaturated aliphatic group, and more preferably a saturated aliphatic group. The saturated aliphatic group is preferably an alkyl group, more preferably an alkyl group having 1 to 10 carbon atoms, and still more preferably an alkyl group having 1 to 4 carbon atoms.
Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, a propan-2-yl group (isopropyl group), a butyl group, and a 2-methylpropyl group (isobutyl group).
R 1 is particularly preferably a methyl group from the standpoint of availability of the raw material compound.
The number q of R 1 substituted for Ar is an integer of 0 or more, and is not particularly limited as long as p + q ≦ t−2 is satisfied. However, it is preferably 0 or 1, and more preferably from the viewpoint of availability of raw material compounds. Is 0. Here, t is the number of substitutable positions of the aromatic ring Ar, and p is the number of X substituted with Ar. When q = 1, R 1 is preferably a methyl group.
（１）式および（２）式中、Ｒ２はアルキル基、アルコキシ基、アリール基、ハロゲン原子、アミノ基またはシアノ基を示し、フルオレン骨格の２個あるベンゼン環部分のそれぞれに置換するＲ２の個数ｓは０≦ｓ≦４を満足する整数である。Ｒ２およびｓは、それぞれ、分子間および／または分子内で互いに同じであっても異なっていてもよいが、好ましくは分子間および分子内で互いに同じである。Ｒ２およびｓがそれぞれ分子間および分子内で同じ種類であると、製造の際に（１）式で示される化合物が合成されやすくなり、工業的に製造する際に有利である。 In the formulas (1) and (2), R 2 represents an alkyl group, an alkoxy group, an aryl group, a halogen atom, an amino group or a cyano group, and R 2 substituted on each of the two benzene ring portions of the fluorene skeleton. The number s is an integer satisfying 0 ≦ s ≦ 4. R 2 and s may be the same or different from each other between molecules and / or within a molecule, but are preferably the same between molecules and within a molecule. When R 2 and s are of the same type between and within the molecule, the compound represented by the formula (1) is easily synthesized during production, which is advantageous for industrial production.
上記アルキル基は、特に限定されないが、好ましくは炭素数３以下のアルキル基であり、より好ましくはメチル基である。炭素数３以下のアルキル基としては、メチル基の他には、エチル基、プロピル基等が挙げられる。
上記アルコキシ基は、特に限定されないが、好ましくは炭素数３以下のアルコキシ基であり、より好ましくはメトキシ基である。炭素数３以下のアルコキシ基としては、メトキシ基の他には、エトキシ基、プロポキシ基等が挙げられる。
上記アリール基は、特に限定されないが、好ましくはフェニル基、ベンジル基、トリル基、キシリル基等が挙げられる。
上記ハロゲン原子は、特に限定されないが、好ましくは塩素原子または臭素原子であり、より好ましくは臭素原子である。
Ｒ２は、原料化合物の入手の容易さから、好ましくはハロゲン原子またはアルキル基であり、より好ましくは臭素原子またはメチル基である。
ｓは、原料化合物の入手の容易さから、好ましくは０である。ｓが０であると原料が入手し易く、工業的に安価で製造しやすいからである。
The alkyl group is not particularly limited, but is preferably an alkyl group having 3 or less carbon atoms, and more preferably a methyl group. Examples of the alkyl group having 3 or less carbon atoms include an ethyl group and a propyl group in addition to the methyl group.
The alkoxy group is not particularly limited, but is preferably an alkoxy group having 3 or less carbon atoms, and more preferably a methoxy group. Examples of the alkoxy group having 3 or less carbon atoms include an ethoxy group and a propoxy group in addition to the methoxy group.
The aryl group is not particularly limited, but preferably includes a phenyl group, a benzyl group, a tolyl group, a xylyl group, and the like.
The halogen atom is not particularly limited, but is preferably a chlorine atom or a bromine atom, and more preferably a bromine atom.
R 2 is preferably a halogen atom or an alkyl group, more preferably a bromine atom or a methyl group, from the viewpoint of easy availability of the raw material compound.
s is preferably 0 because of easy availability of the raw material compound. This is because if s is 0, the raw material is easy to obtain, industrially inexpensive and easy to manufacture.
フルオレン単位の繰返し数ｎは０以上の整数であり、特に限定されないが、好ましくは０以上５以下の整数である。ｎは分子間で互いに同じであっても異なっていてもよい。上記ｎがこの範囲内であると、フルオレン縮合体がより生成しやすくなり、収率がより高くなる。 The repetition number n of the fluorene unit is an integer of 0 or more, and is not particularly limited, but is preferably an integer of 0 or more and 5 or less. n may be the same or different between molecules. When n is in this range, a fluorene condensate is more easily generated, and the yield is further increased.
本発明のフルオレン縮合体組成物中の（１）式で示される化合物および（２）式で示される化合物の合計含有量は８５質量％以上であり、好ましくは９０質量％以上であり、より好ましくは９５質量％以上であり、さらに好ましくは実質的に１００質量％である。ここで「実質的に」とは、不可避的不純物の混入を容認することを意味する。 The total content of the compound represented by the formula (1) and the compound represented by the formula (2) in the fluorene condensate composition of the present invention is 85% by mass or more, preferably 90% by mass or more, more preferably. Is 95% by mass or more, more preferably substantially 100% by mass. Here, “substantially” means accepting inevitable impurities.
（１）式で示される化合物と（２）式で示される化合物との合計の含有量がこの範囲であると、熱重量減少量が極めて少なく、また取扱い時のかゆみがより一層抑制できるからである。 When the total content of the compound represented by the formula (1) and the compound represented by the formula (2) is within this range, the thermal weight loss is extremely small, and itching during handling can be further suppressed. is there.
また、（１）式で示される化合物と（２）式で示される化合物の含有量比（質量比）は、上記含有量に関する条件を満足する限り特に限定されるものではないが、好ましくは（１）式で示される化合物の質量：（２）式で示される化合物の質量＝１２〜９０：８８〜１０であり、より好ましくは（１）式で示される化合物の質量：（２）式で示される化合物の質量＝１５〜８０：８５〜２０である。この範囲内であると、本発明のフルオレン縮合体組成物はさらに結晶が飛散しにくくなり、取扱者が健康被害を受けるおそれがより小さくなる。 Further, the content ratio (mass ratio) of the compound represented by the formula (1) and the compound represented by the formula (2) is not particularly limited as long as the above-described conditions regarding the content are satisfied. 1) Mass of the compound represented by the formula: Mass of the compound represented by the formula (2) = 12 to 90: 88-10, more preferably Mass of the compound represented by the formula (1): The mass of the compound shown = 15-80: 85-20. Within this range, the fluorene condensate composition of the present invention is more difficult to disperse crystals, and the risk of suffering health damage to the handler is further reduced.
本発明のフルオレン縮合体組成物では、特性を損なわない範囲で、反応過程で生じる副生成物を含んでいても良い。副生成物の含有量は特に制限されないが、組成物全量の１５質量％以下、好ましくは１０質量％以下である。このような副生成物は、原料や生成物が酸化された複雑な構造の化合物等が上げられる。 The fluorene condensate composition of the present invention may contain by-products generated in the reaction process as long as the characteristics are not impaired. The content of the by-product is not particularly limited, but is 15% by mass or less, preferably 10% by mass or less of the total amount of the composition. Examples of such a by-product include a compound having a complicated structure in which raw materials and products are oxidized.
［フルオレン縮合体組成物の製造方法］
本発明のフルオレン縮合体組成物の製造方法は、下記（Ａ）式で示される化合物と下記（Ｂ）式で示される化合物とを酸性触媒下で反応させる縮合工程を含み、（Ａ）式で示される化合物と（Ｂ）式で示される化合物の混合比「（Ａ）式で示される化合物の合計モル数／（Ｂ）式で示される化合物の合計モル数」が１．０以上６．０以下であり、かつ、反応温度が１００℃超であることを特徴とする。特に好ましくは混合比が１．０超、２．０未満であり、かつ、反応温度が１００℃超、１５０℃以下である。
なお、本発明において、混合比は仕込比ともいう。
[Method for producing fluorene condensate composition]
The method for producing a fluorene condensate composition of the present invention includes a condensation step in which a compound represented by the following formula (A) and a compound represented by the following formula (B) are reacted in an acidic catalyst, The mixing ratio of the compound represented by the formula (B) and the compound represented by the formula (B) “total number of moles of the compound represented by formula (A) / total number of moles of the compound represented by formula (B)” is 1.0 or more and 6.0. And the reaction temperature is over 100 ° C. Particularly preferably, the mixing ratio is more than 1.0 and less than 2.0, and the reaction temperature is more than 100 ° C. and not more than 150 ° C.
In the present invention, the mixing ratio is also referred to as the charging ratio.
〈（Ａ）式で示される化合物〉 <Compound represented by formula (A)>
（Ａ）式中のＡｒ、Ｘ、Ｒ１、ｐおよびｑは、それぞれ、上記（１）式および（２）式中のＡｒ、Ｘ、Ｒ１、ｐおよびｑと同義である。 (A) in the formula Ar, X, R 1, p and q are, respectively, (1) and (2) the same meaning as Ar, X, R 1, p and q in the formula.
上記（Ａ）式で示される化合物としては、フェノール類および／またはナフトール類のうち、上記（Ａ）式で示すことができるものが好ましい。
このようなフェノール類は、例えば、フェノール、クレゾール類（２−メチルフェノール、３−メチルフェノール、４−メチルフェノール）、キシレノール類（２，３−ジメチルフェノール、２，４−ジメチルフェノール、２，５−ジメチルフェノール、２，６−ジメチルフェノール、３，４−ジメチルフェノール、３，５−ジメチルフェノール）、２−フェノキシエタノール等を挙げることができ、入手容易であることから、好ましくはフェノールまたは２−メチルフェノール（ｏ−クレゾール）であり、より好ましくはフェノールである。
このようなナフトール類は、例えば、１−ナフトール、２−ナフトール、２，６−ナフタレンジオール類等を挙げることができ、入手容易であることから、好ましくは１−ナフトールまたは２−ナフトールである。
As the compound represented by the formula (A), among the phenols and / or naphthols, those that can be represented by the formula (A) are preferable.
Such phenols include, for example, phenol, cresols (2-methylphenol, 3-methylphenol, 4-methylphenol), xylenols (2,3-dimethylphenol, 2,4-dimethylphenol, 2,5 -Dimethylphenol, 2,6-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol), 2-phenoxyethanol, and the like. Phenol (o-cresol), more preferably phenol.
Examples of such naphthols include 1-naphthol, 2-naphthol, 2,6-naphthalenediol, and the like. Since they are easily available, 1-naphthol or 2-naphthol is preferable.
〈（Ｂ）式で示される化合物〉 <Compound represented by formula (B)>
（Ｂ）式中のＲ２およびｓは、それぞれ、上記（１）式および（２）式中のＲ２およびｓと同義である。
式（Ｂ）で示される化合物としては、９−フルオレノン、２−アミノ−９−フルオレノン、２−ブロモ−９−フルオレノン、２，７−ジブロモ−９−フルオレノン等を挙げることができ、入手が容易であることから、好ましくは９−フルオレノンである。
(B) R 2 and s in the formula, respectively, (1) and (2) the same meanings as R 2 and s in the formula.
Examples of the compound represented by the formula (B) include 9-fluorenone, 2-amino-9-fluorenone, 2-bromo-9-fluorenone, 2,7-dibromo-9-fluorenone, and are easily available. Therefore, 9-fluorenone is preferable.
原料の組合せとしては、好ましくは、（Ａ）式で示される化合物として、フェノール、１−ナフトール、２−ナフトール、クレゾール類およびキシレノール類からなる群から選択される少なくとも１種類を用い、（Ｂ）式で示される化合物として、９−フルオレノンを用いるものが挙げられる。 As a combination of raw materials, preferably, as the compound represented by the formula (A), at least one selected from the group consisting of phenol, 1-naphthol, 2-naphthol, cresols and xylenols is used, and (B) Examples of the compound represented by the formula include those using 9-fluorenone.
〈酸性触媒〉
本発明のフルオレン縮合体組成物の製造方法の縮合工程で用いる酸性触媒は、特に限定されるものではないが、例えば、硫酸、塩酸、硝酸、リン酸、ｐ−トルエンスルホン酸、β−メルカプトプロピオン酸、シュウ酸、酢酸、強酸性イオン交換樹脂等を挙げることができ、これらから選択される１種類を単独で、または２種類以上を組み合わせて使用することができる。特に好ましくは、硫酸、ｐ−トルエンスルホン酸およびβ−メルカプトプロピオン酸からなる群から選択される少なくとも１種類である。２種類以上の酸性触媒を組み合わせて使用する場合の量比は特に限定されない。
<Acid catalyst>
The acidic catalyst used in the condensation step of the method for producing the fluorene condensate composition of the present invention is not particularly limited. For example, sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, p-toluenesulfonic acid, β-mercaptopropion An acid, an oxalic acid, an acetic acid, a strong acidic ion exchange resin etc. can be mentioned, One type selected from these can be used individually or in combination of 2 or more types. Particularly preferred is at least one selected from the group consisting of sulfuric acid, p-toluenesulfonic acid and β-mercaptopropionic acid. The amount ratio in the case of using two or more kinds of acidic catalysts in combination is not particularly limited.
〈反応温度〉
本発明のフルオレン縮合体組成物の製造方法の縮合工程における反応温度は、１００℃超であり、好ましくは１００℃超、１５０℃以下である。
反応温度が１００℃以下では、反応速度が遅く、また、（１）式で示される化合物の繰返し数ｎの平均値が小さくなり、熱重量減少率が大きくなり、取扱い時のかゆみの問題を生じるおそれがある。
反応温度が１５０℃以下であると、原料が酸化された複雑な構造の化合物等の副生成物の生成が抑えられる。
<Reaction temperature>
The reaction temperature in the condensation step of the method for producing the fluorene condensate composition of the present invention is more than 100 ° C, preferably more than 100 ° C and not more than 150 ° C.
When the reaction temperature is 100 ° C. or lower, the reaction rate is slow, the average value of the number of repetitions n of the compound represented by the formula (1) is small, the thermal weight loss rate is large, and the problem of itchiness during handling occurs. There is a fear.
When the reaction temperature is 150 ° C. or lower, generation of by-products such as a compound having a complicated structure in which the raw material is oxidized can be suppressed.
〈原料の混合比（仕込比）〉
本発明のフルオレン縮合体組成物の製造方法の縮合工程における原料の混合比（仕込比）は「（Ａ）式で示される化合物の合計モル数／（Ｂ）式で示される化合物の合計モル数」（モル比）であり、その範囲は１．０以上６．０以下である。この範囲内とすることで、フルオレン縮合体の生成量が増加して、上記（１）式で示される化合物の含有量を１０質量％以上とすることができる。
混合比（仕込比）「（Ａ）式で示される化合物の合計モル数／（Ｂ）式で示される化合物の合計モル数」（モル比）は、上記（１）式で示される化合物の含有量が増加することから、好ましくは１．０超、２．０未満、より好ましくは１．１以上１．９以下、さらに好ましくは１．５以上１．８以下である。
<Raw material mixing ratio (feeding ratio)>
The mixing ratio (feeding ratio) of the raw materials in the condensation step of the method for producing the fluorene condensate composition of the present invention is “total number of moles of compound represented by formula (A) / total number of moles of compound represented by formula (B)”. (Molar ratio), and the range is 1.0 or more and 6.0 or less. By setting it within this range, the production amount of the fluorene condensate increases, and the content of the compound represented by the above formula (1) can be 10% by mass or more.
Mixing ratio (feeding ratio) “total number of moles of compound represented by formula (A) / total number of moles of compound represented by formula (B)” (molar ratio) is the content of the compound represented by formula (1) above. Since the amount increases, it is preferably more than 1.0 and less than 2.0, more preferably 1.1 or more and 1.9 or less, and further preferably 1.5 or more and 1.8 or less.
〈溶媒〉
本発明のフルオレン縮合体組成物の製造方法の縮合工程で用いる溶媒は、特に限定されないが、例えば、ベンゼン、トルエン、ｏ−キシレン、ｍ−キシレン、ｐ−キシレン等を挙げることができ、原料および生成物の溶解性に優れる点で、好ましくはトルエン、ｏ−キシレンおよびｐ−キシレンからなる群から選択される少なくとも１種類である。１種類を単独で用いてもよいし、２種類以上を組み合わせて用いてもよい。２種類以上を組み合わせて用いる場合の量比は特に限定されない。
<solvent>
The solvent used in the condensation step of the method for producing the fluorene condensate composition of the present invention is not particularly limited, and examples thereof include benzene, toluene, o-xylene, m-xylene, p-xylene and the like. In view of excellent solubility of the product, it is preferably at least one selected from the group consisting of toluene, o-xylene and p-xylene. One type may be used alone, or two or more types may be used in combination. The amount ratio in the case of using two or more types in combination is not particularly limited.
［エポキシ化組成物］
本発明のエポキシ化組成物は、下記（３）式で示される化合物を１２〜９０質量％、および下記（４）式で示される化合物を８８〜１０質量％含有し、下記（３）式で示される化合物および下記（４）式で示される化合物の合計含有量が８５質量％以上である。
[Epoxidized composition]
The epoxidation composition of the present invention contains 12 to 90% by mass of a compound represented by the following formula (3) and 88 to 10% by mass of a compound represented by the following (4) formula. The total content of the compound shown and the compound shown by the following formula (4) is 85% by mass or more.
本発明のエポキシ化組成物は、好ましくは、下記（３）式で示される化合物を２０〜９０質量％、および下記（４）式で示される化合物を８０〜１０質量％含有し、より好ましくは、下記（３）式で示される化合物を３０〜８０質量％、および下記（４）式で示される化合物を７０〜２０質量％含有する。 The epoxidation composition of the present invention preferably contains 20 to 90% by mass of a compound represented by the following formula (3), and 80 to 10% by mass of a compound represented by the following formula (4), more preferably And 30 to 80% by mass of a compound represented by the following formula (3) and 70 to 20% by mass of a compound represented by the following formula (4).
（３）式および（４）式中のＡｒ、Ｒ１、Ｒ２、ｑおよびｓは、それぞれ、上記（１）式および（２）式中のＡｒ、Ｒ１、Ｒ２、ｑおよびｓと同義である。 (3) and (4) Ar in the formula, R 1, R 2, q and s are each, Ar in the above (1) and (2) wherein the R 1, R 2, q and s It is synonymous.
（３）式および（４）式中、Ｙはグリシドキシ基、ヒドロキシ基および一般式−［Ｏ−（Ｒ３Ｏ）ｍ−Ｈ］によって示される基（ただし、Ｒ３およびｍは、それぞれ、上記（１）式および（２）式中のＸにおけるＲ３およびｍと同義である。）からなる群から選択される置換基を示し、好ましくはグリシドキシ基およびヒドロキシ基からなる群から選択される基を示し、Ｙの総モル数の１０モル％以上、好ましくは２０モル％以上、より好ましくは５０モル％以上がグリシドキシ基である。Ａｒに結合するＹの個数ｐは１以上の整数である。Ｙおよびｐは、それぞれ、分子間および／または分子内で互いに同じであっても異なっていてもよい。
ｐは、ｐ＋ｑ≦ｔ−２を満たせば特に限定されないが、好ましくは１または２であり、原料化合物の入手の容易さから、より好ましくは１である。ここで、ｔは芳香環Ａｒの置換可能な位置の数であり、ｑはＡｒに結合するＲ１の数である。
本発明のエポキシ化組成物は、硬化剤または触媒を添加して硬化させることで、耐熱性に優れたエポキシ樹脂とすることができ、プレポリマー組成物として有用である。硬化剤または触媒としては、プレポリマーの硬化剤または触媒として従来公知のポリアミン、酸無水物等を使用することができる。本発明のエポキシ樹脂は、例えば、電子回路の基板やＩＣパッケージの封入剤、レジスト、接着剤、塗料、積層剤等として用いるのに有用である。
In the formulas (3) and (4), Y represents a glycidoxy group, a hydroxy group, and a group represented by the general formula — [O— (R 3 O) m —H] (wherein R 3 and m are each the above (1) a substituent selected from the group consisting of R 3 and m in X in the formula and (2), and preferably a group selected from the group consisting of a glycidoxy group and a hydroxy group And 10 mol% or more, preferably 20 mol% or more, more preferably 50 mol% or more of the total number of moles of Y is a glycidoxy group. The number p of Y bonded to Ar is an integer of 1 or more. Y and p may be the same as or different from each other between molecules and / or molecules.
Although p will not be specifically limited if p + q <= t-2 is satisfy | filled, Preferably it is 1 or 2, More preferably, it is 1 from the ease of acquisition of a raw material compound. Here, t is the number of substitutable positions of the aromatic ring Ar, and q is the number of R 1 bonded to Ar.
The epoxidized composition of the present invention can be made into an epoxy resin excellent in heat resistance by adding a curing agent or a catalyst and curing, and is useful as a prepolymer composition. As the curing agent or catalyst, conventionally known polyamines, acid anhydrides, and the like can be used as the prepolymer curing agent or catalyst. The epoxy resin of the present invention is useful, for example, for use as an encapsulant, a resist, an adhesive, a paint, a laminating agent, etc. for electronic circuit boards and IC packages.
［エポキシ化組成物の製造方法］
本発明のエポキシ化組成物の製造方法は、上述した本発明のフルオレン縮合体組成物の製造方法の縮合工程で得られたフルオレン縮合体組成物をエポキシ化するエポキシ化工程を含む。
縮合工程は、本発明のフルオレン縮合体組成物の製造方法において記載したとおりであある。
エポキシ化工程におけるエポキシ化の方法は、特に限定されず、従来公知のエポキシ化方法を用いることができるが、例えば、ジメチルスルホキシド等の溶媒中で、フルオレン縮合体組成物に対して、１〜２０モル倍のエピクロロヒドリン等のエポキシ化剤および水酸化ナトリウムを添加し、反応温度０℃〜１５０℃、好ましくは１０℃〜１００℃の間でエポキシ化を行う方法が挙げられる。反応終了後は、メチルイソブチルケトン等の抽出溶媒を添加し、水洗を行って、副生した塩化ナトリウムを除去して、有機層を回収し、有機層は、減圧蒸留して、抽出溶媒を除去し、エポキシ樹脂を回収することが好ましい。
[Method for producing epoxidized composition]
The manufacturing method of the epoxidation composition of this invention includes the epoxidation process of epoxidizing the fluorene condensate composition obtained at the condensation process of the manufacturing method of the fluorene condensate composition of this invention mentioned above.
A condensation process is as having described in the manufacturing method of the fluorene condensate composition of this invention.
The epoxidation method in the epoxidation step is not particularly limited, and a conventionally known epoxidation method can be used. For example, in a solvent such as dimethyl sulfoxide, 1 to 20 with respect to the fluorene condensate composition. Examples include a method in which an epoxidizing agent such as epichlorohydrin and sodium hydroxide are added in a molar ratio and epoxidation is performed at a reaction temperature of 0 ° C. to 150 ° C., preferably 10 ° C. to 100 ° C. After completion of the reaction, an extraction solvent such as methyl isobutyl ketone is added, washed with water to remove by-produced sodium chloride, the organic layer is recovered, and the organic layer is distilled under reduced pressure to remove the extraction solvent. It is preferable to recover the epoxy resin.
以下、実施例により本発明についてさらに詳しく説明する。 Hereinafter, the present invention will be described in more detail with reference to examples.
［評価方法］
１．（１’）式で示される化合物および（２’）式で示される化合物の含有量
製造したフルオレン縮合体組成物中の下記（１’）式で示される化合物および下記（２’）式で示される化合物の含有量は、製造したサンプルの０．５％テトラヒドロフラン（ＴＨＦ）溶液について、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）を用いて測定した標準ポリスチレン換算値から求めた。
（ＧＰＣ条件）
・システム：汎用液体クロマトグラフ“Ｐｒｏｍｉｎｅｎｃｅ”（登録商標）（島津製作所社製）＋示差屈折率検出器“ＲＩＤ−２０Ａ”（島津製作所製）
・カラムの種類：ショウデックス ＫＦ−Ｇ、ＫＦ−８０１、ＫＦ８０２、ＫＦ８０２．５、ＫＦ８０３（昭和電工社製）
・移動相：テトラヒドロフラン（ＴＨＦ）
・カラム温度：４０℃
・流量：１ｍＬ／ｍｉｎ
・サンプル注入量：１０μＬ
[Evaluation method]
1. Content of the compound represented by the formula (1 ′) and the compound represented by the formula (2 ′) In the produced fluorene condensate composition, the compound represented by the following formula (1 ′) and the following formula (2 ′) The content of the compound to be obtained was determined from a standard polystyrene equivalent value measured using gel permeation chromatography (GPC) for a 0.5% tetrahydrofuran (THF) solution of the produced sample.
(GPC conditions)
System: General-purpose liquid chromatograph "Prominence" (registered trademark) (manufactured by Shimadzu Corporation) + differential refractive index detector "RID-20A" (manufactured by Shimadzu Corporation)
Column type: Showdex KF-G, KF-801, KF802, KF802.5, KF803 (manufactured by Showa Denko)
-Mobile phase: tetrahydrofuran (THF)
-Column temperature: 40 ° C
・ Flow rate: 1 mL / min
Sample injection volume: 10 μL
（１’）式および（２’）式中、Ａｒはベンゼン環またはナフタレン環であり、Ｘはヒドロキシ基または２−ヒドロキシエトキシ基であり、ｎは０以上の整数である。 In the formulas (1 ′) and (2 ′), Ar is a benzene ring or a naphthalene ring, X is a hydroxy group or a 2-hydroxyethoxy group, and n is an integer of 0 or more.
２．熱重量減少率
製造したフルオレン縮合体組成物の熱重量減少率は、熱分析装置（島津製作所製，自動ＴＧ／ＤＴＡ同時測定装置ＤＴＧ−６０Ａ）を用いて、空気中、昇温速度１０℃／分の条件で１５０℃〜４００℃の範囲で測定した。
2. Thermal weight reduction rate The thermal weight reduction rate of the produced fluorene condensate composition was measured using a thermal analyzer (manufactured by Shimadzu Corp., automatic TG / DTA simultaneous measurement device DTG-60A) in the air at a heating rate of 10 ° C / It measured in the range of 150 to 400 degreeC on the conditions of a minute.
３．合成作業の時のかゆみの有無
合成作業中にかゆみを感じたか否かによって、以下の判定に従って合成作業の時のかゆみの有無を判定した。
（判定基準）
かゆみを感じた場合・・・・・・あり
かゆみを感じなかった場合・・・なし
3. Presence or absence of itching during composition work According to the following judgment, whether or not itching was felt during composition work was determined.
(Criteria)
If you feel itching ... Yes If you don't feel itchy ... None
［実施例１］
５００ｍＬの三口フラスコに、キシレン３００ｍＬ（溶媒）、フェノール４７．４ｇ（原料；（Ａ）式で示される化合物に該当する）、９−フルオレノン５０．４ｇ（原料；（Ｂ）式で示される化合物に該当する）、ｐ−トルエンスルホン酸５ｇ（酸性触媒）、β―メルカプトプロピオン酸０．１ｇ（酸性触媒）を仕込んで１３５℃に加熱し、１５時間撹拌した（フェノール／フルオレノン仕込比（モル比）＝１．８）。
反応終了後、反応液を分液ロートに移して、３００ｍＬのイオン交換水で１０回水洗した。水洗後の有機層は、ヘプタン５００ｍＬを徐々に加えて、固体を析出させた。固体をろ別し、２２０℃で加熱乾燥した後、粉末の固体は、溶融して均一な褐色の固体に変化した。収量は７５．６ｇであった。
上述した評価方法に従って、（１’）式で示される化合物および（２’）式で示される化合物の含有量を測定し、熱重量減少率を測定し、合成作業の時のかゆみの有無を判定した。結果を表１中の該当欄に示す。また、化合物の含有量を測定した際のＧＰＣスペクトルの１例を図１に、そのＧＰＣスペクトルの各ピークに対応する化合物の保持時間、数平均分子量（測定値）、重量平均分子量（測定値）、分子構造、理論分子量および構造式を表３中の該当欄に示す。
[Example 1]
In a 500 mL three-necked flask, 300 mL of xylene (solvent), 47.4 g of phenol (raw material; corresponding to the compound represented by formula (A)), 90.4-fluorenone (starting material; compound represented by formula (B)) Applicable), 5 g of p-toluenesulfonic acid (acidic catalyst) and 0.1 g of β-mercaptopropionic acid (acidic catalyst) were charged and heated to 135 ° C. and stirred for 15 hours (phenol / fluorenone charge ratio (molar ratio)) = 1.8).
After completion of the reaction, the reaction solution was transferred to a separatory funnel and washed with 300 mL of ion exchange water 10 times. The organic layer after water washing gradually added 500 mL of heptane to precipitate a solid. After the solid was filtered off and dried by heating at 220 ° C., the powdered solid melted and turned into a uniform brown solid. The yield was 75.6g.
According to the evaluation method described above, the content of the compound represented by the formula (1 ′) and the compound represented by the formula (2 ′) is measured, the thermal weight loss rate is measured, and the presence or absence of itching during the synthesis work is determined. did. The results are shown in the corresponding column of Table 1. FIG. 1 shows an example of a GPC spectrum when the content of the compound is measured. The retention time, number average molecular weight (measured value), and weight average molecular weight (measured value) of the compound corresponding to each peak of the GPC spectrum are shown in FIG. The molecular structure, theoretical molecular weight, and structural formula are shown in the corresponding columns of Table 3.
［比較例１］
フェノール／フルオレノンの仕込比（モル比）を１．８から８．０に変更した点、反応温度を１３５℃から５０℃に変更した点、およびβ−メルカプトプロピオン酸（酸性触媒）を０．１ｇ（対フルオレノン０．２質量％）から０．０５ｇ（対フルオレノン０．１質量％）に変更した点を除いて、実施例１と同様の方法によってフルオレン縮合体組成物を製造した。
上述した評価方法に従って、（１’）式で示される化合物および（２’）式で示される化合物の含有量を測定し、熱重量減少率を測定し、合成作業の時のかゆみの有無を判定した。結果を表２中の該当欄に示す。
[Comparative Example 1]
Phenol / fluorenone charge ratio (molar ratio) was changed from 1.8 to 8.0, reaction temperature was changed from 135 ° C. to 50 ° C., and β-mercaptopropionic acid (acidic catalyst) 0.1 g A fluorene condensate composition was produced in the same manner as in Example 1 except that the amount was changed from 0.05 g (0.2% by mass to fluorenone) to 0.05 g (0.1% by mass to fluorenone).
According to the evaluation method described above, the content of the compound represented by the formula (1 ′) and the compound represented by the formula (2 ′) is measured, the thermal weight loss rate is measured, and the presence or absence of itching during the synthesis work is determined. did. The results are shown in the corresponding column of Table 2.
［実施例２］
フェノール／フルオレノンの仕込比（モル比）を１．８から４．０に変更した点を除いて、実施例１と同様の方法によってフルオレン縮合体組成物を製造した。
上述した評価方法に従って、（１’）式で示される化合物および（２’）式で示される化合物の含有量を測定し、熱重量減少率を測定し、合成作業の時のかゆみの有無を判定した。結果を表１中の該当欄に示す。
[Example 2]
A fluorene condensate composition was produced in the same manner as in Example 1 except that the feed ratio (molar ratio) of phenol / fluorenone was changed from 1.8 to 4.0.
According to the evaluation method described above, the content of the compound represented by the formula (1 ′) and the compound represented by the formula (2 ′) is measured, the thermal weight loss rate is measured, and the presence or absence of itching during the synthesis work is determined. did. The results are shown in the corresponding column of Table 1.
［実施例３］
フェノール／フルオレノンの仕込比（モル比）を１．８から２．０に変更した点を除いて、実施例１と同様の方法によってフルオレン縮合体組成物を製造した。
上述した評価方法に従って、（１’）式で示される化合物および（２’）式で示される化合物の含有量を測定し、熱重量減少率を測定し、合成作業の時のかゆみの有無を判定した。結果を表１中の該当欄に示す。
[Example 3]
A fluorene condensate composition was produced in the same manner as in Example 1 except that the feed ratio (molar ratio) of phenol / fluorenone was changed from 1.8 to 2.0.
According to the evaluation method described above, the content of the compound represented by the formula (1 ′) and the compound represented by the formula (2 ′) is measured, the thermal weight loss rate is measured, and the presence or absence of itching during the synthesis work is determined. did. The results are shown in the corresponding column of Table 1.
［実施例４］
フェノールに代えて２−ナフトールを用いた点およびナフトール／フルオレノンの仕込比（モル比）を１．８から１．５に変更した点を除いて、実施例１と同様の方法によってフルオレン縮合体組成物を製造した。
上述した評価方法に従って、（１’）式で示される化合物および（２’）式で示される化合物の含有量を測定し、熱重量減少率を測定し、合成作業の時のかゆみの有無を判定した。結果を表１中の該当欄に示す。
[Example 4]
The fluorene condensate composition was prepared in the same manner as in Example 1 except that 2-naphthol was used instead of phenol and the naphthol / fluorenone charge ratio (molar ratio) was changed from 1.8 to 1.5. The thing was manufactured.
According to the evaluation method described above, the content of the compound represented by the formula (1 ′) and the compound represented by the formula (2 ′) is measured, the thermal weight loss rate is measured, and the presence or absence of itching during the synthesis work is determined. did. The results are shown in the corresponding column of Table 1.
［実施例５］
ｐ−トルエンスルホン酸（酸性触媒）を５．０ｇから２．５ｇに、β―メルカプトプロピオン酸（酸性触媒）を０．１ｇから０．０５ｇに、それぞれ変更した点を除いて、実施例１と同様の方法によってフルオレン縮合体組成物を製造した。
上述した評価方法に従って、（１’）式で示される化合物および（２’）式で示される化合物の含有量を測定し、熱重量減少率を測定し、合成作業の時のかゆみの有無を判定した。結果を表１中の該当欄に示す。
[Example 5]
Example 1 and p-toluenesulfonic acid (acidic catalyst) were changed from 5.0 g to 2.5 g, and β-mercaptopropionic acid (acidic catalyst) was changed from 0.1 g to 0.05 g. A fluorene condensate composition was produced in the same manner.
According to the evaluation method described above, the content of the compound represented by the formula (1 ′) and the compound represented by the formula (2 ′) is measured, the thermal weight loss rate is measured, and the presence or absence of itching during the synthesis work is determined. did. The results are shown in the corresponding column of Table 1.
［実施例６］
ｐ−トルエンスルホン酸（酸性触媒）５．０ｇに代えて硫酸（酸性触媒）５．０ｇを使用した点、およびｐ−キシレン（溶媒）に代えてトルエン（溶媒）を使用した点を除いて、実施例１と同様の方法によってフルオレン縮合体組成物を製造した。
上述した評価方法に従って、（１’）式で示される化合物および（２’）式で示される化合物の含有量を測定し、熱重量減少率を測定し、合成作業の時のかゆみの有無を判定した。結果を表１中の該当欄に示す。
[Example 6]
Except for using 5.0 g of sulfuric acid (acidic catalyst) instead of 5.0 g of p-toluenesulfonic acid (acidic catalyst) and using toluene (solvent) instead of p-xylene (solvent), A fluorene condensate composition was produced in the same manner as in Example 1.
According to the evaluation method described above, the content of the compound represented by the formula (1 ′) and the compound represented by the formula (2 ′) is measured, the thermal weight loss rate is measured, and the presence or absence of itching during the synthesis work is determined. did. The results are shown in the corresponding column of Table 1.
［実施例７］
フェノールに代えて２−フェノキシエタノールを使用した点、ｐ−トルエンスルホン酸（酸性触媒）５．０ｇに代えて硫酸（酸性触媒）５．０ｇを使用した点、およびｐ−キシレン（溶媒）に代えてｏ−キシレン（溶媒）を使用した点を除いて、実施例１と同様の方法によってフルオレン縮合体組成物を製造した。
上述した評価方法に従って、（１’）式で示される化合物および（２’）式で示される化合物の含有量を測定し、熱重量減少率を測定し、合成作業の時のかゆみの有無を判定した。結果を表１中の該当欄に示す。
[Example 7]
The point that 2-phenoxyethanol was used instead of phenol, the point that 5.0 g of sulfuric acid (acidic catalyst) was used instead of 5.0 g of p-toluenesulfonic acid (acidic catalyst), and the point that p-xylene (solvent) was used A fluorene condensate composition was produced in the same manner as in Example 1 except that o-xylene (solvent) was used.
According to the evaluation method described above, the content of the compound represented by the formula (1 ′) and the compound represented by the formula (2 ′) is measured, the thermal weight loss rate is measured, and the presence or absence of itching during the synthesis work is determined. did. The results are shown in the corresponding column of Table 1.
［実施例８］
実施例１で得られたビスフェノールフルオレン組成物２０ｇ、クロロメチルオキシラン４１ｇ、ジメチルスルホキシド１５ｇを４つ口フラスコに入れて、内温を４０℃にした。次に、水酸化ナトリウム（固体）を、０．５ｇずつ、１０分間隔で添加し、合計４．５ｇを加えた。添加終了後、７０℃で２時間撹拌した。さらに、内温を１３０℃にして減圧蒸留し、最後は内圧２０Ｔｏｒｒで１５分間保持した。減圧を解除し、メチルイソブチルケトン２００ｇを添加し、７０℃で３０質量％水酸化ナトリウム水溶液を１．４４ｇ添加して１時間撹拌した。撹拌終了後、反応液を１Ｌの分液ロートに移して、蒸留水２００ｍＬを加えて良くふり、静置して水層のｐＨを測定した。この水洗操作は、水層が中性になるまで繰り返した。有機層はエバポレータでメチルエチルケトンを除去して、エポキシ化組成物を得た。ＪＩＳ Ｋ ７２３６：２００１「エポキシ樹脂のエポキシ当量の求め方」に従ってエポキシ当量を測定した結果、２９２ｇ／当量であり、本発明のフルオレン縮合体組成物からエポキシ樹脂が合成できることが確認された。また、硬化剤として、水素化メチル無水フタル酸（和光製、１７３ｇ／当量）を用い、硬化促進剤としてトリフェニルホスフィンを用いて、本発明の組成物１．５ｇ、水素化メチル無水フタル酸硬化物０．８９ｇ、トリフェニルホスフィンをアルミ容器中で１５０℃で均一に混合した後、１５０℃で２時間、１６０℃で２時間、１８０℃で２時間、加熱硬化させて、硬化物を作成した。
[Example 8]
20 g of the bisphenolfluorene composition obtained in Example 1, 41 g of chloromethyloxirane, and 15 g of dimethyl sulfoxide were placed in a four-necked flask, and the internal temperature was set to 40 ° C. Next, sodium hydroxide (solid) was added in 0.5 g increments at 10 minute intervals, and a total of 4.5 g was added. After completion of the addition, the mixture was stirred at 70 ° C. for 2 hours. Further, the internal temperature was reduced to 130 ° C. and distilled under reduced pressure, and finally, the internal pressure was maintained at 20 Torr for 15 minutes. The decompression was released, 200 g of methyl isobutyl ketone was added, and 1.44 g of a 30% by mass aqueous sodium hydroxide solution was added at 70 ° C., followed by stirring for 1 hour. After completion of the stirring, the reaction solution was transferred to a 1 L separatory funnel, 200 mL of distilled water was added, and the mixture was shaken well and allowed to stand to measure the pH of the aqueous layer. This washing operation was repeated until the aqueous layer became neutral. Methyl ethyl ketone was removed from the organic layer with an evaporator to obtain an epoxidized composition. As a result of measuring the epoxy equivalent according to JIS K 7236: 2001 “How to Determine Epoxy Equivalent of Epoxy Resin”, it was 292 g / equivalent, and it was confirmed that the epoxy resin can be synthesized from the fluorene condensate composition of the present invention. Moreover, hydrogenated methyl phthalic anhydride (manufactured by Wako, 173 g / equivalent) is used as a curing agent, triphenylphosphine is used as a curing accelerator, 1.5 g of the composition of the present invention, hydrogenated methyl phthalic anhydride cured 0.89 g of the product and triphenylphosphine were uniformly mixed at 150 ° C. in an aluminum container, and then heat-cured at 150 ° C. for 2 hours, 160 ° C. for 2 hours, and 180 ° C. for 2 hours to prepare a cured product. .
［比較例２］
フェノール／フルオレノンの仕込比（モル比）を１．８から８．０に変更した点を除いて、実施例１と同様の方法によってフルオレン縮合体組成物を製造した。
上述した評価方法に従って、（１’）式で示される化合物および（２’）式で示される化合物の含有量を測定し、熱重量減少率を測定し、合成作業の時のかゆみの有無を判定した。結果を表２中の該当欄に示す。
[Comparative Example 2]
A fluorene condensate composition was produced in the same manner as in Example 1 except that the feed ratio (molar ratio) of phenol / fluorenone was changed from 1.8 to 8.0.
According to the evaluation method described above, the content of the compound represented by the formula (1 ′) and the compound represented by the formula (2 ′) is measured, the thermal weight loss rate is measured, and the presence or absence of itching during the synthesis work is determined. did. The results are shown in the corresponding column of Table 2.
［比較例３］
フェノール／フルオレノンの仕込比（モル比）を１．８から１．０に変更した点、および反応温度を１３５℃から５０℃に変更した点を除いて、実施例１と同様の方法によってフルオレン縮合体組成物を製造した。
上述した評価方法に従って、（１’）式で示される化合物および（２’）式で示される化合物の含有量を測定し、熱重量減少率を測定し、合成作業の時のかゆみの有無を判定した。結果を表２中の該当欄に示す。
[Comparative Example 3]
Fluorene condensation was carried out in the same manner as in Example 1 except that the feed ratio (molar ratio) of phenol / fluorenone was changed from 1.8 to 1.0 and the reaction temperature was changed from 135 ° C to 50 ° C. A body composition was produced.
According to the evaluation method described above, the content of the compound represented by the formula (1 ′) and the compound represented by the formula (2 ′) is measured, the thermal weight loss rate is measured, and the presence or absence of itching during the synthesis work is determined. did. The results are shown in the corresponding column of Table 2.
［比較例４］
反応温度を１３５℃から５０℃に変更した点を除いて、実施例１と同様の方法によってフルオレン縮合体組成物を製造した。
上述した評価方法に従って、（１’）式で示される化合物および（２’）式で示される化合物の含有量を測定し、熱重量減少率を測定し、合成作業の時のかゆみの有無を判定した。結果を表２中の該当欄に示す。
[Comparative Example 4]
A fluorene condensate composition was produced in the same manner as in Example 1 except that the reaction temperature was changed from 135 ° C to 50 ° C.
According to the evaluation method described above, the content of the compound represented by the formula (1 ′) and the compound represented by the formula (2 ′) is measured, the thermal weight loss rate is measured, and the presence or absence of itching during the synthesis work is determined. did. The results are shown in the corresponding column of Table 2.
［実施例・比較例の説明］
実施例１〜７で製造したフルオレン縮合体組成物はいずれも比較例１〜４のフルオレン縮合体組成物に比べて、熱重量減少量率が小さく、しかも、取扱い時のかゆみの問題もなく、性能および作業性の両面で優れた特性を示した。また、実施例８で製造したエポキシ化組成物はエポキシ樹脂の原料として有用であることが示唆された。
以下により詳細に考察する。
[Description of Examples and Comparative Examples]
The fluorene condensate compositions produced in Examples 1 to 7 each have a smaller thermal weight loss rate than the fluorene condensate compositions of Comparative Examples 1 to 4, and there is no problem of itching during handling. Excellent characteristics in both performance and workability. Moreover, it was suggested that the epoxidation composition manufactured in Example 8 is useful as a raw material of an epoxy resin.
Consider in more detail below.
〈仕込比および反応温度〉
実施例１、２および３（表１を参照）、ならびに比較例２（表２を参照）は、フェノールと９−フルオレノンの仕込比「（フェノールのモル数）／（９−フルオレノンのモル数）」（モル比）が異なる例である。仕込比（モル比）が１．０以上６．０以下の範囲内である実施例１（仕込比＝１．８）、実施例２（仕込比＝４．０）および実施例３（仕込比＝２．０）は、仕込比（モル比）が１．０以上６．０以下の範囲外である比較例２（仕込比＝８．０）に比べ、熱重量減少率が小さく、半分未満であり、かゆみも無く、性能および作業性の両面で優れた特性を持つが、仕込比（モル比）が１．０超、２．０未満である実施例１（仕込比＝１．８）は、熱重量減少率が特に小さく、比較例２の約１／４以下に過ぎず、極めて優れた性能を示した。
実施例１（表１を参照）および比較例４（表２を参照）は、反応温度が異なる例である。反応温度が１００℃超の実施例１（反応温度＝１３５℃）は反応温度が１００℃以下の比較例４（反応温度＝５０℃）に比べて、熱重量減少率が約１／４と小さく、かゆみも無く、性能および作業性の両面で優れた特性を示した。
実施例１（表１を参照）および比較例１（表２を参照）は、仕込比（モル比）および反応温度が異なる例である。仕込比（モル比）が８．０、反応温度が５０℃と、いずれも本発明の製造方法の範囲外である比較例１は、熱重量減少率が５５．３質量％と大きい上に、かゆみの問題もあり、性能および作業性の両面で劣っていた。
仕込比および反応温度の一方でも本発明の製造方法に規定する範囲の外となる場合には、フルオレン縮合体組成物中の（１’）式で示される化合物および（２’）式で示される化合物の含有量、ならびにこれらの合計含有量のうち少なくとも１つが本発明のフルオレン縮合体組成物に規定する範囲外となり、熱重量減少率が大きい上に、かゆみの問題もあり、性能および作業性の両面で劣っていた。
<Feed ratio and reaction temperature>
Examples 1, 2 and 3 (see Table 1), and Comparative Example 2 (see Table 2) are charged ratios of phenol and 9-fluorenone "(number of moles of phenol) / (number of moles of 9-fluorenone)" (Molar ratio) is an example. Example 1 (feeding ratio = 1.8), Example 2 (feeding ratio = 4.0), and Example 3 (feeding ratio) in which the feed ratio (molar ratio) is in the range of 1.0 to 6.0. = 2.0) is less than half of the thermal weight reduction rate compared to Comparative Example 2 (feed ratio = 8.0) where the feed ratio (molar ratio) is outside the range of 1.0 or more and 6.0 or less. Example 1 in which the feed ratio (molar ratio) is more than 1.0 and less than 2.0, with no itching and excellent properties in both performance and workability (feed ratio = 1.8) The thermal weight loss rate was particularly small, which was only about 1/4 or less that of Comparative Example 2, and showed extremely excellent performance.
Example 1 (see Table 1) and Comparative Example 4 (see Table 2) are examples with different reaction temperatures. In Example 1 (reaction temperature = 135 ° C.) with a reaction temperature exceeding 100 ° C., the thermogravimetric reduction rate was as small as about ¼ compared to Comparative Example 4 (reaction temperature = 50 ° C.) with a reaction temperature of 100 ° C. or less. There was no itching, and it showed excellent characteristics in both performance and workability.
Example 1 (see Table 1) and Comparative Example 1 (see Table 2) are examples in which the charging ratio (molar ratio) and reaction temperature are different. The charge ratio (molar ratio) is 8.0, the reaction temperature is 50 ° C., and Comparative Example 1, which is outside the range of the production method of the present invention, has a large thermal weight loss rate of 55.3% by mass, There was also a problem of itching, and both performance and workability were inferior.
When either the charging ratio or the reaction temperature falls outside the range specified in the production method of the present invention, the compound represented by the formula (1 ′) and the formula (2 ′) in the fluorene condensate composition are used. The content of the compound, and at least one of these total contents is outside the range specified in the fluorene condensate composition of the present invention, the thermal weight loss rate is large, there is also a problem of itchiness, performance and workability It was inferior in both sides.
〈原料、酸性触媒、溶媒〉
実施例１、５〜７（表１を参照）から、原料の種類、酸性触媒の種類、組合せおよび添加量、ならびに溶媒の種類を変更しても、（１’）式で示される化合物および（２’）式で示される化合物の含有量、ならびにこれらの合計含有量が規定範囲内であり、性能および作業性の両面で優れた特性を持つ本発明のフルオレン縮合体組成物を製造できることが示された。
<Raw material, acidic catalyst, solvent>
From Examples 1 and 5 to 7 (see Table 1), the compound represented by the formula (1 ′) and the compound (1 ′) and ( 2 ′) It is shown that the fluorene condensate composition of the present invention can be produced with the content of the compound represented by the formula and the total content thereof within the specified range and having excellent properties in both performance and workability. It was done.
〈ＧＰＣスペクトル〉
図１に示すＧＰＣスペクトルおよび表３に示す各ピークに対応する化合物の同定結果から、本発明のフルオレン縮合体組成物の製造方法によって製造したフルオレン縮合体組成物は、ビスフェノールフルオレン（ＢＰＦＬ：Ｂｉｓｐｈｅｎｏｌ ｆｌｕｏｒｅｎｅ）の２量体、３量体および４量体を含むことが示された。
<GPC spectrum>
From the GPC spectrum shown in FIG. 1 and the identification results of the compounds corresponding to the respective peaks shown in Table 3, the fluorene condensate composition produced by the method for producing the fluorene condensate composition of the present invention is bisphenol fluorene (BPFL: Bisphenol fluorene). ) Dimer, trimer and tetramer.
Claims (10)
下記（２）式で示される化合物を８８〜１０質量％含有し、
下記（１）式で示される化合物および下記（２）式で示される化合物の合計含有量が８５質量％以上である、フルオレン縮合体組成物。
A fluorene condensate composition in which the total content of the compound represented by the following formula (1) and the compound represented by the following formula (2) is 85% by mass or more.
下記（４）式で示される化合物を８８〜１０質量％含有し、
下記（３）式で示される化合物および下記（４）式で示される化合物の合計含有量が８５質量％以上である、エポキシ化組成物。
An epoxidized composition having a total content of a compound represented by the following formula (3) and a compound represented by the following formula (4) of 85% by mass or more.
前記（Ａ）式で示される化合物と前記（Ｂ）式で示される化合物の混合比「（Ａ）式で示される化合物の合計モル数／（Ｂ）式で示される化合物の合計モル数」が１．０以上６．０以下であり、かつ、反応温度が１００℃超である、フルオレン縮合体組成物の製造方法。
The mixing ratio of the compound represented by the formula (A) and the compound represented by the formula (B) “the total number of moles of the compound represented by the formula (A) / the total number of moles of the compound represented by the formula (B)” is The manufacturing method of the fluorene condensate composition which is 1.0 or more and 6.0 or less, and reaction temperature is over 100 degreeC.
前記縮合工程で得られたフルオレン縮合体組成物をエポキシ化するエポキシ化工程を含み、
前記（Ａ）式で示される化合物と前記（Ｂ）式で示される化合物の混合比「（Ａ）式で示される化合物の合計モル数／（Ｂ）式で示される化合物の合計モル数」が１．０以上６．０以下であり、かつ、反応温度が１００℃超である、エポキシ化組成物の製造方法。
The mixing ratio of the compound represented by the formula (A) and the compound represented by the formula (B) “the total number of moles of the compound represented by the formula (A) / the total number of moles of the compound represented by the formula (B)” is A method for producing an epoxidized composition, which is 1.0 or more and 6.0 or less and the reaction temperature is higher than 100 ° C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015248877A JP6734645B2 (en) | 2015-12-21 | 2015-12-21 | Fluorene condensate composition, epoxidized composition, and methods for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015248877A JP6734645B2 (en) | 2015-12-21 | 2015-12-21 | Fluorene condensate composition, epoxidized composition, and methods for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2017114947A true JP2017114947A (en) | 2017-06-29 |
| JP6734645B2 JP6734645B2 (en) | 2020-08-05 |
Family
ID=59233602
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2015248877A Active JP6734645B2 (en) | 2015-12-21 | 2015-12-21 | Fluorene condensate composition, epoxidized composition, and methods for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP6734645B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107501490A (en) * | 2017-08-17 | 2017-12-22 | 四川金和成科技有限公司 | A kind of preparation method of the polyether-ether-ketone of the pyridine structure containing phthalazone |
| WO2018230394A1 (en) * | 2017-06-15 | 2018-12-20 | 田岡化学工業株式会社 | Method for producing alcohols having fluorene skeleton |
| WO2020226126A1 (en) * | 2019-05-09 | 2020-11-12 | 帝人株式会社 | Compound having fluorene skeleton and method for producing same |
| JP2020186220A (en) * | 2019-05-09 | 2020-11-19 | 帝人株式会社 | Compound having fluorene skeleton and production method of the same |
| JP2021031401A (en) * | 2019-08-19 | 2021-03-01 | 帝人株式会社 | Compound having fluorene skeleton and method for producing the same |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07165657A (en) * | 1993-12-10 | 1995-06-27 | Osaka Gas Co Ltd | Production of fluorene derivative and its purification |
| JPH08234422A (en) * | 1995-02-27 | 1996-09-13 | Nippon Zeon Co Ltd | Positive type resist composition |
| JPH08234423A (en) * | 1995-02-27 | 1996-09-13 | Nippon Zeon Co Ltd | Positive type resist composition |
| JP2007023016A (en) * | 2005-06-16 | 2007-02-01 | Taoka Chem Co Ltd | Method for producing fluorene derivative |
| JP2007197367A (en) * | 2006-01-26 | 2007-08-09 | Taoka Chem Co Ltd | Method for producing fluorene derivative |
| WO2013047106A1 (en) * | 2011-09-30 | 2013-04-04 | 三菱瓦斯化学株式会社 | Resin having fluorene structure and underlayer film-forming material for lithography |
| KR20130039864A (en) * | 2011-10-13 | 2013-04-23 | 주식회사 동진쎄미켐 | Polymer having aromatic ring and under-layer composition of resist including the same |
| WO2014157881A1 (en) * | 2013-03-26 | 2014-10-02 | 주식회사 동진쎄미켐 | Resist underlayer composition and method for forming pattern using same |
| JP2014189520A (en) * | 2013-03-27 | 2014-10-06 | Osaka Gas Chem Kk | Polyhydroxy compound having fluorene skeleton |
-
2015
- 2015-12-21 JP JP2015248877A patent/JP6734645B2/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07165657A (en) * | 1993-12-10 | 1995-06-27 | Osaka Gas Co Ltd | Production of fluorene derivative and its purification |
| JPH08234422A (en) * | 1995-02-27 | 1996-09-13 | Nippon Zeon Co Ltd | Positive type resist composition |
| JPH08234423A (en) * | 1995-02-27 | 1996-09-13 | Nippon Zeon Co Ltd | Positive type resist composition |
| JP2007023016A (en) * | 2005-06-16 | 2007-02-01 | Taoka Chem Co Ltd | Method for producing fluorene derivative |
| JP2007197367A (en) * | 2006-01-26 | 2007-08-09 | Taoka Chem Co Ltd | Method for producing fluorene derivative |
| WO2013047106A1 (en) * | 2011-09-30 | 2013-04-04 | 三菱瓦斯化学株式会社 | Resin having fluorene structure and underlayer film-forming material for lithography |
| KR20130039864A (en) * | 2011-10-13 | 2013-04-23 | 주식회사 동진쎄미켐 | Polymer having aromatic ring and under-layer composition of resist including the same |
| WO2014157881A1 (en) * | 2013-03-26 | 2014-10-02 | 주식회사 동진쎄미켐 | Resist underlayer composition and method for forming pattern using same |
| JP2014189520A (en) * | 2013-03-27 | 2014-10-06 | Osaka Gas Chem Kk | Polyhydroxy compound having fluorene skeleton |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018230394A1 (en) * | 2017-06-15 | 2018-12-20 | 田岡化学工業株式会社 | Method for producing alcohols having fluorene skeleton |
| CN107501490A (en) * | 2017-08-17 | 2017-12-22 | 四川金和成科技有限公司 | A kind of preparation method of the polyether-ether-ketone of the pyridine structure containing phthalazone |
| CN107501490B (en) * | 2017-08-17 | 2019-07-09 | 四川金和成科技有限公司 | A kind of preparation method of the polyether-ether-ketone of the pyridine structure containing phthalazone |
| WO2020226126A1 (en) * | 2019-05-09 | 2020-11-12 | 帝人株式会社 | Compound having fluorene skeleton and method for producing same |
| JP2020186220A (en) * | 2019-05-09 | 2020-11-19 | 帝人株式会社 | Compound having fluorene skeleton and production method of the same |
| CN113795476A (en) * | 2019-05-09 | 2021-12-14 | 帝人株式会社 | Compound having fluorene skeleton and method for producing same |
| JP7303055B2 (en) | 2019-05-09 | 2023-07-04 | 帝人株式会社 | Compound having fluorene skeleton and method for producing the same |
| CN113795476B (en) * | 2019-05-09 | 2024-04-09 | 帝人株式会社 | Compound having fluorene skeleton and method for producing same |
| JP2021031401A (en) * | 2019-08-19 | 2021-03-01 | 帝人株式会社 | Compound having fluorene skeleton and method for producing the same |
| JP7303062B2 (en) | 2019-08-19 | 2023-07-04 | 帝人株式会社 | Compound having fluorene skeleton and method for producing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP6734645B2 (en) | 2020-08-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6734645B2 (en) | Fluorene condensate composition, epoxidized composition, and methods for producing the same | |
| JP5249578B2 (en) | Epoxy compound having fluorene skeleton | |
| TWI633096B (en) | Method for purification of compound or resin | |
| JP4998271B2 (en) | Phenolic resin and resin composition | |
| JP5613284B2 (en) | Thermosetting resin composition and cured product thereof | |
| KR20160021085A (en) | Epoxy compound, epoxy resin, curable compound, cured product thereof, semiconductor sealing material, and printed circuit board | |
| JP6925853B2 (en) | New benzoxazine resin composition and cured product thereof | |
| US20160122269A1 (en) | Compound containing phenolic hydroxyl group, phenolic resin, curable composition, cured product thereof, semiconductor sealing material, and printed circuit board | |
| JP6087738B2 (en) | Fluorene compound having phenolic hydroxyl group and epoxy compound thereof | |
| JP2011046837A (en) | Modified dimethylnaphtalene formaldehyde resin | |
| JP5870918B2 (en) | Method for purifying alkylnaphthalene formaldehyde polymer | |
| JP6160777B2 (en) | Epoxy resin, production method thereof, epoxy resin composition and cured product thereof | |
| KR20160019888A (en) | Compound containing phenolic hydroxyl group, phenolic resin, curable composition, cured product thereof, semiconductor sealing material, and printed circuit board | |
| US9200105B2 (en) | Naphthalene formaldehyde resin, deacetalized naphthalene formaldehyde resin, and modified naphthalene formaldehyde resin | |
| JP2011231024A (en) | Anthracene derivative, curable composition, and the cured product | |
| JP5353546B2 (en) | Process for producing modified dimethylnaphthalene formaldehyde resin | |
| JP5719631B2 (en) | Compound, derivative, composition, cured product, and method for producing compound and derivative | |
| TW201833165A (en) | Active ester resin and cured product thereof | |
| JP2012087103A (en) | Anthracene derivative, curable composition, and cured product | |
| JPH04255714A (en) | Polyfunctional epoxy resin and its production | |
| JP7158229B2 (en) | Aromatic modified polyhydric hydroxy resin, aromatic modified epoxy resin, epoxy resin composition and cured product thereof | |
| JPH0730151B2 (en) | Method for producing phenolic novolac composition | |
| JPH04275317A (en) | New novolak type resin and its production | |
| JP3104915B2 (en) | Novolak resin manufacturing method | |
| WO2018173499A1 (en) | Polyester resin and cured product thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20180206 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20180808 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20181002 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20181122 |
|
| RD02 | Notification of acceptance of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7422 Effective date: 20181122 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20190423 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20190605 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20191203 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20200128 |
|
| A911 | Transfer to examiner for re-examination before appeal (zenchi) |
Free format text: JAPANESE INTERMEDIATE CODE: A911 Effective date: 20200204 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20200421 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20200601 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20200707 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20200710 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 6734645 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |