公开(公告)号：FR2763066B1

公开(公告)日：2001-01-05

申请号：FR9803379

申请日：1998-03-19

Applicant: AGENCY IND SCIENCE TECHN

Inventor： MATSUDA HIROO ,  FUKUDA TAKASHI ,  YAMADA SHINJI ,  KIMURA TATSUMI ,  KATO MASAO ,  BUAN XUAN MING ,  OKADA SHUJI ,  NAKANISHI HACHIRO

IPC: C07C69/92 ,  C07C205/43 ,  C07C255/55 ,  C08F2/00 ,  G02F1/361 ,  G02F1/35

Abstract: Disclosed is a novel aromatic ester compound represented by the general formula in which Pn is a 1,4-phenylene group, R1 is an alkyl group having 1 to 4 carbon atoms, R2 is a group selected from the group consisting of perfluoroalkyl groups having 1 to 4 carbon atoms, cyano group, nitro group, 2,2-dicyanoethenyl group and methylsulfonyl group and the subscript n is a number of 2, 3 or 4. These aromatic ester compounds are useful as a second-order non-linear optical material in the ultraviolet wavelength range so that a resin film containing the compound has a good second-order non-linear optical coefficient d33 of 2-4x10-9 esu.

公开(公告)号：FR2763066A1

公开(公告)日：1998-11-13

申请号：FR9803379

申请日：1998-03-19

Applicant: AGENCY IND SCIENCE TECHN

Inventor： MATSUDA HIROO ,  FUKUDA TAKASHI ,  YAMADA SHINJI ,  KIMURA TATSUMI ,  KATO MASAO ,  BUAN XUAN MING ,  OKADA SHUJI ,  NAKANISHI HACHIRO

IPC: C07C69/92 ,  C07C205/43 ,  C07C255/55 ,  C08F2/00 ,  G02F1/361 ,  G02F1/35

Abstract: Disclosed is a novel aromatic ester compound represented by the general formula in which Pn is a 1,4-phenylene group, R1 is an alkyl group having 1 to 4 carbon atoms, R2 is a group selected from the group consisting of perfluoroalkyl groups having 1 to 4 carbon atoms, cyano group, nitro group, 2,2-dicyanoethenyl group and methylsulfonyl group and the subscript n is a number of 2, 3 or 4. These aromatic ester compounds are useful as a second-order non-linear optical material in the ultraviolet wavelength range so that a resin film containing the compound has a good second-order non-linear optical coefficient d33 of 2-4x10-9 esu.

公开(公告)号：JPH1180275A

公开(公告)日：1999-03-26

申请号：JP25590997

申请日：1997-09-04

Applicant: AGENCY IND SCIENCE TECHN ,  MATSUDA HIROO ,  FUKUDA TAKASHI

Inventor： MATSUDA HIROO ,  FUKUDA TAKASHI ,  YAMADA SHINJI ,  KATO MASAO ,  NAKANISHI HACHIRO

IPC: G02F1/35 ,  C08F8/30 ,  C08F220/60 ,  C08F222/40 ,  G02F1/355 ,  G02F1/361

Abstract: PROBLEM TO BE SOLVED: To obtain a novel polymeric substance suppressed in the relaxation of an aligned structure at high temperatures and having good heat stability and secondary nonlinear optical properties by using an acrylamide copolymer comprising three types of repeating units having specified structures and having a specified weight-average molecular weight. SOLUTION: The acrylamide copolymer comprises repeating units represented by formula I, repeating units represented by formula II (wherein R is H or methyl; and R is H or methyl bonded in an o- or m-position) and repeating units represented by formula III (wherein R and R are as defined in formula II) and has a weight-average molecular weight of 50,000-300,000. This copolymer can be produced by radical-copolymerizing N-phenylmaleimide with N-(N-phenyl- N-methyl)aminoethylacrylamide and effecting the diazo coupling of the obtained copolymer with nitroaniline. The ratio of the compound of formula I to the compound of formula II is 2: 1 to 1:2 by mole.

公开(公告)号：JPH1121272A

公开(公告)日：1999-01-26

申请号：JP13437198

申请日：1998-04-28

Applicant: AGENCY IND SCIENCE TECHN ,  MATSUDA HIROO ,  FUKUDA TAKASHI

Inventor： MATSUDA HIROO ,  FUKUDA TAKASHI ,  YAMADA SHINJI ,  KIMURA TATSUMI ,  KATO MASAO ,  DAN NOBUAKI ,  OKADA SHUJI ,  NAKANISHI HACHIRO

IPC: G02F1/35 ,  C07C67/14 ,  C07C69/92 ,  C07C69/94 ,  C07C201/12 ,  C07C205/43 ,  C07C255/01 ,  C07C255/38 ,  C07C255/55 ,  C07C317/22 ,  G02F1/355 ,  G02F1/361

Abstract: PROBLEM TO BE SOLVED: To obtain the subject new compound excellent in secondary nonlinear optical characteristics, having excellent optical transparency. SOLUTION: This compound is that one expressed by formula I [R is a lower alkyl; R is perfluoroalkyl, cyano, nitro, 2,2-dicyanoethenyl or methylsulfonyl; (n) is 1-3], e.g. 4-anisic acid 4-cyanophenyl-ester. The compound of formula I is obtained by adding p-substituted phenol expressed by formula III little by little into a solvent contg. an aromatic carboxylic halide expressed by formula II (X is a halide) at room temperature or under iced conditions, reacting with each other in the presence of a hydrogen halide catcher (e.g. a tertiary amine, such as trimethylamine, triethylamine, pyridine), preferably, in an inert solvent (e.g. acetone, methylethylketone, diethylether) for 1-30 hrs., washing the resulting product with water and separating the organic layer to remove the solvent.

公开(公告)号：JPH1180276A

公开(公告)日：1999-03-26

申请号：JP25935597

申请日：1997-09-08

Applicant: AGENCY IND SCIENCE TECHN ,  MATSUDA HIROO ,  FUKUDA TAKASHI

Inventor： MATSUDA HIROO ,  FUKUDA TAKASHI ,  YAMADA SHINJI ,  KATO MASAO ,  NAKANISHI HACHIRO

IPC: G02F1/35 ,  C08F8/30 ,  C08F212/12 ,  C08F222/40 ,  G02F1/355 ,  G02F1/361

Abstract: PROBLEM TO BE SOLVED: To obtain a novel polymeric substance which does not show the relaxation of an aligned structure at high temperatures and having good heat stability and quadratic nonlinear optical properties by using a maleimide/styrene copolymer comprising three types of structural units having specified structures and having a specified number-average molecular weight. SOLUTION: This copolymer comprises structural units of formulas I, II and III (wherein R is H or methyl) and has a number-average molecular weight of 10,000-200,000. This is obtained by the following reactions. A mixture of N-(4-hydroxyphenyl)maleimide represented by formula I with an α-methylstyrene represented by formula II is heated to 50-100 deg.C in the presence of a radical polymerization initiator (e.g. acetyl peroxide) in a polymerization solvent (the ratio between the constituents of the mixture is in the range of 2:1 to 1:2). The obtained white solid is reacted with a red dye represented by formula IV (wherein R is H or methyl) in the presence of a condensing agent in a reaction solvent to obtain a compound comprising structural units of formulas I to III and being in the form of a reddish brown solid.

公开(公告)号：JPH10306132A

公开(公告)日：1998-11-17

申请号：JP13432297

申请日：1997-05-08

Applicant: AGENCY IND SCIENCE TECHN ,  MATSUDA HIROO ,  FUKUDA TAKASHI

Inventor： MATSUDA HIROO ,  FUKUDA TAKASHI ,  YAMADA SHINJI ,  KATO MASAO ,  NAKANISHI HACHIRO

IPC: G02F1/35 ,  C08F220/60 ,  G02F1/355 ,  G02F1/361

Abstract: PROBLEM TO BE SOLVED: To obtain a high-molecular material which undergoes controlled relaxation of an orientation structure at high temperature and has secondary nonlinear optical characteristics with good heat stability by subjecting a polymer obtained through the radical polymerization of a specified aniline derivative to diazo coupling with nitroaniline. SOLUTION: An aniline derivative of formula I (wherein R is H or methyl; and R is H, or methyl bound at a position other than the 4-position) is subjected to radical polymerization in the presence of 0.05-5.0 wt.% radical polymerization initiator at 50-100 deg.C for 10-50 hr to give a polymer having a weight-average molecular weight of 42,000 to 270,000. This polymer is subjected to diazo coupling with nitroaniline to introduce at least 20 mol.%, preferably 25-95 mol.%, azo groups, thus giving a nonlinear acrylamide polymer consisting of constituent units of formula II and those of formula II, and having a weight-average molecular weight of 50,000 to 300,000, an optimum poling temperature of 150-170 deg.C, and an initial d33 value at 80 deg.C of at least 200×10 esu.

公开(公告)号：JPH10306130A

公开(公告)日：1998-11-17

申请号：JP13433697

申请日：1997-05-08

Applicant: AGENCY IND SCIENCE TECHN ,  MATSUDA HIROO ,  FUKUDA TAKASHI

Inventor： MATSUDA HIROO ,  FUKUDA TAKASHI ,  YAMADA SHINJI ,  KATO MASAO ,  NAKANISHI HACHIRO

IPC: G02F1/35 ,  C08F212/06 ,  C08F212/08 ,  C08F212/14 ,  C08F220/52 ,  C08F222/40 ,  G02F1/355 ,  G02F1/361

Abstract: PROBLEM TO BE SOLVED: To obtain a new high-molecular material which does not show the relaxation of an orientation structure at high temperature and has secondary nonlinear optical characteristics with good heat stability by heating a mixture of N-phenylmaleimide and 4-hydroxy-α-methylstyrene in a polymerization solvent in the presence of a radical polymerization initiator and reacting the obtained copolymer with a red dye having a specified structure. SOLUTION: This material comprises a maleimide-styrene copolymer consisting of constituent units represented by formula I, those represented by formula I and those represented by formula III (wherein R is H or methyl) and having a number-average molecular weight of 10,000 to 200,000. The molar ratio of constituent units of formula I to those of formula II is (2:1) to (1:2). The radical polymerization initiator used comprises, e.g. benzoyl peroxide, which is used in an amount of 0.05-5.0 wt.% based on the total weight of monomers. The copolymerization temperature is 50-100 deg.C, and the polymerization time is 10-50 hr. The amount of the red dye introduced is 50-95 mol.%. It is obtained as a reddish brown solid with a glass transition temperature of 190 deg.C.