JP5742439B2 - Fluorescent compound and fluorescent resin composition - Google Patents

Description

  The present invention relates to a novel fluorescent organic compound and a fluorescent resin composition.

  An organic compound having a fluorescent chromophore (hereinafter referred to as a “fluorescent compound”) is less expensive than a fluorescent inorganic compound, so that a colorant such as paper, fiber, or resin is used as a fluorescent ink or fluorescent pigment. However, there are various other uses. A fluorescent compound having a reactive substituent is used for bioimaging as a fluorescent tag. In addition, a fluorescent compound can also be used in the light emitting layer of the organic electroluminescent element, and the fluorescent compound is used for the color filter in the color conversion type organic electroluminescent element (Patent Document 1: Japanese Patent Application Laid-Open No. 2007-213993). Issue gazette). A fluorescent compound is also used to adjust the color tone and brightness of the light emitting diode (Patent Document 2: Japanese Patent Application Laid-Open No. 2008-98687). Here, the fluorescence means that fluorescence is emitted at room temperature by light irradiation.

  Colorants can be broadly classified into two types: dyes and pigments. A pigment is an aggregate of molecules having a chromophore and has a large particle size. In contrast, a dye is a chromophore-containing molecule that can be dissolved in a medium such as a solvent or a resin, and is agglomerated in a solid state depending on the molecular structure, but does not agglomerate in the medium. Is low. The size of molecular aggregates is optically important, and in general, materials colored with pigments have a larger particle size of colorant than materials colored with dyes, so transparency, brightness, and saturation are inferior. .

  Except for the case where a chemical reaction is carried out between molecules such as a fluorescent tag, in general, a fluorescent compound is often used as a pigment. One of the reasons is to improve light resistance, but typical fluorescent compounds such as rhodamine, fluorescein, and cyanine are (1) highly polar ionic aromatic compounds that interact with each other. (2) These compounds often have a donor site (heteroatom-hydrogen bond) and an acceptor site (carbonyl group, etc.) that form hydrogen bonds in the molecule. Another reason is that the solubility in a low-polarity medium is low.

  For the above reasons, when coloring a resin with a fluorescent compound, it is possible to use a dye in the case of a relatively high polarity resin such as an acrylic resin or a polyester resin, but a polyolefin resin or a silicone resin. In the case of a resin having a low polarity such as the above, a pigment is inevitably used because the solubility of the dye is low. When coloring with a pigment, in order to obtain a transparent resin composition, it is necessary to disperse the pigment uniformly in the resin to a size smaller than the wavelength of light, which requires much energy and time. Is a process of consuming.

  As a method for improving the compatibility with a resin having a low polarity, there is a method of binding a fluorescent compound to the resin. For example, Patent Document 3 (Japanese Patent Application Laid-Open No. 2007-169535) describes a silicone resin in which an aminosilicone resin and a fluorescent compound are bonded. However, this method is not preferable because it is difficult to completely remove the unreacted fluorescent compound, and this aggregates and precipitates during storage and use, which changes the appearance and optical characteristics. Moreover, since it is a polymer, it has a molecular weight distribution and the chemical structure of each molecule is non-uniform, so it is difficult to make the fluorescent compound uniformly dispersed inside the resin. Furthermore, when a plurality of fluorescent substituents are present close to each other in the molecule, the color tone may change due to excimer emission.

  In addition to the above-mentioned representative fluorescent compounds, there are compounds with a simple structure such as coumarin and quinolinone that emit strong fluorescence. For example, coumarin derivatives are used as fluorescent whitening agents for fibers and papers. (Patent Document 4: Japanese Patent Laid-Open No. 6-294097). In Patent Documents 5 and 6 (JP-A-7-278133 and JP-2010-201002), a coumarin derivative may be added to the photopolymerizable composition as a sensitizer or a photopolymerization initiator. It is disclosed. Furthermore, Patent Document 7 (Japanese Patent Application Laid-Open No. 2003-268107) discloses a polyfunctional monomer that is polymerized by a photodimerization reaction of a coumarin moiety.

  However, when viewed as a fluorescent compound, a compound that easily undergoes a photochemical reaction such as photodimerization or radical generation is not preferable because it has a low fluorescence quantum yield and is not chemically stable. Further, the general characteristics of the above-described fluorescent compounds also correspond to coumarin derivatives and quinolinone derivatives, which are poorly compatible with low polarity resins and are difficult to use as colorants.

JP 2007-213993 A JP 2008-98687 A JP 2007-169535 A JP-A-6-294097 JP 7-278133 A JP 2010-198002 A JP 2003-268107 A

  The present invention has been made in view of the above circumstances, and is excellent in solubility in an organic solvent and compatibility with a resin or a prepolymer or a monomer, in particular, compatibility with a silicone resin, and a resin composition by a simple method. It aims at providing the fluorescent compound which can be produced, and the fluorescent resin composition containing this.

  As a result of intensive studies to achieve the above object, the present inventors have found a novel fluorescent compound having a specific structure, and have found that the above problem can be solved by using this, and the present invention is It came to an eggplant.

（式（１）において、Ｘは−Ｏ−又は−ＮＲ−を表す。Ｒ¹は炭素数１〜２０のフッ素原子で置換されていてもよい一価炭化水素基を表す。Ｒ²は水素原子及び炭素数１〜２０のフッ素原子で置換されていてもよい一価炭化水素基から選ばれる基である。Ｒ³、Ｒ⁴、Ｒ⁵及びＲ⁶は同一でも異なってもよく、水素原子、炭素数１〜２０のハロゲン原子で置換されていてもよい一価炭化水素基、下記式（４）で表されるジオルガノアミノ基、下記式（５）で表されるオルガノキシ基、下記式（６）で表されるオルガノスルファニル基、及び下記式（２）のシロキサン含有基から独立に選ばれる置換基である。Ｒ³とＲ⁴、Ｒ⁴とＲ⁵、Ｒ⁵とＲ⁶はそれぞれ互いに結合してそれらが結合する二つの炭素原子を含む構成炭素原子数が５〜８の環構造を形成してもよい。但し、Ｒ ³、Ｒ⁴、Ｒ⁵及びＲ⁶のうち少なくとも一つは、下記式（２）で表されるシロキサン含有基であるか又はそれを置換基として含有する基である。Ｒは炭素数１〜２０の一価炭化水素基であって、式（１）の化合物に複数のＲ及び／又はＲ¹が含まれる場合、それらは同一でも異なっていてもよい。）

（式（２）において、Ｓｘはケイ素原子数２〜１０であって、該ケイ素原子に炭素数１〜２０の一価炭化水素基が結合した直鎖状、分岐鎖状又は環状のオルガノシロキサニル基を表し、ケイ素原子がＡと結合している。Ａは炭素数１〜２０の二価炭化水素基を表す。Ａ¹は−Ｏ−、−Ｓ−、−ＮＲ−、−Ｏ−Ｃ（Ｏ）−、−Ｃ（Ｏ）−Ｏ−、−ＮＲ¹−Ｃ（Ｏ）−、−Ｃ（Ｏ）−ＮＲ¹−及び単結合のいずれかを表す。）

（式（４）において、Ｒ⁸は同一でも異なってもよく、炭素数１〜２０の一価炭化水素基又は上記式（２）で表されるシロキサン含有基を表す。但し、酸素原子、硫黄原子及び窒素原子のヘテロ原子同士は隣接しない。）

（式（５）において、Ｒ⁹は炭素数１〜２０の一価炭化水素基又は上記式（２）で表されるシロキサン含有基を表す。但し、酸素原子、硫黄原子、及び窒素原子のヘテロ原子同士は隣接しない。）

（式（６）において、Ｒ¹⁰は炭素数１〜２０の一価炭化水素基又は上記式（２）で表されるシロキサン含有基を表す。但し、酸素原子、硫黄原子、及び窒素原子のヘテロ原子同士は隣接しない。）
請求項２：
一般式（１）において、Ｒ ⁴ 又はＲ ⁵ が式（４）〜（６）で表されるいずれかの置換基である請求項１に記載の蛍光性化合物。
請求項３：
一般式（１）において、Ｒ²が水素原子である請求項１又は２に記載の蛍光性化合物。
請求項４：
請求項１〜３のいずれか１項に記載の蛍光性化合物及び樹脂を含有する蛍光性樹脂組成物。
請求項５：
前記樹脂が、シリコーン樹脂である請求項４に記載の蛍光性樹脂組成物。
That is, the present invention provides the following fluorescent compound and a resin composition containing the same.
Claim 1:
A fluorescent compound represented by the following general formula (1).

(In the formula (1), X represents —O— or —NR—. R ¹ represents a monovalent hydrocarbon group which may be substituted with a fluorine atom having 1 to 20 carbon atoms. R ² represents a hydrogen atom. and .R ³ is a group selected good monovalent hydrocarbon radical or et be substituted with a fluorine atom having 1 to 20 carbon atoms, R ^4, R ⁵ and R ⁶ may be the same or different, a hydrogen atom , A monovalent hydrocarbon group optionally substituted with a halogen atom having 1 to 20 carbon atoms, a diorganoamino group represented by the following formula (4), an organoxy group represented by the following formula (5), the following formula The substituent is independently selected from the organosulfanyl group represented by (6) and the siloxane-containing group of the following formula (2): R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁵ and R ⁶ are each A ring structure having 5 to 8 carbon atoms, which includes two carbon atoms bonded to each other and bonded to each other. Provided that at least one of R ³ , R ⁴ , R ⁵ and R ⁶ is a siloxane-containing group represented by the following formula (2) or a group containing it as a substituent: R is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and when the compound of the formula (1) includes a plurality of R and / or R ¹ , they may be the same or different. )

(In Formula (2), Sx has 2 to 10 silicon atoms, and a linear, branched or cyclic organosiloxa group in which a monovalent hydrocarbon group having 1 to 20 carbon atoms is bonded to the silicon atom. Represents a nyl group, and a silicon atom is bonded to A. A represents a divalent hydrocarbon group having 1 to 20 carbon atoms, A ¹ represents —O—, —S—, —NR—, —O—C. (O) -, - C ( O) -O -, - NR 1 -C (O) -, - C (O) -NR 1 - and represents either a single bond).

(In Formula (4), R ⁸ may be the same or different and represents a monovalent hydrocarbon group having 1 to 20 carbon atoms or a siloxane-containing group represented by Formula (2) above, provided that an oxygen atom, sulfur Atom and nitrogen heteroatoms are not adjacent to each other.)

(In the formula (5), R ⁹ represents a monovalent hydrocarbon group having 1 to 20 carbon atoms or a siloxane-containing group represented by the above formula (2), provided that an oxygen atom, a sulfur atom, and a nitrogen atom are heterogeneous. Atoms are not adjacent.)

(In the formula (6), R ¹⁰ represents a monovalent hydrocarbon group having 1 to 20 carbon atoms or a siloxane-containing group represented by the above formula (2), provided that an oxygen atom, a sulfur atom, and a nitrogen atom are heterogeneous. Atoms are not adjacent.)
Claim 2:
The fluorescent compound according to claim 1, wherein in the general formula (1), R ⁴ or R ⁵ is any substituent represented by the formulas (4) to (6).
Claim 3:
The fluorescent compound according to claim 1 or 2, wherein in the general formula (1), R ² is a hydrogen atom.
Claim 4:
The fluorescent resin composition containing the fluorescent compound and resin of any one of Claims 1-3.
Claim 5:
The fluorescent resin composition according to claim 4, wherein the resin is a silicone resin.

  The fluorescent compound of the present invention does not contain a heteroelement-hydrogen bond serving as a hydrogen bond donor, has excellent compatibility with an organic solvent or a resin, and can be uniformly dispersed in various media. In addition, a fluorescent resin composition having high brightness and chroma can be easily obtained. In addition, since it is a single compound having no molecular weight distribution, it can be purified to high purity and has high fluorescence efficiency.

The fluorescent compound of the present invention is represented by the following general formula (1).

  In the general formula (1), X represents —O— or —NR—. Here, R is a monovalent hydrocarbon group having 1 to 20 carbon atoms, particularly 1 to 12 carbon atoms, specifically, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, cyclopentyl group, isopentyl group, 2-pentyl group, 3-pentyl group, tert-pentyl group, hexyl group, cyclohexyl group, octyl group, decyl group, dodecyl group, tetradecyl group Group, hexadecyl group, octadecyl group, icosyl group, etc., linear, branched, cyclic saturated hydrocarbon group; vinyl group, allyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, undecenyl group, octadecenyl group, etc. Unsaturated hydrocarbon group: phenyl group, naphthyl group, benzyl group, phenethyl group, phenylpropyl group, 2-methyl An aromatic hydrocarbon group such as an phenyl group, 3-methylphenyl group, 4-methylphenyl group, 2,4-dimethylphenyl group, 3,5-dimethylphenyl group, 3,5-di-tert-butylphenyl group; Can be mentioned. Among these, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, vinyl Group, allyl group and phenyl group are preferred. The compound of formula (1) may contain a plurality of R, which may be the same or different.

In the general formula (1), R ¹ is a monovalent hydrocarbon group which may be substituted with a fluorine atom having 1 to 20 carbon atoms, particularly 1 to 6 carbon atoms, and a siloxane represented by the following formula (2). Represents a group selected from the containing groups. Specific examples of the monovalent hydrocarbon group R ¹ which may be substituted with a fluorine atom include, in addition to the monovalent hydrocarbon groups mentioned as specific examples of R, a trifluoromethyl group, a pentafluoroethyl group, a heptafluoro group. Propyl group, 2,2,2-trifluoroethyl group, 3,3,3-trifluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, 3,3,4,4,5, 5,6,6,6-nonafluorohexyl group, 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl group, 3,3,4 4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl group, pentafluorophenyl group, pentafluorobenzyl group, trifluoromethylphenyl group Monovalent hydrocarbon groups substituted with fluorine atoms such as It is below. Among these, in particular, methyl group, ethyl group, propyl group, phenyl group, benzyl group, trifluoromethyl group, 2,2,2-trifluoroethyl group, pentafluoroethyl group, 3,3,3-trifluoro A propyl group, a pentafluorophenyl group and a pentafluorobenzyl group are preferred. The compound of formula (1) may contain a plurality of R ^{1 s,} which may be the same or different.

一般式（２）において、Ｓｘはケイ素原子数２〜１０、特にケイ素原子数２〜５であって該ケイ素原子が炭素数１〜２０、特に炭素数１〜６の一価炭化水素基、例えばアルキル基で置換されていてもよい、直鎖状、分岐鎖状、又は環状のオルガノシロキサニル基を表す。Ｓｘはケイ素原子がＡと結合しており、ケイ素−水素結合やケイ素−アルコキシ結合のような反応性の置換基を含まない。Ｓｘの具体例としては、ペンタメチルジシロキサン−１−イル基、３，３，３−トリエチル−１，１−ジメチルジシロキサン−１−イル基、ペンタエチルジシロキサン−１−イル基、３−ビニル−１，１，３，３−テトラメチルジシロキサン−１−イル基、３−ｔｅｒｔ−ブチル−１，１，３，３−テトラメチルジシロキサン−１−イル基、３，３，３−トリイソプロピル−１，１−ジメチルジシロキサン−１−イル基、１，１−ジフェニル−３，３，３−トリメチルジシロキサン−１−イル基、３−メチル−１，１，３，３−テトラフェニルジシロキサン−１−イル基、１−シクロヘキシル−１，３，３，３−テトラメチルジシロキサン−１−イル基、ヘプタメチルトリシロキサン−１−イル基、ノナメチルテトラシロキサン−１−イル基、ウンデカメチルペンタシロキサン−１−イル基、トリデカメチルヘキサシロキサン−１−イル基、ペンタデカメチルヘプタシロキサン−１−イル基、ヘプタデカメチルオクタシロキサン−１−イル基、ノナデカメチルノナシロキサン−１−イル基、ヘンイコサメチルデカシロキサン−１−イル基等の直鎖状オルガノシロキサニル基；１−トリメチルシロキシ−１，３，３，３−テトラメチルジシロキサン−１−イル基、１−トリメチルシロキシ−１，３，３，５，５，５−ヘプタメチルトリシロキサン−１−イル基、１−ペンタメチルジシロキサニルオキシ−１，３，３，５，５，５−ヘキサメチルトリシロキサン−１−イル基、１−トリメチルシロキシ−１，３，３，５，５，７，７，７−オクタメチルテトラシロキサン−１−イル基、１，１−ビス（トリメチルシロキシ）−３，３，３−トリメチルジシロキサン−１−イル基等の分岐鎖状オルガノシロキサニル基；１，３，３，５，５，７，７−ヘプタメチルシクロテトラシロキサン−１−イル基、１，３，５，７−テトラメチル−３，５，７−テトラビニルシクロテトラシロキサン−１−イル基等の環状オルガノシロキサニル基等が挙げられる。これらのなかでも、特にペンタメチルジシロキサン−１−イル基、ヘプタメチルトリシロキサン−１−イル基、ノナメチルテトラシロキサン−１−イル基、ウンデカメチルペンタシロキサン−１−イル基、１−トリメチルシロキシ−１，３，３，３−テトラメチルジシロキサン−１−イル基、１，３，３，５，５，７，７−ヘプタメチルシクロテトラシロキサン−１−イル基が好ましい。

In the general formula (2), Sx has 2 to 10 silicon atoms, particularly 2 to 5 silicon atoms, and the silicon atom is a monovalent hydrocarbon group having 1 to 20 carbon atoms, particularly 1 to 6 carbon atoms. It represents a linear, branched, or cyclic organosiloxanyl group that may be substituted with an alkyl group. In Sx, a silicon atom is bonded to A and does not contain a reactive substituent such as a silicon-hydrogen bond or a silicon-alkoxy bond. Specific examples of Sx include pentamethyldisiloxane-1-yl group, 3,3,3-triethyl-1,1-dimethyldisiloxane-1-yl group, pentaethyldisiloxane-1-yl group, 3- Vinyl-1,1,3,3-tetramethyldisiloxane-1-yl group, 3-tert-butyl-1,1,3,3-tetramethyldisiloxane-1-yl group, 3,3,3- Triisopropyl-1,1-dimethyldisiloxane-1-yl group, 1,1-diphenyl-3,3,3-trimethyldisiloxane-1-yl group, 3-methyl-1,1,3,3-tetra Phenyldisiloxane-1-yl group, 1-cyclohexyl-1,3,3,3-tetramethyldisiloxane-1-yl group, heptamethyltrisiloxane-1-yl group, nonamethyltetrasiloxane-1-yl group Undecamethylpentasiloxane-1-yl group, tridecamethylhexasiloxane-1-yl group, pentadecamethylheptasiloxane-1-yl group, heptadecamethyloctasiloxane-1-yl group, nonadecamethylnonasiloxane- Linear organosiloxanyl groups such as 1-yl group, henicosamethyldecasiloxane-1-yl group; 1-trimethylsiloxy-1,3,3,3-tetramethyldisiloxane-1-yl group, 1-trimethylsiloxy-1,3,3,5,5,5-heptamethyltrisiloxane-1-yl group, 1-pentamethyldisiloxanyloxy-1,3,3,5,5,5-hexa Methyltrisiloxane-1-yl group, 1-trimethylsiloxy-1,3,3,5,5,7,7,7-octamethyltetrasiloxane-1-yl group, 1,3-bis (trimethylsiloxy) -3,3,3-trimethyldisiloxane-1-yl group and other branched organosiloxanyl groups; 1,3,3,5,5,7,7-heptamethyl Examples include cyclic organosiloxanyl groups such as cyclotetrasiloxane-1-yl group and 1,3,5,7-tetramethyl-3,5,7-tetravinylcyclotetrasiloxane-1-yl group. Among these, in particular, pentamethyldisiloxane-1-yl group, heptamethyltrisiloxane-1-yl group, nonamethyltetrasiloxane-1-yl group, undecamethylpentasiloxane-1-yl group, 1-trimethyl Siloxy-1,3,3,3-tetramethyldisiloxane-1-yl group and 1,3,3,5,5,7,7-heptamethylcyclotetrasiloxane-1-yl group are preferred.

In the general formula (2), A is a divalent hydrocarbon group having 1 to 20 carbon atoms, particularly 1 to 12 carbon atoms, or one or more discontinuous —O—, —S—, —NR— (R Is the same as above.) Or represents a divalent hydrocarbon group having 2 to 20 carbon atoms, particularly 2 to 12 carbon atoms, which may contain a combination thereof. Examples of the group represented by A include a methylene group, 1,2-ethanediyl group, 1,1-ethanediyl group, 1,2-ethenediyl group, 1,1-ethenediyl group, 1,3-propanediyl group, 1,2-propanediyl group, 2-methyl-1,3-propanediyl group, 1,3-butanediyl group, 1,4-butanediyl group, 1,5-pentanediyl group, 1,6-hexanediyl group, 1 , 4-cyclohexanediyl group, 1,7-heptanediyl group, 1,8-octanediyl group, 1,9-nonanediyl group, 1,10-decanediyl group, 1,11-undecanediyl group, 1,12-dodecanediyl group 1,13-tridecanediyl group, 1,14-tetradecanediyl group, 1,15-pentadecanediyl group, 1,16-hexadecanediyl group, 1,17-heptadecane Linear, branched or cyclic aliphatic divalent hydrocarbon groups such as yl, 1,18-octadecandiyl, 1,19-nonadecandiyl, 1,20-icosanediyl; 1,3-benzenediyl Group, 1,4-benzenediyl group, 2-methyl-1,4-benzenediyl group, 3-methyl-1,4-benzenediyl group, 2,5-dimethyl-1,4-benzenediyl group, 1, Aromatic divalent hydrocarbon groups such as 8-naphthalenediyl group, 2,7-naphthalenediyl group, 4-ethylbenzene-1,2'-diyl group, 4-propylbenzene-1,3'-diyl group; Oxa-1,3-propanediyl group, 3-oxa-1,5-pentanediyl group, 3-oxa-2-methyl-1,5-pentanediyl group, 3-oxa-1,6-hexanediyl group, 3- Oxa-2-methyl -1,5-hexanediyl group, 3-oxa-2-methyl-1,6-hexanediyl group, 3,6-dioxa-1,8-octanediyl group, 3,7-dioxa-1,9-nonanediyl Group, 3-methyl-3-aza-1,5-pentanediyl group, 3-methyl-3-aza-1,6-hexanediyl group, 3-phenyl-3-aza-1,6-hexanediyl group, 3 Divalent containing a hetero atom such as -methyl-3-aza-7-oxa-1,9-nonanediyl group, 3-thia-1,5-pentanediyl group, 3,6-dithia-1,8-octanediyl group A hydrocarbon group etc. are mentioned. Among these, in particular, a methylene group, 1,2-ethanediyl group, 1,3-propanediyl group, 2-methyl-1,3-propanediyl group, 1,4-butanediyl group, 1,5-pentanediyl group, A 1,11-undecandiyl group, a 1,3-benzenediyl group, and a 1,4-benzenediyl group are preferred.
A is bonded to Sx and A ′, but when A is an asymmetric substituent such as a 1,2-propanediyl group, the bonding direction to Sx and A ′ is arbitrary.

In the general formula (2), A ¹ is —O—, —S—, —NR—, —O—C (O) —, —C (O) —O—, —NR ¹ —C (O) —. , -C (O) -NR < ¹ >-and a single bond. R is a monovalent hydrocarbon group having 1 to 20 carbon atoms as described above, and R ¹ is a monovalent hydrocarbon group that may be substituted with a fluorine atom having 1 to 20 carbon atoms as described above. is there.

In the general formula (2), Sx, A, and A ¹ can be arbitrarily combined. Illustrating the case where Sx is a pentamethyldisiloxane-1-yl group, specific examples of the siloxane-containing group represented by the general formula (2) include pentamethyldisiloxane-1-ylmethyl group, 2- (penta Methyldisiloxane-1-yl) ethyl group, 1- (pentamethyldisiloxane-1-yl) ethyl group, 2- (pentamethyldisiloxane-1-yl) ethenyl group, 3- (pentamethyldisiloxane-1) -Yl) propyl group, 2-methyl-3- (pentamethyldisiloxane-1-yl) propyl group, 4- (pentamethyldisiloxane-1-yl) butyl group, 5- (pentamethyldisiloxane-1- Yl) pentyl group, 6- (pentamethyldisiloxane-1-yl) hexyl group, 7- (pentamethyldisiloxane-1-yl) heptyl group, 8 (Pentamethyldisiloxane-1-yl) octyl group, 9- (pentamethyldisiloxane-1-yl) nonyl group, 10- (pentamethyldisiloxane-1-yl) decyl group, 11- (pentamethyldisiloxane) -1-yl) undecyl group, 12- (pentamethyldisiloxane-1-yl) dodecyl group, 14- (pentamethyldisiloxane-1-yl) tetradecyl group, 16- (pentamethyldisiloxane-1-yl) Hexadecyl group, 18- (pentamethyldisiloxane-1-yl) octadecyl group, 20- (pentamethyldisiloxane-1-yl) icosyl group, 4- (pentamethyldisiloxane-1-yl) phenyl group, 3- (Pentamethyldisiloxane-1-yl) phenyl group, 4- [2- (pentamethyldisiloxane-1-yl) ester Ru] phenyl group, 4- [3- (pentamethyldisiloxane-1-yl) propyl] phenyl group, 4- [2- (pentamethyldisiloxane-1-yl) propyl] phenyl group, 2- {2- (Pentamethyldisiloxane-1-yl) ethoxy} ethyl group, 3- {2- (pentamethyldisiloxane-1-yl) ethoxy} propyl group, 2- {3- (pentamethyldisiloxane-1-yl) Propoxy} ethyl group, 2- {3- (pentamethyldisiloxane-1-yl) propoxy} propyl group, 2- {2- {3- (pentamethyldisiloxane-1-yl) propoxy} ethoxy} ethyl group, 2- {2- {3- (pentamethyldisiloxane-1-yl) propoxy} propoxy} ethyl group, 2- {2- {3- (pentamethyldisiloxane-1-yl) propyl Substituted hydrocarbon groups such as Roxy} propoxy} propyl group; (pentamethyldisiloxane-1-yl) methoxy group, 2- (pentamethyldisiloxane-1-yl) ethoxy group, 3- (pentamethyldisiloxane-1) -Yl) propoxy group, 2-methyl-3- (pentamethyldisiloxane-1-yl) propoxy group, 3- (pentamethyldisiloxane-1-yl) butoxy group, 4- (pentamethyldisiloxane-1- Yl) butoxy group, 4- (pentamethyldisiloxane-1-yl) phenoxy group, 2- {2- (pentamethyldisiloxane-1-yl) ethoxy} ethoxy group, 3- {2- (pentamethyldisiloxane) -1-yl) ethoxy} propoxy group, 2- {3- (pentamethyldisiloxane-1-yl) propoxy} ethoxy group, 2- {3 (Pentamethyldisiloxane-1-yl) propoxy} propoxy group, 2- {2- {3- (pentamethyldisiloxane-1-yl) propoxy} ethoxy} ethoxy group, 2- {2- {3- (penta Methyldisiloxane-1-yl) propoxy} propoxy} ethoxy group, 2- {2- {3- (pentamethyldisiloxane-1-yl) propoxy} propoxy} propoxy group, 2- [N-methyl-N- { 3- (pentamethyldisiloxane-1-yl) propyl} amino] ethoxy group, 2- [N-methyl-N- {3- (pentamethyldisiloxane-1-yl) propyl} amino] ethoxy group, 1- Methyl-2- [N-methyl-N- {3- (pentamethyldisiloxane-1-yl) propyl} amino] ethoxy group, 2- {2- (pentamethyldishiro) (San-1-yl) ethylsulfanyl} ethoxy group and other substituted organoxy groups; (pentamethyldisiloxane-1-yl) methylsulfanyl group, 2- (pentamethyldisiloxane-1-yl) ethylsulfanyl group, 3- ( Pentamethyldisiloxane-1-yl) propylsulfanyl group, 4- (pentamethyldisiloxane-1-yl) phenylsulfanyl group, 2- {2- (pentamethyldisiloxane-1-yl) ethylsulfanyl} ethylsulfanyl group 3- {3- (pentamethyldisiloxane-1-yl) propylsulfanyl} propylsulfanyl group, 1-methyl-2- {2- (pentamethyldisiloxane-1-yl) ethoxy} ethylsulfanyl group, 3- {2- (pentamethyldisiloxane-1-yl) ethoxy} propi Rusulfanyl group, 2- {3- (pentamethyldisiloxane-1-yl) propoxy} ethylsulfanyl group, 2- {3- (pentamethyldisiloxane-1-yl) propoxy} propylsulfanyl group, 2- {2 -Substituted organosulfanyl groups such as {3- (pentamethyldisiloxane-1-yl) propoxy} ethoxy} ethylsulfanyl group; N- (pentamethyldisiloxane-1-yl) methyl-N-methylamino group, N- [2- (pentamethyldisiloxane-1-yl) ethyl] -N-methylamino group, N- [2- (pentamethyldisiloxane-1-yl) ethyl] -N-ethylamino group, N- [2 -(Pentamethyldisiloxane-1-yl) ethyl] -N-propylamino group, N-{(pentamethyldisiloxane-1-yl) pro L} -N-methylamino group, N-{(pentamethyldisiloxane-1-yl) propyl} -N-ethylamino group, N- [3- (pentamethyldisiloxane-1-yl) propyl] -N -Propylamino group, N- [3- (pentamethyldisiloxane-1-yl) propyl] -N-isopropylamino group, N- [3- (pentamethyldisiloxane-1-yl) propyl] -N-allylamino Group, N- [3- (pentamethyldisiloxane-1-yl) propyl] -N-butylamino group, N- [3- (pentamethyldisiloxane-1-yl) propyl] -N-hexylamino group, N- [3- (pentamethyldisiloxane-1-yl) propyl] -N-octylamino group, N- [3- (pentamethyldisiloxane-1-yl) propyl] -N-decyl Mino group, N- [3- (pentamethyldisiloxane-1-yl) propyl] -N-phenylamino group, N- [3- (pentamethyldisiloxane-1-yl) propyl] -N-naphthylamino group N- [2-Methyl-3- (pentamethyldisiloxane-1-yl) propyl] -N-methylamino group, N- [2-methyl-3- (pentamethyldisiloxane-1-yl) propyl] -N-ethylamino group,
N- [2-methyl-3- (pentamethyldisiloxane-1-yl) propyl] -N-propylamino group, N- [2-methyl-3- (pentamethyldisiloxane-1-yl) propyl]- N-phenylamino group, N- [2-methyl-3- (pentamethyldisiloxane-1-yl) propyl] -N-naphthylamino group, N- [4- (pentamethyldisiloxane-1-yl) butyl ] -N-methylamino group, N- [4- (pentamethyldisiloxane-1-yl) phenyl] -N-methylamino group, N- [4- [2- (pentamethyldisiloxane-1-yl)] Ethyl] phenyl] -N-methylamino group, N- [4- [2- (pentamethyldisiloxane-1-yl) propyl] phenyl] -N-methylamino group, 2- {2- (pentamethyldisiloxane) 1-yl) ethoxy} ethyl-N-methylamino group, 3- {2- (pentamethyldisiloxane-1-yl) ethoxy} propyl-N-methylamino group, 2- {3- (pentamethyldisiloxane- 1-yl) propoxy} ethyl-N-methylamino group, 2- {3- (pentamethyldisiloxane-1-yl) propoxy} propyl-N-methylamino group, 2- {2- {3- (pentamethyl) Disiloxane-1-yl) propoxy} ethoxy} ethyl-N-methylamino group, 2- {2- {3- (pentamethyldisiloxane-1-yl) propoxy} propoxy} ethyl-N-methylamino group, 2 -{2- {3- (pentamethyldisiloxane-1-yl) propoxy} propoxy} propyl-N-methylamino group, N, N-bis [3- (pentamethyl Substituted diorganoamino groups such as (siloxane-1-yl) propyl] amino group, (pentamethyldisiloxane-1-yl) methoxycarbonyl group, 2- (pentamethyldisiloxane-1-yl) ethoxycarbonyl group, 3- (Pentamethyldisiloxane-1-yl) propoxycarbonyl group, 2-methyl-3- (pentamethyldisiloxane-1-yl) propoxycarbonyl group, 3- (pentamethyldisiloxane-1-yl) butoxycarbonyl group, 4- (pentamethyldisiloxane-1-yl) phenoxycarbonyl group, 2- {2- (pentamethyldisiloxane-1-yl) ethoxy} ethoxycarbonyl group, 3- {2- (pentamethyldisiloxane-1- Yl) ethoxy} propoxycarbonyl group, 2- {3- (pentamethyldisiloxane- 1-yl) propoxy} ethoxycarbonyl group, 2- {3- (pentamethyldisiloxane-1-yl) propoxy} propoxycarbonyl group, 2- {2- {3- (pentamethyldisiloxane-1-yl) propoxy } Ethoxy} ethoxycarbonyl group, 2- {2- {3- (pentamethyldisiloxane-1-yl) propoxy} propoxy} ethoxycarbonyl group, 2- {2- {3- (pentamethyldisiloxane-1-yl) ) Propoxy} propoxy} propoxycarbonyl group, 2- [N-methyl-N- {3- (pentamethyldisiloxane-1-yl) propyl} amino] ethoxycarbonyl group, 2- [N-methyl-N- {3 -(Pentamethyldisiloxane-1-yl) propyl} amino] ethoxycarbonyl group, 1-methyl-2- [N-methyl] Substituted organoxy groups such as -N- {3- (pentamethyldisiloxane-1-yl) propyl} amino] ethoxycarbonyl group, 2- {2- (pentamethyldisiloxane-1-yl) ethylsulfanyl} ethoxycarbonyl group Carbonyl group; (pentamethyldisiloxane-1-yl) acetoxy group, 3- (pentamethyldisiloxane-1-yl) propionyloxy group, 2-methyl-3- (pentamethyldisiloxane-1-yl) propionyloxy Group, 5- (pentamethyldisiloxane-1-yl) pentanoyloxy group, 6- (pentamethyldisiloxane-1-yl) hexanoyloxy group,
11- (pentamethyldisiloxane-1-yl) undecanoyloxy group, 4- (pentamethyldisiloxane-1-yl) benzoyloxy group, {2- (pentamethyldisiloxane-1-yl) ethoxy} acetyl Group, 3- {2- (pentamethyldisiloxane-1-yl) ethoxy} propionyloxy group, {3- (pentamethyldisiloxane-1-yl) propoxy} acetoxy group, 3- {3- (pentamethyldioxy) Siloxane-1-yl) propoxy} propionyloxy group, {2- {3- (pentamethyldisiloxane-1-yl) propoxy} ethoxy} acetoxy group, {2- {3- (pentamethyldisiloxane-1-yl) ) Propoxy} propoxy} acetoxy group, 3- [N-methyl-N- {3- (pentamethyldisiloxane-1-yl) Substituted acyloxy groups such as propyl} amino] propionyloxy group, 3- [N-methyl-N- {3- (pentamethyldisiloxane-1-yl) propyl} amino] propionyloxy group; N- (pentamethyldisiloxane -1-yl) methyl-N-methylcarbamoyl group, N- [2- (pentamethyldisiloxane-1-yl) ethyl] -N-methylcarbamoyl group, N- [2- (pentamethyldisiloxane-1- Yl) ethyl] -N-ethylcarbamoyl group, N- [2- (pentamethyldisiloxane-1-yl) ethyl] -N-propylcarbamoyl group, N-{(pentamethyldisiloxane-1-yl) propyl} -N-methylcarbamoyl group, N-{(pentamethyldisiloxane-1-yl) propyl} -N-ethylcarbamoyl group, N- 3- (pentamethyldisiloxane-1-yl) propyl] -N-propylcarbamoyl group, N- [3- (pentamethyldisiloxane-1-yl) propyl] -N-isopropylcarbamoyl group, N- [3- (Pentamethyldisiloxane-1-yl) propyl] -N-allylcarbamoyl group, N- [3- (pentamethyldisiloxane-1-yl) propyl] -N-butylcarbamoyl group, N- [3- (penta Methyldisiloxane-1-yl) propyl] -N-hexylcarbamoyl group, N- [3- (pentamethyldisiloxane-1-yl) propyl] -N-octylcarbamoyl group, N- [3- (pentamethyldiethyl) Siloxane-1-yl) propyl] -N-decylcarbamoyl group, N- [3- (pentamethyldisiloxane-1-yl) propyl] -N-phenylcarbamoyl group, N- [3- (pentamethyldisiloxane-1-yl) propyl] -N-naphthylcarbamoyl group, N- [2-methyl-3- (pentamethyldisiloxane-1-yl) Propyl] -N-methylcarbamoyl group, N- [2-methyl-3- (pentamethyldisiloxane-1-yl) propyl] -N-ethylcarbamoyl group, N- [2-methyl-3- (pentamethyldi) Siloxane-1-yl) propyl] -N-propylcarbamoyl group, N- [2-methyl-3- (pentamethyldisiloxane-1-yl) propyl] -N-phenylcarbamoyl group, N- [2-methyl- 3- (pentamethyldisiloxane-1-yl) propyl] -N-naphthylcarbamoyl group, N- [4- (pentamethyldisiloxane-1-yl) buty ] -N-methylcarbamoyl group, N- [4- (pentamethyldisiloxane-1-yl) phenyl] -N-methylcarbamoyl group, N- [4- [2- (pentamethyldisiloxane-1-yl) Ethyl] phenyl] -N-methylcarbamoyl group, N- [4- [2- (pentamethyldisiloxane-1-yl) propyl] phenyl] -N-methylcarbamoyl group, 2- {2- (pentamethyldisiloxane) -1-yl) ethoxy} ethyl-N-methylcarbamoyl group, 3- {2- (pentamethyldisiloxane-1-yl) ethoxy} propyl-N-methylcarbamoyl group, 2- {3- (pentamethyldisiloxane) -1-yl) propoxy} ethyl-N-methylcarbamoyl group, 2- {3- (pentamethyldisiloxane-1-yl) propoxy} propi -N-methylcarbamoyl group, 2- {2- {3- (pentamethyldisiloxane-1-yl) propoxy} ethoxy} ethyl-N-methylcarbamoyl group, 2- {2- {3- (pentamethyldisiloxane) -1-yl) propoxy} propoxy} ethyl-N-methylcarbamoyl group, 2- {2- {3- (pentamethyldisiloxane-1-yl) propoxy} propoxy} propyl-N-methylcarbamoyl group, N, N -Substituted carbamoyl groups such as bis [3- (pentamethyldisiloxane-1-yl) propyl] carbamoyl group; N-methyl- (pentamethyldisiloxane-1-yl) acetamide group, N-methyl-3- (penta Methyldisiloxane-1-yl) propionamide group, N-methyl-5- (pentamethyldisiloxane-1-yl) penta N-methyl-6- (pentamethyldisiloxane-1-yl) hexanamide group, N-methyl-11- (pentamethyldisiloxane-1-yl) undecanamide group, N-methyl-4- ( Pentamethyldisiloxane-1-yl) benzamide group, N-methyl- {2- (pentamethyldisiloxane-1-yl) ethoxy} acetamide group, N-methyl-3- {2- (pentamethyldisiloxane-1) -Yl) ethoxy} propionamide group, N-methyl- {3- (pentamethyldisiloxane-1-yl) propoxy} acetamide group, N-methyl-3- {3- (pentamethyldisiloxane-1-yl) Propoxy} propionamide group, N-methyl- {2- {3- (pentamethyldisiloxane-1-yl) propoxy} ethoxy} acetami Group, N-methyl- {2- {3- (pentamethyldisiloxane-1-yl) propoxy} propoxy} acetamide group, N-methyl-3- [N-methyl-N- {3- (pentamethyldisiloxane) -1-yl) propyl} amino] propionamide group, substituted amides such as N-methyl-3- [N-methyl-N- {3- (pentamethyldisiloxane-1-yl) propyl} amino] propionamide group Groups and the like.

As the group represented by the formula (2), a preferable example of Sx, a preferable example of A, and a group obtained by combining A ¹ are preferable. In particular, 3- (pentamethyldisiloxane-1-yl) propyl group, 3- (heptamethyltrisiloxane-1-yl) propyl group, 3- (nonamethyltetrasiloxane-1-yl) propyl group, 3- (un Decamethylpentasiloxane-1-yl) propyl group, 3- (1-trimethylsiloxy-1,3,3,3-tetramethyldisiloxane-1-yl) propyl group, 3- (1,3,3,5) , 5,7,7-heptamethylcyclotetrasiloxane-1-yl) propyl group, 3- (pentamethyldisiloxane-1-yl) propoxy group, 3- (heptamethyltrisiloxane-1-yl) propoxy group, 3- (nonamethyltetrasiloxane-1-yl) propoxy group, 3- (undecamethylpentasiloxane-1-yl) propoxy group, 3- (1-trime Lucyloxy-1,3,3,3-tetramethyldisiloxane-1-yl) propoxy group, 3- (1,3,3,5,5,7,7-heptamethylcyclotetrasiloxane-1-yl) propoxy A group, N- [3- (pentamethyldisiloxane-1-yl) propyl] -N-propylamino group, N- [3- (heptamethyltrisiloxane-1-yl) propyl] -N-propylamino group, N- [3- (nonamethyltetrasiloxane-1-yl) propyl] -N-propylamino group, N- [3- (undecamethylpentasiloxane-1-yl) propyl] -N-propylamino group, N -[3- (1-trimethylsiloxy-1,3,3,3-tetramethyldisiloxane-1-yl) propyl] -N-propylamino group, N- [3- (1,3,3,5, 5, , 7-Heptamethylcyclotetrasiloxane-1-yl) propyl] -N-propylamino group, N, N-bis [3- (pentamethyldisiloxane-1-yl) propyl] amino group, N, N-bis [3- (Heptamethyltrisiloxane-1-yl) propyl] amino group, N, N-bis [3- (nonamethyltetrasiloxane-1-yl) propyl] amino group, N, N-bis [3- ( Undecamethylpentasiloxane-1-yl) propyl] amino group, N, N-bis [3- (1-trimethylsiloxy-1,3,3,3-tetramethyldisiloxane-1-yl) propyl] amino group N, N-bis [3- (1,3,3,5,5,7,7-heptamethylcyclotetrasiloxane-1-yl) propyl] amino group, 3- (pentamethyldisiloxane-1- Yl) propoxycarbonyl group, 3- (heptamethyltrisiloxane-1-yl) propoxycarbonyl group, 3- (nonamethyltetrasiloxane-1-yl) propoxycarbonyl group, 3- (undecamethylpentasiloxane-1-yl) ) Propoxycarbonyl group, 3- (1-trimethylsiloxy-1,3,3,3-tetramethyldisiloxane-1-yl) propoxycarbonyl group, 3- (1,3,3,5,5,7,7) -Heptamethylcyclotetrasiloxane-1-yl) propoxycarbonyl group, N- [3- (pentamethyldisiloxane-1-yl) propyl] -N-propylcarbamoyl group, N- [3- (heptamethyltrisiloxane- 1-yl) propyl] -N-propylcarbamoyl group, N- [3- (nonamethyltetrasiloxane- -Yl) propyl] -N-propylcarbamoyl group, N- [3- (undecamethylpentasiloxane-1-yl) propyl] -N-propylcarbamoyl group, N- [3- (1-trimethylsiloxy-1, 3,3,3-tetramethyldisiloxane-1-yl) propyl] -N-propylcarbamoyl group, N- [3- (1,3,3,5,5,7,7-heptamethylcyclotetrasiloxane- 1-yl) propyl] -N-propylcarbamoyl group, N, N-bis [3- (pentamethyldisiloxane-1-yl) propyl] carbamoyl group, N, N-bis [3- (heptamethyltrisiloxane- 1-yl) propyl] carbamoyl group, N, N-bis [3- (nonamethyltetrasiloxane-1-yl) propyl] carbamoyl group, N, N-bis [3- Undecamethylpentasiloxane-1-yl) propyl] carbamoyl group, N, N-bis [3- (1-trimethylsiloxy-1,3,3,3-tetramethyldisiloxane-1-yl) propyl] carbamoyl group N, N-bis [3- (1,3,3,5,5,7,7-heptamethylcyclotetrasiloxane-1-yl) propyl] carbamoyl group is more preferable.

In the general formula (1), R ² is a hydrogen atom, a monovalent hydrocarbon group which may be substituted with a fluorine atom having 1 to 20 carbon atoms, particularly 1 to 12 carbon atoms, and represented by the above formula (2). A siloxane-containing group, an organoxycarbonyl group represented by —C (O) —OR, a diorganocarbamoyl group represented by —C (O) —NR ₂ , a cyano group, and the following formula (3): A group selected from among the above heterocyclic substituents. R is a monovalent hydrocarbon group having 1 to 20 carbon atoms as described above. Specific examples of the monovalent hydrocarbon group for R ² are the same as those described for R ¹ .

Examples of the organoxycarbonyl group represented by —C (O) —OR include methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group, tert-butoxycarbonyl group, cyclohexyloxycarbonyl group, allyloxycarbonyl Group, butenyloxycarbonyl group, phenoxycarbonyl group, tolyloxycarbonyl group, benzyloxycarbonyl group and the like.
Examples of the diorganocarbamoyl group represented by —C (O) —NR ₂ include a dimethylcarbamoyl group, a diethylcarbamoyl group, a methylpropylcarbamoyl group, a diisopropylcarbamoyl group, a methylallylcarbamoyl group, a diallylcarbamoyl group, and a dibutylcarbamoyl group. Cyclohexylmethylcarbamoyl group, octylmethylcarbamoyl group, decylmethylcarbamoyl group, dodecylmethylcarbamoyl group, tetradecylmethylcarbamoyl group, hexadecylmethylcarbamoyl group, octadecylmethylcarbamoyl group and the like.

In the above formula (3), X ¹ represents —O—, —S— or —NR—, and R represents a monovalent hydrocarbon group having 1 to 20 carbon atoms as described above. R ⁷ may be the same or different and is a monovalent hydrocarbon group optionally substituted by a halogen atom having 1 to 20 carbon atoms, particularly 1 to 6 carbon atoms, a siloxane-containing group represented by the above formula (2) , A group independently selected from a halogen atom and a hydrogen atom. Specific examples of R ⁷ include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, in addition to the groups listed as specific examples of formula (2). , Pentyl, cyclopentyl, isopentyl, 2-pentyl, 3-pentyl, tert-pentyl, hexyl, cyclohexyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, icosyl Linear, branched and cyclic saturated hydrocarbon groups such as vinyl groups; unsaturated hydrocarbon groups such as vinyl, allyl, propynyl, butenyl, pentenyl, hexenyl, undecenyl and octadecenyl; phenyl groups Naphthyl group, benzyl group, phenethyl group, phenylpropyl group, 2-methylphenyl group, 3-methylphenyl group, Nyl group, 4-methylphenyl group, 2,4-dimethylphenyl group, 3,5-dimethylphenyl group, aromatic hydrocarbon group such as 3,5-di-tert-butylphenyl group; trifluoropropyl group, 2 , 2,2-trifluoroethyl group, 3,3,3-trifluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, 3,3,4,4,5,5,6, 6,6-nonafluorohexyl group, 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl group, 3,3,4,4,5 5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl group, pentafluorophenyl group, trifluoromethylphenyl group, chloromethyl group, 3-chloropropyl Group, 4-chlorophenyl group, 3-chlorophenyl group, Monovalent hydrocarbon groups substituted by halogen atoms such as bromomethyl group, 3-bromopropyl group, 3-iodopropyl group, 3-iodobutyl group; fluorine atom, chlorine atom, bromine atom, iodine atom, hydrogen atom, etc. It is done.

In the above general formula (1), R ³ , R ⁴ , R ⁵ and R ⁶ may be the same or different, and are substituted with a hydrogen atom, a halogen atom having 1 to 20 carbon atoms, particularly a halogen atom having 1 to 12 carbon atoms. A monovalent hydrocarbon group, a diorganoamino group represented by the following formula (4), an organoxy group represented by the following formula (5), an organosulfanyl group represented by the following formula (6), and the above formula It is a substituent selected independently from the siloxane-containing group of (2). Specific examples of R ^{3 to} R ⁶ monovalent hydrocarbon groups include, in addition to the groups described for R ¹ , a chloromethyl group, a chloropropyl group, a chlorohexyl group, a chlorophenyl group, a bromopropyl group, a bromophenyl group, And monovalent hydrocarbon groups substituted with a halogen atom such as a dibromophenyl group, an iodopropyl group, and an iodophenyl group.

In the above formula (4), R ⁸ may be the same or different and is a monovalent hydrocarbon group having 1 to 20 carbon atoms, particularly 1 to 12 carbon atoms, a siloxane-containing group represented by the above formula (2), or It represents a monovalent hydrocarbon group having 2 to 20 carbon atoms, particularly 2 to 12 carbon atoms, which may contain one or more discontinuous —O—, —S—, —NR—, or a combination thereof. However, hetero atoms of oxygen atom, sulfur atom and nitrogen atom are not adjacent to each other, and therefore R ⁸ has a carbon atom bonded to a nitrogen atom.

In the above formula (5), R ⁹ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, particularly 1 to 12 carbon atoms, a siloxane-containing group represented by the above formula (2), or one or more discontinuous groups. A monovalent hydrocarbon group having 2 to 20 carbon atoms, particularly 2 to 12 carbon atoms, which may contain -O-, -S-, -NR- or a combination thereof. However, hetero atoms of oxygen atom, sulfur atom, and nitrogen atom are not adjacent to each other, and therefore R ⁹ has a carbon atom bonded to an oxygen atom.

In the formula (6), R ¹⁰ represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, particularly 1 to 12 carbon atoms, a siloxane-containing group represented by the above formula (2), or one or more discontinuous —O—. , -S-, -NR- or a combination thereof, which represents a monovalent hydrocarbon group having 2 to 20 carbon atoms, particularly 2 to 12 carbon atoms. However, hetero atoms of oxygen atom, sulfur atom, and nitrogen atom are not adjacent to each other, and therefore R ¹⁰ has a carbon atom bonded to a sulfur atom.

Specific examples of R ⁸ , R ⁹ and R ¹⁰ include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, cyclopentyl group and isopentyl group. , 2-pentyl group, 3-pentyl group, tert-pentyl group, hexyl group, cyclohexyl group, octyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, icosyl group, etc. A cyclic saturated hydrocarbon group; an unsaturated hydrocarbon group such as a vinyl group, an allyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, an undecenyl group, and an octadecenyl group; a phenyl group, a naphthyl group, a benzyl group, and a phenethyl group , Phenylpropyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl Group, aromatic hydrocarbon group such as 2,4-dimethylphenyl group, 3,5-dimethylphenyl group, 3,5-di-tert-butylphenyl group; methoxymethyl group, 2-methoxyethyl group, 3-methoxy Propyl group, 2-ethoxyethyl group, 3-ethoxypropyl group, dimethylaminomethyl group, 2- (dimethylamino) ethyl group, 3- (dimethylamino) propyl group, 2- (diethylamino) ethyl group, 3- (diethylamino) ) Propyl group, 3- (diisopropylamino) propyl group, 2- (methylsulfanyl) ethyl group, 3- (methylsulfanyl) propyl group, 2- (2-methoxyethoxy) ethyl group, 2- (2-ethoxyethoxy) Ethyl group, 2- (2-butoxyethoxy) ethyl group, 3- (2-methoxyethoxy) propyl group, 3- (2- Toxiethoxy) propyl group, 2- {2- (2-methoxyethoxy) ethoxy} ethyl group, 2- {2- (2-ethoxyethoxy) ethoxy} ethyl group, 3- {2- (2-methoxyethoxy) ethoxy } Propyl group, 3- {2- (2-ethoxyethoxy) ethoxy} propyl group, 2-[{2- (dimethylamino) ethyl} (methyl) amino] ethyl group, 2-[{2- (diethylamino) ethyl } (Methyl) amino] ethyl group, 2-[{2- (dimethylamino) ethyl} (ethyl) amino] ethyl group, 2-[{2- (diethylamino) ethyl} (ethyl) amino] ethyl group, 3- [{2- (dimethylamino) ethyl} (methyl) amino] propyl group, 3-[{2- (diethylamino) ethyl} (methyl) amino] propyl group, 2- {2- (methyl Sulfanyl) ethylsulfanyl} ethyl group, 2- {2- (ethylsulfanyl) ethylsulfanyl} ethyl group, 2- [2- (dimethylamino) ethoxy] ethyl group, 2- [2- (diethylamino) ethoxy] ethyl group, Monovalent hydrocarbon groups containing an oxygen atom, a nitrogen atom, a sulfur atom, such as a 3- [2- (dimethylamino) ethoxy] propyl group, a 3- [2- (diethylamino) ethoxy] propyl group, and the formulas exemplified above Examples include (2) siloxane-containing groups. However, among the groups listed as examples of formula (2), substituted organoxy groups, substituted diorganoamino groups, substituted organosulfanyl groups, substituted acyloxy groups, and substituted amide groups are defined as R ⁸ , R ⁹ , and R ^10. Not included.

In the general formula (1), the substituents R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁵ and R ⁶ are bonded to each other, and the number of constituent carbon atoms including two carbon atoms bonded to each other is 5 to 8 The ring structure may be formed. In this case, the structure of the general formula (1) specifically forms a condensed ring structure represented by the following formulas (7a) to (7f). However, when forming a ring structure, R ^3a , R ^4a , R ^5a , and R ^6a in formula (7) below must exclude one or two hydrogen atoms from R ³ , R ⁴ , R ⁵ , and R ⁶ , respectively. Is a divalent or trivalent group obtained.

In the fluorescent compound of the present invention represented by the general formula (1), at least one of the substituents R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ is represented by the formula (2). It is a siloxane-containing group represented or a group containing it as a substituent. Therefore, the compound represented by the general formula (1) includes one or more groups represented by the general formula (2). Further, the fluorescent compound represented by the general formula (1) does not include a heteroatom-hydrogen bond serving as a hydrogen bond donor, such as a nitrogen-hydrogen bond, an oxygen-hydrogen bond, or the like.

  The fluorescent compound represented by the general formula (1) of the present invention contains a siloxane-containing group, but the structure of the siloxane portion is clearly defined and is not a siloxane mixture having a molecular weight distribution. Therefore, the compound represented by the general formula (1) is not a mixture but a single compound. In preparing the composition, since the molar concentration of the fluorescent chromophore is an important factor in determining the fluorescent properties of the composition, it is desirable to be a single compound to accurately determine the molar concentration.

  The fluorescent compound of the present invention is preferably purified to the highest possible purity in order to maximize the fluorescence characteristics. As described above, since the fluorescent compound of the present invention represented by the general formula (1) is a single compound, it can be purified to high purity. Examples of the purification method include methods such as recrystallization and crystallization, washing with a solvent, silica gel column chromatography, gel filtration chromatography, and preparative liquid chromatography, as in the case of ordinary organic compounds. The purity of the fluorescent compound of the present invention is preferably 95% or more, more preferably 98% or more, and still more preferably 99% or more by liquid chromatography. When a large amount of impurities is contained, the fluorescent property of the compound of formula (1) itself may be deteriorated, and turbidity may be produced when the fluorescent resin composition is produced. There is a case. The purity determination by the liquid chromatography method can be performed under both normal phase and reverse phase conditions. In the normal phase, for example, an Inertsil (registered trademark) Diol column manufactured by GL Science can be used, and in the reverse phase, for example, an XBridge (registered trademark) C18 column manufactured by Waters can be used. Size exclusion chromatography is also an effective method, and for example, a TSK-GEL SuperH2000 column manufactured by Tosoh Corporation can be used. In the present invention, the measurement is performed using an Inertsil (registered trademark) Diol column manufactured by GL Science.

  The fluorescent resin composition of the present invention is a resin containing the fluorescent compound of the present invention inside. The resin used as the matrix is not limited, but for example, polyethylene, polypropylene, polystyrene, cycloolefin polymer, polyacrylate, polyvinyl chloride, polycarbonate, polyester, polyamide, polyimide, polysiloxane, polyvinyl alcohol, ethylene-vinyl alcohol copolymer resin, ethylene- Vinyl acetate copolymer resin, ABS resin, epoxy resin, phenol resin, melamine resin, thermoplastic or thermosetting resin such as polyurethane, natural rubber, nitrile rubber, urethane rubber, EPDM, styrene butadiene rubber, fluoro rubber, silicone rubber, etc. And the like. Particularly preferred are silicone resins such as silicone oil, silicone rubber, silicone resin, and silicone gel. The fluorescent resin composition of the present invention may be in any state of liquid, solid, rubber, gel and the like.

  In the fluorescent resin composition of the present invention, the fluorescent compound is preferably uniformly dispersed without aggregating. Moreover, in the fluorescent resin composition of this invention, you may contain 2 or more types of fluorescent compounds including the fluorescent compound of this invention.

  In the fluorescent resin composition of the present invention, the content of the fluorescent compound is arbitrary, but is usually 0.001 to 10% by mass, preferably 0.01 to 1% by mass. It is preferable to determine the content of the fluorescent compound within a range compatible with the matrix resin. Depending on the nature of the fluorescent compound and the nature of the matrix resin, if the content of the fluorescent compound is too high, the fluorescence intensity may decrease due to concentration quenching, and if the content is too low, the fluorescence intensity may not be sufficient. is there.

  The fluorescent resin composition of the present invention may contain components other than the resin. For example, water, methanol, ethanol, hexane, isooctane, decane, toluene, xylene, dimethylformamide, dimethylacetamide, methylpyrrolidone, dimethylsulfoxide and other solvents, silica gel, titanium oxide, zinc oxide, carbon, magnesium hydroxide filler, silane Coupling agents, silicon compounds such as tetramethoxysilane, tetraethoxysilane, hexamethyldisiloxane, decamethylcyclopentasiloxane, radical polymerization initiators such as azobisisobutyronitrile and benzoyl peroxide, 2-hydroxy-2- Photopolymerization initiators such as methylpropiophenone and diphenyliodonium hexafluorophosphate, chloroplatinic acid, platinum (0) divinyltetramethyldisiloxane complex, benzylidenedichlorobisbis Metal compounds such as (rohexylphosphine) ruthenium, fibers such as glass fibers and carbon fibers, UV absorbers and light stabilizers such as benzophenone derivatives and hindered amine compounds, plasticizers such as phthalates and adipates, phosphates, etc. Flame retardants and the like. The content of these components can be arbitrarily determined within a range that does not interfere with the light emission characteristics of the composition, and is usually in the range of 0.01 to 80% by mass.

  The fluorescent compound of the present invention can be produced by, for example, forming a coumarin structure or a quinolinone structure by a known method and then bonding a siloxane-containing group. Examples of the method for bonding a siloxane-containing group include a hydrosilylation reaction to an aliphatic unsaturated group using a siloxane having a Si—H bond, a nucleophilic substitution reaction using a siloxane having a halogenated hydrocarbon group, and the like. However, it is not limited to this.

  As a method for adding the fluorescent compound to the fluorescent resin composition of the present invention, for example, a method of kneading and dispersing the resin and the fluorescent compound, or mixing and dissolving the fluorescent compound in a liquid resin monomer or prepolymer in advance. And addition polymerization or condensation polymerization, and a method of dissolving a fluorescent compound in a resin varnish.

  EXAMPLES Next, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not limited at all by the following examples. In the following structural formulas, Me represents a methyl group.

Example 1 7- {N-propyl-N- [3- (1-trimethylsiloxy-1,3,3,3-tetramethyldisiloxane-1-yl) propyl] amino} -4-trifluoromethyl Synthesis of Coumarin (Compound 1) In a nitrogen atmosphere, 73.4 (N-allyl-N-propylamino) -4-trifluoromethylcoumarin 693.4 mg (2.22 mmol), platinum (0) 1,3-divinyl-1 , 1,3,3-tetramethyldisiloxane complex, 10.2 mg of a 2% by weight xylene solution is charged, and 551.4 mg (2.48 mmol) of 1,1,1,3,5,5,5-heptamethyltrisiloxane is charged. Was added dropwise over 10 minutes. After completion of dropping, the reaction solution was stirred at room temperature for 1 hour. The obtained solution was concentrated under reduced pressure, water and toluene were added, and then the organic layer was extracted by a liquid separation operation. The resulting solution was dried over magnesium sulfate, concentrated under reduced pressure using a rotary evaporator, and purified by preparative liquid chromatography to obtain 844.6 mg of a yellow liquid.
As a result of measuring the NMR spectrum and MS spectrum of this solution, 7- {N-propyl-N- [3- (1-trimethylsiloxy-1,3,3,3-tetramethyldisiloxane-1-yl) propyl] was obtained. It was confirmed to be amino} -4-trifluoromethylcoumarin. The purity determined by high performance liquid chromatography (HPLC, column: Inertsil (registered trademark) Diol, manufactured by GL Science, mobile phase: hexane / chloroform = 7/3 (mass ratio), UV detector, wavelength 254 nm) is 99.2. %Met.

¹ H-NMR (600 MHz, d in CDCl ₃ ): 0.01 (s, 3H), 0.06-0.08 (m, 18H), 0.42-0.45 (m, 2H), 0. 94 (t, 3H), 1.59-1.65 (m, 4H), 3.27-3.31 (m, 4H), 6.33 (s, 1H), 6.47 (d, 1H) , 6.57 (dd, 1H), 7.44 (dd, 1H)
MS (EI) m / z: 533 (M ^<+> ), 518, 504, 284

The structure of Compound 1 produced in Example 1 is shown in the following formula (8).

The UV-visible absorption spectrum and fluorescence spectrum of Compound 1 were measured in ethanol. The longest absorption maximum wavelength was 404 nm, the molar extinction coefficient was 2.28 × 10 ⁴ , and the maximum fluorescence wavelength was 513 nm (excitation wavelength: 404 nm).

[Example 2] Synthesis of 7- {N-propyl-N- [3- (undecamethylpentasiloxane-1-yl) propyl] amino} -4-trifluoromethylcoumarin Under nitrogen atmosphere, 7- (N- Allyl-N-propylamino) -4-trifluoromethylcoumarin 577.6 mg (1.40 mmol), 2% by mass of platinum (0) 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex 6.9 mg of xylene solution was charged, and 574.5 mg (1.54 mmol) of 1,1,3,3,5,5,7,7,9,9,9-undecamethylpentasiloxane was added dropwise over 10 minutes. . After completion of dropping, the reaction solution was stirred at room temperature for 2 hours. The obtained solution was concentrated under reduced pressure, water and toluene were added, and then the organic layer was extracted by a liquid separation operation. The resulting solution was dried over magnesium sulfate, concentrated under reduced pressure using a rotary evaporator, and then purified by preparative liquid chromatography to obtain 731.6 mg of a yellow liquid. As a result of measuring the NMR spectrum and MS spectrum of this solution, 7- {N-propyl-N- [3- (undecamethylpentasiloxane-1-yl) propyl] amino} -4-trifluoromethylcoumarin (Compound 2) ). The purity determined by HPLC (same conditions as in Example 1) was 99.6%.

¹ H-NMR (600 MHz, d in CDCl ₃ ): 0.02 (s, 6H), 0.030 (s, 1H), 0.032 (s, 1H), 0.06 (s, 1H), 0 .08 (s, 1H), 0.50-0.54 (m, 2H), 0.94 (t, 3H), 1.59-1.65 (m, 4H), 3.27-3.31 (M, 4H), 6.34 (s, 1H), 6.47 (d, 1H), 6.57 (dd, 1H), 7.44 (dd, 1H)
MS (EI) m / z: 681 (M ^<+> ), 666, 284

The structure of compound 2 produced in Example 2 is shown in the following formula (9).

The ultraviolet-visible absorption spectrum and fluorescence spectrum of Compound 2 were measured in ethanol. The longest absorption maximum wavelength was 404 nm, the molar absorption coefficient was 2.14 × 10 ⁴ , and the maximum fluorescence wavelength was 513 nm (excitation wavelength: 404 nm).

Example 3 7- {N-propyl-N- [3- (1-trimethylsiloxy-1,3,3,3-tetramethyldisiloxane-1-yl) propyl] amino} -4-methylcoumarin ( Synthesis of Compound 3) Under a nitrogen atmosphere, 77.1 (N-allyl-N-propylamino) -4-methylcoumarin 707.1 mg (2.75 mmol), platinum (0) 1,3-divinyl-1,1,3 , 3-tetramethyldisiloxane complex 10.2 mg of 2% by weight xylene solution was charged, and 678.5 mg (3.05 mmol) of 1,1,1,3,5,5,5-heptamethyltrisiloxane was charged over 10 minutes. And dripped. After completion of dropping, the reaction solution was stirred at 40 ° C. for 2 hours. The obtained solution was concentrated under reduced pressure, water and toluene were added, and then the organic layer was extracted by a liquid separation operation. The resulting solution was dried over magnesium sulfate, concentrated under reduced pressure using a rotary evaporator, and then purified by preparative liquid chromatography to obtain 903.6 mg of a pale yellow liquid. As a result of measuring the NMR spectrum and MS spectrum of this solution, 7- {N-propyl-N- [3- (1-trimethylsiloxy-1,3,3,3-tetramethyldisiloxane-1-yl) propyl] was obtained. It was confirmed to be amino} -4-methylcoumarin. The purity determined by HPLC (same conditions as in Example 1) was 99.9%.

¹ H-NMR (600 MHz, d in CDCl ₃ ): 0.01 (s, 3H), 0.06-0.08 (m, 18H), 0.41-0.45 (m, 2H), 0. 93 (t, 3H), 1.58-1.64 (m, 4H), 2.30 (s, 1H), 3.25-3.30 (m, 4H), 5.90 (s, 1H) , 6.44 (d, 1H), 6.53 (dd, 1H), 7.33 (d, 1H)
MS (EI) m / z: 479 (M ⁺ ), 464, 450, 230

The structure of compound 3 produced in Example 3 is shown in the following formula (10).

The UV-visible absorption spectrum and fluorescence spectrum of Compound 3 were measured in ethanol. The longest absorption maximum wavelength was 375 nm, the molar extinction coefficient was 1.99 × 10 ⁴ , and the maximum fluorescence wavelength was 449 nm (excitation wavelength: 375 nm).

Example 4 Production of Silicone Resin Composition Containing Compound 1 In a glass vial, 53.4 mg of Compound 1 produced in Example 1 was weighed and a transparent silicone resin SIM-360 base agent (manufactured by Shin-Etsu Chemical Co., Ltd.). ) Was added in small portions with stirring at room temperature. It was judged that the solution was dissolved when it became transparent, and the solubility was calculated to be 130 mmol / L. To this mixture, 10% by mass of a curing agent relative to the main agent was added and mixed. After defoaming, the mixture was cured by heating at 150 ° C. for 30 minutes to obtain a fluorescent silicone resin composition. The concentration of Compound 1 could be arbitrarily changed below the above concentration.

Example 5 Production of Silicone Resin Composition Containing Compound 2 The solubility of Compound 2 in the SIM-360 main ingredient was measured in the same manner as in Example 4 and found to be 190 mmol / L. To this mixture, 10% by mass of a curing agent relative to the main agent was added and mixed. After defoaming, the mixture was cured by heating at 150 ° C. for 30 minutes to obtain a fluorescent silicone resin composition. The concentration of Compound 2 could be arbitrarily changed within the above concentration range.

[Comparative Example 1] Solubility measurement of 7- (N-allyl-N-propylamino) -4-trifluoromethylcoumarin (Compound 4) in silicone resin The structure of Compound 4 used in Comparative Example 1 is represented by the following formula ( 11). It was 25 mmol / L when the solubility to the SIM-360 main ingredient of the compound 4 was measured like Example 4. Compound 4 has no siloxane-containing substituents and is clearly less soluble than Examples 4 and 5.

[Comparative Example 2] 7- {N- [3- (1-trimethylsiloxy-1,3,3,3-tetramethyldisiloxane-1-yl) propyl] amino} -4-trifluoromethylcoumarin (Compound 5) Measurement of Solubility in Silicone Resin The structure of Compound 5 used in Comparative Example 2 is shown in the following formula (12). When the solubility of the compound 5 in the SIM-360 main ingredient was measured in the same manner as in Example 4, it was 0.9 mmol / L. Although the compound 5 has a siloxane-containing substituent, it has a nitrogen-hydrogen bond serving as a hydrogen bond donor, and is clearly less soluble than Example 4 and Example 5.

Example 6 Production of Silicone Resin Composition Containing Compound 3 The solubility of Compound 3 in the SIM-360 main ingredient was measured in the same manner as in Example 4, and the result was 40 mmol / L. To this mixture, 10% by mass of a curing agent relative to the main agent was added and mixed. After defoaming, the mixture was cured by heating at 150 ° C. for 30 minutes to obtain a fluorescent silicone resin composition. It should be noted that the concentration of Compound 3 could be arbitrarily changed below the above concentration.

  The fluorescent compound of the present invention can be used for fluorescent inks, wavelength conversion materials and the like. For example, since a low-polarity resin such as a silicone resin can be colored without impairing transparency, a highly transparent fluorescent resin composition can be obtained and is highly useful.

Claims (5)

A fluorescent compound represented by the following general formula (1).

(In the formula (1), X represents —O— or —NR—. R ¹ represents a monovalent hydrocarbon group which may be substituted with a fluorine atom having 1 to 20 carbon atoms. R ² represents a hydrogen atom. and .R ³ is a group selected good monovalent hydrocarbon radical or et be substituted with a fluorine atom having 1 to 20 carbon atoms, R ^4, R ⁵ and R ⁶ may be the same or different, a hydrogen atom , A monovalent hydrocarbon group optionally substituted with a halogen atom having 1 to 20 carbon atoms, a diorganoamino group represented by the following formula (4), an organoxy group represented by the following formula (5), the following formula The substituent is independently selected from the organosulfanyl group represented by (6) and the siloxane-containing group of the following formula (2): R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁵ and R ⁶ are each A ring structure having 5 to 8 carbon atoms, which includes two carbon atoms bonded to each other and bonded to each other. Provided that at least one of R ³ , R ⁴ , R ⁵ and R ⁶ is a siloxane-containing group represented by the following formula (2) or a group containing it as a substituent: R is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and when the compound of the formula (1) includes a plurality of R and / or R ¹ , they may be the same or different. )

(In Formula (2), Sx has 2 to 10 silicon atoms, and a linear, branched or cyclic organosiloxa group in which a monovalent hydrocarbon group having 1 to 20 carbon atoms is bonded to the silicon atom. Represents a nyl group, and a silicon atom is bonded to A. A represents a divalent hydrocarbon group having 1 to 20 carbon atoms, A ¹ represents —O—, —S—, —NR—, —O—C. (O) -, - C ( O) -O -, - NR 1 -C (O) -, - C (O) -NR 1 - and represents either a single bond).

(In Formula (4), R ⁸ may be the same or different and represents a monovalent hydrocarbon group having 1 to 20 carbon atoms or a siloxane-containing group represented by Formula (2) above, provided that an oxygen atom, sulfur Atom and nitrogen heteroatoms are not adjacent to each other.)

(In the formula (5), R ⁹ represents a monovalent hydrocarbon group having 1 to 20 carbon atoms or a siloxane-containing group represented by the above formula (2), provided that an oxygen atom, a sulfur atom, and a nitrogen atom are heterogeneous. Atoms are not adjacent.)

(In the formula (6), R ¹⁰ represents a monovalent hydrocarbon group having 1 to 20 carbon atoms or a siloxane-containing group represented by the above formula (2), provided that an oxygen atom, a sulfur atom, and a nitrogen atom are heterogeneous. Atoms are not adjacent.) In the general formula (1), R ^Four Or R ^Five The fluorescent compound according to claim 1, wherein is a substituent represented by any of formulas (4) to (6). The fluorescent compound according to claim 1 or 2, wherein in the general formula (1), R ² is a hydrogen atom.   The fluorescent resin composition containing the fluorescent compound and resin of any one of Claims 1-3.   The fluorescent resin composition according to claim 4, wherein the resin is a silicone resin.