WO1997034877A1 - Cyanopyrazine derivatives, polymers, production process, and molded articles - Google Patents

Abstract

A novel cyanopyrazine compound useful as a functional dyestuff, which is represented by general formula (I), wherein R?1, R2, R3, and R4¿ are each independently an optionally substituted divalent hydrocarbon group which may have an ether, ester or amide linkage; and X?1, X2, X3 and X4¿ are each hydrogen, acryloyloxy or methacryloyloxy, with the proviso that at least one of X?1, X2, X3 and X4¿ must be acryloyloxy or methacryloyloxy. Molded articles produced therefrom have excellent light stability and therefore can stand long-term outdoor use.

Description

 Shen cyano virazine derivative, polymer, manufacturing method and molded body

 The present invention relates to novel cyano virazine derivatives and polymers useful as functional dyes, a method for producing them, and molded articles.

Background art:

 The 3,6-diamino 2,5-virazine dicarbonyl RNyls in which the amino group is substituted with a lower alkyl group described in JP-A-5-32640 are sublimated. When it is used by dissolving it in water with a small amount of S and dissolving it into plastics, etc., the light resistance is not always practically sufficient depending on the use scene XR. X

 Two

Disclosure of the invention:

 An object of the present invention is to provide a 3.6-diamino-2,5-virazine dicarbonitrile derivative excellent in light stability that can withstand long-term outdoor use, and a molded article containing the same. Structure of the invention

 (1) General formula (I)

N C .N [I]

X ³ R ³ -N 8 ヽ CN

R ⁴ X ⁴

[Wherein, R ¹ , R ² , R ³ , and R each independently represent a divalent hydrocarbon group which may have an ether bond, an ester bond, or an amide bond; May have a substituent, X ¹ , X ² , X ^3. X ⁴ is a hydrogen atom, an acryloyloxy group or a methacryloyloxy group, and X ′, X ² , X ³ And at least one of X ^{4 is} an acryloyloxy group or a methacryloyloxy group. ] The compound represented by these.

 (2) Polymer

The compound represented by the general formula [I] undergoes radical polymerization to polymerize at an acryloyl or methacryloyl moiety. The polymer is intended to mean a homopolymer and a copolymer of the monomer unit represented by the general formula [I], and a copolymer including a monomer unit other than the monomer unit represented by the general formula [I]. I do.

 This is because a compound of the general formula [I] or a mixture of the compound of the general formula [I] and a radically polymerizable compound is subjected to radical polymerization in the presence of a radical polymerization initiator to form a crosslinked or non-crosslinked product. It is a crosslinked polymer.

 (3) Cross-linking or non-cross-linking obtained by radical polymerization of a compound of the general formula [I] or a mixture of the compound of the general formula [I] and a radically polymerizable compound in the presence of a radical polymerization initiator And a method for producing the same.

 (4) A polymer compound molded article containing the polymer according to (3).

Embodiment of the invention:

 (1) Compound

The divalent hydrocarbon group which may have an ether bond, an ester bond, or an amide bond of R ¹ , R ² , R ³ , and R ⁴ is a saturated or unsaturated linear or branched chain. A branched chain hydrocarbon group, a phenylene group, a naphthylene group or a combination thereof, for example, a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group And methylene, octamethylene, nonamethylene, decamethylene, ethylethylene, propylene, propylene, vinylene, propynylene, ethynylene, etc., which may be substituted with a substituent.

Further divalent hydrocarbon group having an ether bond, an ester bond, an amino-de-binding, for example, - (r ') _t one A- (r ²⁾ _u - (wherein, r', r ² is independently A saturated or unsaturated, linear or branched chained hydrocarbon group, phenylene group, naphthylene group or a combination thereof, wherein A is 10-, 1-C00 —,-0 C 0-, one CONH— or — NH CO—, t and u each independently represent 0 or 1.) or this — (r ¹ ) one A— (r ² ) one Further, it is a group containing 10-, one COO-, -0C0-, one CONH- or one NHC0-, which may be substituted with a substituent.

Examples of the substituent of the hydrocarbon group include a hydroxyl group, an amino group, a mono- or di-alkylamino group, a carboxyl group, an acyl group, a formyl group, an alkoxyl group, an alkylyl group, an aryl group such as phenyl, and the like. Alkylsilyl group, halogen atom, heterocyclic group, etc. These substituents include, for example, an alkyl group, a hydroxyl group, an amino group, a mono- or dialkylamino group, a carboxyl group, an acyl group, a formyl group, an alkoxyl group, an alkenyloxy group, and an alkynyloxy group. , An alkylthio group, an alkenylthio group, an alkynylthio group, an aryl group, an alkylsilyl group, an alkylsulfonyl group, an aryl group or a heterocyclic group which may be substituted with a halogen atom or a heterocyclic group. May be. In the present invention, the chain hydrocarbon group usually has 2 to 22 carbon atoms, 1 to 6 for alkyl, and 2 to 6 for alkenyl and alkynyl.

 (2) Polymer

Examples of the compound capable of radical polymerization include methyl methacrylate, methyl methacrylate, propyl methacrylate, butyl methacrylate, isobutyl methacrylate, methyl methacrylate Tertiary butyl acrylate, 2-methacrylic acid 2-ethylhexyl, octyl methacrylate, indecyl methacrylate, lauryl methacrylate, lauryl methacrylate Tridecyl, tridecyl methacrylate, cetyl-stearyl methacrylate, stearyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, methacrylic acid, methacrylic acid 2—Hydrox-kishetil, 2-hydroxypropyl methacrylate, dimethylaminoethyl methacrylate, getylaminoethyl methacrylate, metal Tertiary butyl aminoethyl acrylate, glycidyl methacrylate, tetrahydrofurfur methacrylate, ethylene dimethacrylate, diethylene glycol dimethacrylate, triethylene dimethacrylate Glycol, tetraethylene glycol dimethacrylate, decaethylene glycol dimethacrylate, pentadecaethylene glycol dimethacrylate, pentaethylene glycol dimethacrylate, phthalethylene glycol 1,3-Dimethacrylic acid 1,3-butylene, acrylyl methacrylate, trimethylolpropane trimethacrylate, pentyl tetramethacrylate, erythritol dimethacrylate, diethylene glycol phthalate Such as methacrylate, methyl acrylate, ethyl acrylate Butyl acrylate, 2-ethyl hexyl acrylate, dimethyl aminoethyl acrylate, isoptyl acrylate, acetylene glycol alcohol acrylate, 2-ethyl ethoxylate , Epoxyacrylate, n-stearylacrylate, tetrahydrofurfuryl acrylate, trimethylolpropane triacrylate, 1,4-butanediol diacrylate, 1,6 — Acrylates such as hexanediol diacrylate, pentaerythritol and phenol reacrylate, acrylonitrile, styrene, butyl acetate, butadiene, acrylamide, and vinyl alcohol Gin, crotonic acid And crotonates such as methyl crotonate, divinylbenzene, acrolein, diarylorthophthalate, diarylisophthalate, aryl acetate, maleic anhydride and the like.

 The radical polymerization initiator used for the polymerization of the compound of the general formula [I] or the mixture of the compound of the general formula [I] and the radically polymerizable compound may be azobisisobutyronitrile, azobis — 2,4-Dimethylpa X relonitrile, azobiscyclohexanecarbonitrile, azobi

 Four

Sue 2-amidinopropane hydrochloride, potassium peroxodisulfate, monoxide peroxodisulfate, t-butyl hydroperoxide, di-t-peroxide-t-butyl methoxide dropoperoxide, acetyl peroxide, benzoyl peroxide And lauroyl peroxide.

 (3) Manufacturing method

 i) monomer

 General formula (I) of the present invention

R ¹ X ¹

R ² X ²

 [I

(Wherein, R ¹ , R ² , R ³ , X ′, X ² , X ³ , and X ⁴ have the same meanings as described above.) A known reaction or a similar reaction is appropriately selected. Can be manufactured.

R 'X ¹

 (I)

 T

i) L ⁵ -R and L ⁶ , L ⁷ -R ² -L * L ⁹ -R ³ -L ¹⁰

Or L ¹ '-R ⁴ -L ¹²

ii) HOCOCR = CH ₂ where L ¹ , L ² , L ³ , L ⁴ , L ^3. L ^G , L ⁷ , L ⁸ , L ⁰ , LL ", L ¹² are OH, halogen atom, methane Represents a leaving group such as a sulfonyloxy group, a p-toluenesulfonyl group, etc. R represents a hydrogen atom or a methyl group.

 The reactions 1) to 4) may be performed simultaneously. If necessary, use a base and a dehydrating condensing agent. Examples of the base and the dehydrating condensing agent include, for example, sodium hydroxide, sodium hydroxide, sodium carbonate, sodium carbonate, cesium carbonate, lithium hydroxide, and sodium hydroxide. Ride, metallic sodium, metallic lithium, sodium methylate, sodium methylate, potassium acetate, potassium bromide, potassium bivalinate, potassium acetate Sodium acrylate, sodium methacrylate, sodium acetate, sodium bromoacetate, sodium bivalinate, sodium trichloroacetate, acrylyl Sodium acid, sodium methacrylate, 1,5-diazabicyclo [4.3.0] 111-one-5-ene (DBN), 1,8-diazabicyclo [5. 4.0] Power 7-Den (DBu) Examples of dehydrating condensing agents such as pyridine and triethylamine include mineral acids such as sulfuric acid and hydrochloric acid, organic acids such as aromatic sulfonic acid, 1,3-dicyclohexylcarpoimide (DCC), and 1-ethyl- Examples include organic condensing agents such as 3- (3'-dimethylaminopropyl) carbodiimide (WSCI).

The solvent used in the reaction is not particularly limited as long as it is inert to the reaction reagent. Examples thereof include dimethylformamide (DMF), dimethylacetamide (DMAC), dimethylsulfoxide (DMSO), Dimethyethane (DME), tetrahydrofuran (THF), etc. BTX-based solvents such as ethers and benzene, chlorine-based solvents such as black form, acetate nitrile

And alcohols. Further, the reaction may be carried out without a solvent by using an excess of the reaction reagent.

When R ¹ , R, R ³ , and R ¹ have an ether bond, an ester bond, or an amide bond, these bonds can be formed by an ordinary method.

0 H + L ^{, 3} -one 0-

C 0-L + HO--C 00-OH + ⁵ -C 0 1 0 C 0-

C 0-L + H ₂ N--C 0 NH

NH ₂ + i ⁷ — C 0-NH C 0

^{L '3, L 14, L} ' 5, L 16, L 17 represents a leaving group as described above.

For example, when R ¹ , R ³ , and R ⁴ are a methylene group, R ² is a polymethylene group, X ¹ , X ³ , and X ⁴ are a hydrogen atom, and X ² is a methacryloyloxy group, Scheme I and Scheme II It can be produced by the method shown in Scheme III.

 In the formula, n represents an integer of 1 to 8.

Scheme I

CH CH ₃

C

CT/JP96/00663 スキーム ,)„ OSiCCH,,)

CT / JP96 / 00663 scheme,) „OSiCCH ,,)

CH _;

., N (CH ₂ ) „OH CH ₂ = C (CH ₃ ) C0C e

 TBAF Pyridine

CH ₃ NN CN

CH ₃ CH ₂ -C (CH ₃ ) C00H

 DCC

 (TBAF: Tetra Petit) Lean ゥ Mufluorate ')

CH ₅ scheme 1Π

C

CH ₃

CH

CH, Further, the compound of the present invention is also produced by the following method.

Y '

 I

NCN NH ₂ R ⁹ C 00 ZNCNN— Y

HaKC H ₂ ), hal

H ₂ NNCNC, -Ce Alkylating agent Y ³ -N ■ NN

 I

 [II] Y [HI]

c, -c ₆ alkyl- x ^; NCN

 Transesterification

R ⁷ -N "N RI N

 I

R ⁸ [门 'R

(In the formula, Hal and hal represent a halogen atom, Y ¹ , Y ² , Y ³ , and Y ¹ each independently represent C, C alkyl, (CH ₂ ) _n 0 C 0 R ⁸ , and (iC , ~ C ₂₂ alkyl, C, ~ C ₂₂ haloalkyl, C ₂ -C ₂₂ alkenyl, optionally substituted phenyl, aralkyl, haloaralalkyl, Z represents sodium or potassium, and n represents 1 X ⁵ represents an acryloyloxy group or a methyl acryloyloxy group; R ⁵ , R ⁶ , R ⁷ , and R ⁸ each independently represent C, -C ₆ alkyl, (CH _{2) n} 0 C oR ^9, a ^{_{(CH 2) n X 5,}} R 5, R 6, R 7, one or more of R ⁸ is ^{_{(CH 2) "X 5.}} )

 ii) Polymer

 The polymer of the present invention can be prepared by subjecting a compound represented by the general formula [I] or a mixture of the compound represented by the general formula [I] and a compound capable of radical polymerization to a known radical polymerization method, for example, bulk polymerization, solution polymerization, and the like. In this case, it can be produced by polymerization using a method such as emulsion polymerization or suspension polymerization. Degree of polymerization: 10 to 10

0, preferably 200 to 50,000. The amount of the radical polymerization initiator is 0.05 to 5 parts by weight based on 100 parts by weight of the monomer. A known method may be applied to obtain a polymer having a crosslinked structure. That is, a copolymer with a monomer having two or more polymerizable double bonds or a monomer having a functional group such as a carboxyl group ゃ hydroxyl group, for example, methacrylic acid タ 2-hydroxyhexyl methacrylate After copolymerization with such a compound, a polymer having a cross-linked structure can be obtained by using in combination with an appropriate cross-linking agent, for example, an amino resin, an isocyanate compound, or an epoxy resin. Models with two or more polymerizable double bonds The degree of cross-linking, expressed in mol% of nomer, is between 0.11 and 99.999%, preferably between 0.1 and 50%.

 The mixing ratio between the compound of the general formula [1] and the compound capable of undergoing radical polymerization is from 1: 0 to 1: 100,000, preferably from 1: 5 to 1: 200, by weight.

 When the polymer is pulverized or emulsion polymerization or suspension polymerization for easy use, it can be used as it is as a fluorescent powder.

 (4) Molded body

 In the present invention, the molded article may be the polymer of the present invention as it is, or may be contained in a polymer compound.

 Examples of the high molecular compound include (soft, semi-rigid, and rigid) PVC; polyethylene; polypropylene; polyvinyl alcohol; polymethyl acrylate; polymethyl methacrylate; poly (vinylidene chloride); Ril; Polybutadiene; Polystyrene; Ethylene-vinyl acetate copolymer; Vinyl chloride-vinyl acetate copolymer; Polyvinyl butyral; Polyvinyl formal; Polyesters such as PET and PBT; Polyarylates; Polyester carbonate; phenoxy resin; polyamides such as nylon 6, nylon 6Z6, nylon 11, nylon 12, and MXD6 nylon; polydimethylsiloxane; polytrimethylsilylpropyl; N; ionomers; serov Emission: polyether Chirenserofa emissions; cellulose § cetearyl Ichito; cellulose propionate Bok; Echiruseruro scan; two Bok b cellulose; 钦質 such hard resins.

 In the present invention, the molded article is, for example, a plate, a film, a fiber, a nonwoven fabric, a fiber, a powder, a fine particle, or the like.

 There are no particular restrictions on the manufacturing method of the molded body, and extrusion molding (single layer or laminated), inflation molding (single layer or fertile layer), calender molding, injection molding, It can be manufactured by transfer molding or the like, or by coating or impregnating a varnish containing the polymer of the present invention on glass, plastic, a reflector, a film, a woven fabric, a nonwoven fabric, a paper, or the like. .

 The type and amount of the molded article satisfying the conditions for use and do not impair the object of the present invention, such as UV absorbers, antioxidants, hindered amine light stabilizers, lubricants, anti-S agents, dropping agents, etc. Of additives can be distributed.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described more specifically by way of representative examples.

Example 1 Synthesis of Compound A of the Present Invention

 ① 3 —Amino 6 -Benzylamino 2, 5 —Synthesis of pyrazinedicarbonitrinole (compound a)

 3,6—Diamino 2,5—Pyrazinedicarbonitrile 4.50 g was dissolved in 15 ml of dimethylacetamide, and 5.13 g of benzoyl chloride was added. The reaction was performed at 70 and 45 minutes. After cooling the reaction mixture, add 2.8 m of toluene, add 28 ml of water and about 5 g of 50% NaOH, collect the precipitated crystals by filtration, wash with water and ethyl acetate, and dry to obtain yellow crystals. 7.28 g were obtained. Yield 98%, DSC measurement: 270 (endothermic peak)

 ② Synthesis of 3-dimethylamino 6-methylbenzoylamino 2,5 —pyrazinedicarbotriol (compound!)

 Compound a 7.20 g, dimethyl acetate amide 110.m1, methyl iodide 35.53 g, and anhydrous carbonated carbonate 15.09 g were mixed at 60 to 70 ° C. The reaction was performed for 4 hours. To the reaction mixture was added 220 ml of water, extracted with 220 ml of dichloromethane, washed with water, dried and concentrated, and reprecipitated from ethyl acetate / n-hexane to obtain 5.02 g of yellow crystals. .

 Yield 60% m.p. 15 9-15 .5 ° C

 ③ Synthesis of 3-dimethylamino 6-methylamino 1,2, 5-virazine dicarboditrinole (compound c)

 Compound b (5.00 g), methyl alcohol (180 m) and 10% HClaqi (0100 ml) were mixed and reacted at 80-90 ° C for 20 hours. The reaction solution was cooled, and the precipitated crystals were collected by filtration, washed with water, and dried to obtain 1.88 g of dark red crystals. Yield 60%, m.p. 208 to 209.5 ° C

④ Synthesis of 3-dimethylamino 6-methyl (6-iodohexyl) amino 2,5-pyrazine dicarboditril (compound d)

化合物 c 3 gと 1 , 6 —ジョ一 ドへキサン 9. 7 gのジメチルァセ トア ミ ド （ 1 0 0 m 1 ) 溶液に撹拌しながら炭酸セシウム 6. 3 gを加え室温下、 3 0時間反応を行なった。 反応液に水 2 0 0 m l を加え不溶物を濾取しェ一テルで抽出した。 エーテル層を水洗し、 無水硫酸マグネシゥムで乾燥後減圧濃縮し、 シリカゲルカラ厶クロマ 卜 グラフ （流出溶媒 ： ベンゼン） で精製した。 更にへキサンで再結晶することにより赤色結晶の目的物を 3. 0 g得た。 収率 4 9 %、 m. p . 5 5 °C CH

Compound c 3 g and 1,6—Jodium 9.7 g of dimethylacetamide (100 m 1) 6.3 g of cesium carbonate was added to the solution while stirring, and the mixture was reacted at room temperature for 30 hours. 200 ml of water was added to the reaction solution, and the insoluble matter was collected by filtration and extracted with ether. The ether layer was washed with water, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and purified by silica gel column chromatography (solvent: benzene). Further recrystallization from hexane gave 3.0 g of the desired product as red crystals. Yield 49%, m.p. 55 ° C

lHNMR (2 0 0 MH z, CDC 1 3) 5 ppm:. 1. 2~ 1. 3 (8 H, m), 3 1~ 3. 3 (1 1 H, m), 3. 4~ 3. 6 C 2 H, t)

⑤ formula (I) in _{R 'X' = (CH 2} ) OCOC (M e) = CH 2, R 2 2 - Synthesis of ^{R 3 X 3 = R 4 X} 4 = is M e present compound A

CH ₃

 CH; Compound A Compound d 2.5 g and 0.8 g of methacrylic acid in a solution of acetonitrile (31 m 1) were stirred with stirring to give 8-diazabicyclo [5.4.0] pendecar 7 Then, 1.1 g of DBU was added dropwise, and the mixture was reacted for 4 hours under reflux. After allowing to cool, water was added, and the mixture was extracted with ether. The ether layer was washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain 2.2 g of the target substance as a red oil. Yield 95%

'HNMR (200 MHz, C DCl ₃ ) op pm: l. 2 to 1.8 (8H, m),). 95 (3H, s), 3.15 (3Η, s), 3.16 (6 Η, s), 3.5 1 (2 Η, t), 4.15 (2 Η, t), 5.55 (1 Η, m), 6.1 (1 Η, s)

 Visible 'ultraviolet absorption spectrum max: 2 4 1, 3 0 0, 5 0 9 nm (i n

CHC 1 a) Fluorescence spectra A em: 5 9 2 (scan ex 500 nm) (in CHC 1 3) Example 2 invention Synthesis of Compound B

 3, 6-diamino_2,5—pyrazinedicarbotriol 0.64 g, 1-bromo-6-chlorohexane 2.39 g, sodium iodide 3.60 g, potassium acetate 0.79 g, stearyl trimethylammonium chloride (surfactant) 0.10 g, N-methyl bilolidinone 15 ml, and mixed. Initiate the reaction at ° C. During the reaction, 0.39 g of acetic anhydride was added after 2 hours, 0.39 g after 4 hours, 0.78 g after 6 hours, and 3.00 g of dimethyl sulfate after 6 hours. The reaction is terminated after 9 hours. After cooling, the reaction solution was extracted with 100 ml of ethyl acetate, washed with water and dried to obtain 1.91 g of an oily dye mixture. The mixture is H P L C

 I

After NMR, the following structure (mixture) was confirmed by NMR and MASS.

Y ³

^{Υ ', Υ 2, Υ 3} , Υ 4: (CH 2) B C 0 CH 3, CH 3

 The pyrazine ring yield determined by absorbance measurement was 75.9%.

Dissolve 1.8 g of the obtained dye mixture in 30 ml of methyl methacrylate, add 1.2 g of paratoluenesulfonic acid, and react at 60 ° C for 14 hours (ester exchange reaction). went. -The conversion from (CH ₂ ) ₆ COCH ₃ to 1 (CH ₂ ) ₆ C 0 C (CH ₃ ) = CH ₂ was 81%, and the yield was 1.86 g.

Visible and ultraviolet absorption scan _{Bae-vector; i raax: 240. 300, 504} nm (CHC1 3)

Fluorescence spectrum scan em: 590 nm (λ ex 500nm , CHC1 3)

Example 3 (Production of polymer)

 Compound A (0.05 g), methyl methacrylate (1.35 g), and azobisisoptyronitrile (45 mg) were mixed. The obtained homogeneous solution was sealed after purging with nitrogen, and polymerized in a water bath at 70 ° C. After 3 hours of polymerization and curing, the polymer was dissolved in chloroform, reprecipitated with methanol, and dried under reduced pressure. The obtained polymer had a red fluorescent color. The degree of polymerization was determined by a viscosity equation to be 2,200. Yield 1.23 g. Yield 88%.

Example 4 (Production of crosslinked polymer) Compound A 0.05 g, methylmethacrylate 1.35 g, trimethylolpropane trimethacrylate 0.12 g, and azobisisoptirononitrile 49 mg were mixed. The resulting homogeneous solution was sealed after purging with nitrogen, and polymerized and cured in a 70 ° C. water bath for 3 hours. Force of immersing the obtained base body in black-hole form; polymer did not dissolve. It was immersed in a black-mouthed form for further 20 hours, crushed, filtered and washed with a black-mouthed form. The polymer slightly swollen with a black hole form was dried under reduced pressure. The obtained polymer exhibited a red fluorescent color as in Example 2. Yield 1.

2 g. Yield 78%.

Example 5 (Production of film)

 Each of the polymers obtained in Example 3 and Example 4 was ground using a mortar. The resulting powder

The powder having a particle size of 32 μm or less was prepared by passing through a 32 μm sieve. The powder of Example 2 is powder (A), and the powder of Example 3 is powder (B).

 The mixing ratio shown in Table 1 is 0. A soft PVC film with a thickness of ~ 0.2 mm was formed by hot pressing. Powder (A) was dissolved in PVC during kneading and film (A) became a transparent film, but powder (B) did not dissolve and film (B) became a fine particle-dispersed film.

Reference example

A soft salt bifilm (C) was prepared in the same manner as in Example 4 by using 3,6-dimethylamino 2,5-virazin dicarponitrile (F) described in JP-A-5-32640. . Compound (F) dissolved in PVC during kneading, and film (C) became a transparent film.

Table 1 PVC film compounding ratio Example 4 Reference example Film (A) Film (B) Film (C) PVC SUNAR SAS1000D "100 parts 100 parts 100 parts D 0 P ² ) 4 5 4 δ 4 5

TC P (tricresyl phosphate) ³ ) 5 5 5

DPDP (Gif) M Sodecyl sulfite) "0.5 0.5 0.5 0.5 Epoxy monomer DER33 / J ⁵¹ 1 1 1 Epoxidized soybean oil Daimac S-300K ⁶ '1 1 1 Barium stearate ⁷ ) 0.5 0.5 0.5 0.5 Zinc stearate ⁷⁾ 1 1 1

Polyoxyethylene sorbitan monostearate ⁸⁾ 1 1 1 Megafox F-120 ^e > 0.1 0.1 0.1 0.1 ubinal N- 539 ¹⁰¹ 3 3 3 Powder (A) 14.6

 Powder (B) 15.8

 3, 6-di) reamino-2.5-pyrazine dicarbonate) KF) 0.16 Note) 1) Sun Arrow Chemical Co., Ltd. 2) Sekisui Chemical Co., Ltd. 3) Daihachi Chemical Co., Ltd.

4) Sanko Chemical Co., Ltd. 5) Dow Chemical Japan Co., Ltd. 6) Daicel Chemical Industries, Ltd. 7) Nippon Oil & Fats Co., Ltd. 8) Wako Pure Chemical Co., Ltd. 9) Dainippon Ink Chemical Industry Co., Ltd. 1 0) BASF Japan Co., Ltd.

Test example 1

 The films (A) and (C) were subjected to a fading test by irradiation with a positive light. Table 2 shows the results. Table 2 Discoloration test by "sunlight lamp" irradiation

Note) 1) 90 ° C, 200,000 lux, Toshiba Lighting & Technology Corporation

 Reflective D R 400 / T (L)

 2) Measured using Hitachi 850 fluorescence spectrophotometer, excitation wavelength 500 nm

Industrial applicability:

 (1) The compound (molded product) of the present invention has excellent light fastness and water fastness because the dye component is chemically bonded to the polymer chain.

 (2) The compound of the present invention can be expected to be used as an intermediate for agricultural chemicals, fragrances, polymers, etc., and is expected to be used as a functional material such as electoruluminescence, wavelength conversion material, etc. Is done.

(3) The molded article having a wavelength conversion function of the present invention is not limited to a light collector for a solar cell or a covering material of a greenhouse, but also a multi-film, a reflection (multi) film, and sunlight are averagely radiated in the house. It can be used in reflectors, plastic nets, woven fabrics, non-woven fabrics, bags for bagging fruits, etc., as well as in prepaid cards, traffic signs, decoration, and display fields. You.

Claims

The scope of the claims  1. —General formula [I]

[Wherein, R ′, R ² , R ³ , and R ⁴ are each independently a divalent hydrocarbon group which may have an ether bond, an ester bond, or an amide bond; The group may have a substituent, and X ¹ , X ² , X ³ , and X ⁴ are a hydrogen atom, an acryloyloxy group, or a methacryloyloxy group, and X ¹ , X ² , X ³ , At least one of X "is an acryloyloxy group or a methacryloyloxy group.]  2. The compound represented by the general formula [I] is a compound represented by the formula [I] ′ R ⁵ NC .N, / N-R ⁶  [I] ' R ⁷ NNCN R ⁸ (Wherein, R ⁵ , R ⁶ , R ⁷ , and R ⁶ are each independently a d-Co alkyl group, (CH ₂ ) _n 0 COR ⁹ , or (CH ₂ ) _n X ⁵ , and R ⁹ iiC , ~ C ₂₂ alkyl, -C ₂₂ haloalkyl, c ₂ ~ c ₂₂ alkenyl, phenyl which may have a substituent, represents Ararukiru, the Haroa aralkyl, n represents an integer of 1 to 8, X ⁵ is § A compound represented by the formula: a cryloyloxy group or a methacryloyloxy group, wherein at least one of R ⁵ , R ⁶ , R ⁷ and R ⁸ is (CH ₂ ) _n X ⁵ . 3. 3, 6-diamine 2, 5-pyrazine dicarbonitrile, formula R ⁹ C〇 OZ (R ⁹ has the same meaning as above, and Z is a sodium or power beam. A carboxylate represented by the following formula: Ha (CH ₂ ) „-al (wherein Hal and hal each independently represent a halogen atom, and n represents the same meaning as described above), and C , ~ C ₆ alkylating agent to react with the general formula [III] Y ¹ Y ³

^{(Wherein, Y ', Y 2, Y} 3, Υ 4 are each independently C i ~ C _{g alkyl, (CH 2) n 0 C} 0 R 9 represents, R ^9, n is the same meaning as described above the expressed.) represented by the compound, then, C, -C ₆ Arukiruaku Li rate Moshiku general formula, characterized in that to C, -C ₆ Arukirume data click relays Bok and ester exchange reaction [I] ' R ⁷

(Wherein, R ^5, R ⁶ , R ⁷ , and R ⁸ have the same meanings as described above.).  4. —Crosslinking or crosslinking obtained by radical polymerization of a compound of the general formula [I] or a mixture of the compound of the general formula [I] and a radically polymerizable compound in the presence of a radical polymerization initiator Non-crosslinked polymer.  5. —Crosslinking characterized by radically polymerizing a compound of the general formula [I] or a mixture of the compound of the general formula [I] and a radically polymerizable compound in the presence of a radical polymerization initiator is also possible. Or a method for producing a non-crosslinked polymer.  6. A polymer compound molded article containing the polymer described in 4. above.