公开(公告)号：WO2006103371A2

公开(公告)日：2006-10-05

申请号：PCT/FR2006050272

申请日：2006-03-29

Applicant: ESSILOR INT ,  GUERRET OLIVIER ,  JAFFRENNOU BORIS ,  LESARTRE NOEMIE ,  MECHIN FRANCOISE ,  PASCAULT JEAN-PIERRE

Inventor： GUERRET OLIVIER ,  JAFFRENNOU BORIS ,  LESARTRE NOEMIE ,  MECHIN FRANCOISE ,  PASCAULT JEAN-PIERRE

CPC classification number: C08L75/04 ,  C08G2270/00 ,  C08L33/08 ,  G02B1/041 ,  C08L33/00 ,  C08L2666/04

Abstract: The invention relates to a polymerisable liquid mixture comprising: (a) a polymerisable thermosetting composition which is a precursor by polymerisation of a first thermoset polymer material, said composition containing at least one polythiol and/or one polyol, preferably a polythiol, and at least one polyiso(thio)cyanate; and (b) a second polymer material solubilised in the aforementioned polymerisable thermosetting composition, whereby the second material (i) contains at least one block copolymer comprising at least two polymer blocks A and B, namely an elastomer block A and a hydrophilic block B, and, following polymerisation of the polymerisable mixture, (ii) forms domains which are rich in elastomer block A and which are dispersed throughout the first material, said domains being smaller than 80 nanometers and preferably smaller than 50 nanometers. The invention also relates to a transparent article having improved toughness, which is produced by means of polymerisation of the above-mentioned polymerisable mixture, comprising an alloy of a first thermoset polymer material forming the matrix of said article and of a second polymer material which is dispersed throughout said first material. The aforementioned articles have improved resistance to impact and to crack propagation. The invention is suitable for use in ophthalmic optics.

Abstract translation: 本发明涉及一种可聚合液体混合物，其包含：（a）可聚合热固性组合物，其是通过第一热固性聚合物材料的聚合的前体，所述组合物含有至少一种多硫醇和/或一种多元醇，优选多硫醇，并且至少 一种多异（硫）氰酸酯; 并且（b）溶解在上述可聚合的热固性组合物中的第二聚合物材料，其中第二材料（i）含有至少一种包含至少两个聚合物嵌段A和B的嵌段共聚物，即弹性体嵌段A和亲水嵌段B， 并且在可聚合混合物聚合之后，（ii）形成富含弹性体嵌段A并且分散在整个第一材料中的畴，所述畴小于80纳米，优选小于50纳米。 本发明还涉及具有改进的韧性的透明制品，其通过上述可聚合混合物的聚合制备，其包含形成所述制品的基质的第一热固性聚合物材料和第二聚合物材料的合金，所述第二聚合物材料是 分散在所述第一材料中。 上述制品具有改善的抗冲击性和抗裂纹性。 本发明适用于眼科镜片。

公开(公告)号：FR2896506B1

公开(公告)日：2008-04-04

申请号：FR0600551

申请日：2006-01-20

Applicant: ESSILOR INT

Inventor： JAFFRENNOU BORIS ,  LESARTRE NOEMIE ,  MECHIN FRANCOISE ,  PASCAULT JEAN PIERRE

IPC: C08L75/00 ,  C08L53/02 ,  G02B1/04 ,  G02C7/02

Abstract: Polymerizable composition comprises: a polyurethane prepolymer obtained by polycondensation of poly-isocyanates (I) e.g. xylylene isocyanate, and polyols (II) e.g. polypropoxylated bisphenol-A having 1-10 propylene oxide units on both sides of the bisphenol-A; an aromatic diamine like diethyltoluene diamine or amine, where the ratio of the amine function number of the diamine to the number of isocyanate function number of the prepolymer is 0.92-0.98; and a copolymer of polystyrene-block-polybutadiene-block-polymethyl methacrylate block at 5 wt.%. Polymerizable composition comprises: a polyurethane prepolymer obtained by polycondensation of poly-isocyanates (I) e.g. xylylene isocyanate, m-tetramethylxylene isocyanate, cycloaliphatic diisocyanates, isophorone diisocyanate trimer or hexamethylene isocyanate trimer, and polyols (II) e.g. polypropoxylated bisphenol-A having 1-10 propylene oxide units on both sides of the bisphenol-A, polyethoxylated bisphenol-A having 1-15 units of ethylene oxide on both sides of the bisphenol-A, or bi-, tri- or tetra-functional polycaprolactone alcoholic; an aromatic diamine like diethyltoluene diamine or amine of formula (a), where the ratio of the number of amine functional groups to the number of isocyanate functional groups is 0.92-0.98; and a copolymer of polystyrene-block-polybutadiene-block-polymethyl methacrylate block at 5 wt.%. R1, R3 : methyl, ethyl, n-propyl or isopropyl; and R2 : H or Cl. Independent claims are included for: (1) a transparent polymerized material obtained by thermal hardening of the polymerizable composition; (2) an optical article comprising the transparent material; and (3) a process of preparing the composition comprising preparing a first component by mixing the prepolymer with the copolymer at a 95:5-20/80 weight ratio, preparing a second component by mixing the diamine with copolymer at a 95/5 and 20/80 weight ratio, and mixing the components in a way that the ratio of the number of the amine groups to the number of isocyanate groups is 0.92-0.98. [Image].

公开(公告)号：DE602006004035D1

公开(公告)日：2009-01-15

申请号：DE602006004035

申请日：2006-03-29

Applicant: ESSILOR INT

Inventor： GUERRET OLIVIER ,  JAFFRENNOU BORIS ,  LESARTRE NOEMIE ,  MECHIN FRANCOISE ,  PASCAULT JEAN-PIERRE

IPC: G02B1/04

Abstract: The invention relates to a polymerisable liquid mixture comprising: (a) a polymerisable thermosetting composition which is a precursor by polymerization of a first thermoset polymer material, said composition containing at least one polythiol and/or one polyol, preferably a polythiol, and at least one polyiso(thio)cyanate; and (b) a second polymer material solubilized in the aforementioned polymerisable thermosetting composition, whereby the second material (i) contains at least one block copolymer comprising at least two polymer blocks A and B, namely an elastomer block A and a hydrophilic block B, and, following polymerization of the polymerisable mixture, (ii) forms domains which are rich in elastomer block A and which are dispersed throughout the first material, said domains being smaller than 80 nanometers and preferably smaller than 50 nanometers. The invention also relates to a transparent article having improved toughness, which is produced by means of polymerization of the above-mentioned polymerisable mixture, comprising an alloy of a first thermoset polymer material forming the matrix of said article and of a second polymer material which is dispersed throughout said first material. The aforementioned articles have improved resistance to impact and to crack propagation. The invention is suitable for use in ophthalmic optics.

公开(公告)号：FR2896507A1

公开(公告)日：2007-07-27

申请号：FR0600552

申请日：2006-01-20

Applicant: ESSILOR INT

Inventor： JAFFRENNOU BORIS ,  LESARTRE NOEMIE ,  MECHIN FRANCOISE ,  PASCAULT JEAN PIERRE

IPC: C08L75/00 ,  C08L53/02 ,  G02B1/04 ,  G02C7/02

Abstract: Composition polymérisable comprenant (a) un ou plusieurs polyisocyanates particuliers ou un prépolymère de polyuréthane obtenu par polycondensation d'un polyisocyanate en excès, choisi parmi lesdits polyisocyanates, et d'un ou plusieurs polyols comprenant au moins deux fonctions alcools libres, choisis parmi les bisphénols A polypropoxylés ou polyéthoxylés, et les polycaprolactones-alcools polyfonctionnels; (b) un ou plusieurs polyols comprenant au moins deux fonctions alcools libres, choisis parmi les bisphénols A polypropoxylés ou polyéthoxylés et les polycaprolactones-alcools polyfonctionnels, et les prépolymères de polyuréthane obtenus par polycondensation d'un ou plusieurs polyols en excès, choisis parmi les polyols ci-dessus et d'un ou plusieurs polyisocyanates particuliers; le rapport du nombre de fonctions isocyanate du composant polyisocyanate (a) au nombre de fonctions alcool du composant polyol (b) étant compris entre 1,00 et 1,20; et (c) de 5 % à 80% en poids, rapporté à la masse totale de (a), (b) et (c), d'un ou plusieurs copolymères à blocs polystyrène-bloc-polybutadiène-bloc-poly(méthacrylate de méthyle) ; procédé de préparation d'une telle composition et matériau optique transparent obtenu par chauffage de ladite composition.

公开(公告)号：FR2896506A1

公开(公告)日：2007-07-27

申请号：FR0600551

申请日：2006-01-20

Applicant: ESSILOR INT

Inventor： JAFFRENNOU BORIS ,  LESARTRE NOEMIE ,  MECHIN FRANCOISE ,  PASCAULT JEAN PIERRE

IPC: C08L75/00 ,  C08L53/02 ,  G02B1/04 ,  G02C7/02

Abstract: Composition polymérisable comprenant (a) un prépolymère de type polyuréthanne et (b) une diamine aromatique notamment de formule (I), en une quantité telle que le rapport du nombre de fonctions aminé de la diamine de formule (I) au nombre de fonctions isocyanate du prépolymère (a) est compris entre 0,92 et 0,98, et au moins 5 % en poids, rapporté à la masse totale de (a), (b) et (c), d'un copolymère à blocs polystyrène-bloc-polybutadiène-bloc-poly(méthacrylate de méthyle); procédé de préparation d'une telle composition et matériau optique transparent obtenu par traitement thermique de ladite composition.

公开(公告)号：AT416392T

公开(公告)日：2008-12-15

申请号：AT06726287

申请日：2006-03-29

Applicant: ESSILOR INT

Inventor： GUERRET OLIVIER ,  JAFFRENNOU BORIS ,  LESARTRE NOEMIE ,  MECHIN FRANCOISE ,  PASCAULT JEAN-PIERRE

IPC: G02B1/04

Abstract: The invention relates to a polymerisable liquid mixture comprising: (a) a polymerisable thermosetting composition which is a precursor by polymerization of a first thermoset polymer material, said composition containing at least one polythiol and/or one polyol, preferably a polythiol, and at least one polyiso(thio)cyanate; and (b) a second polymer material solubilized in the aforementioned polymerisable thermosetting composition, whereby the second material (i) contains at least one block copolymer comprising at least two polymer blocks A and B, namely an elastomer block A and a hydrophilic block B, and, following polymerization of the polymerisable mixture, (ii) forms domains which are rich in elastomer block A and which are dispersed throughout the first material, said domains being smaller than 80 nanometers and preferably smaller than 50 nanometers. The invention also relates to a transparent article having improved toughness, which is produced by means of polymerization of the above-mentioned polymerisable mixture, comprising an alloy of a first thermoset polymer material forming the matrix of said article and of a second polymer material which is dispersed throughout said first material. The aforementioned articles have improved resistance to impact and to crack propagation. The invention is suitable for use in ophthalmic optics.

公开(公告)号：FR2896507B1

公开(公告)日：2008-04-04

申请号：FR0600552

申请日：2006-01-20

Applicant: ESSILOR INT

Inventor： JAFFRENNOU BORIS ,  LESARTRE NOEMIE ,  MECHIN FRANCOISE ,  PASCAULT JEAN PIERRE

IPC: C08L75/00 ,  C08L53/02 ,  G02B1/04 ,  G02C7/02

Abstract: Polymerizable composition comprises: polyisocyanates comprising at least two free isocyanate functions e.g. (1) xylylene-diisocyanate, (2) polyurethane prepolymers obtained by polycondensation of polyisocyanates, and polyols comprising (3) at least two free alcohol functions e.g. polypropoxylated bisphenol A comprising 1-10 propylene oxide unit on both sides of the central bisphenol A group; polyols comprising e.g. polyurethane prepolymers obtained by polycondensation of excess polyol; and polystyrene-block-polybutadiene-block-poly(methyl methacrylate) blocks copolymer (5-80 wt.%). Polymerizable composition comprises: polyisocyanates comprising at least two free isocyanate functions such as (1) xylylene-diisocyanate, meta-tetramethyl-xylylene-diisocyanate, cycloaliphatic diisocyanates, isophorone-diisocyanate trimer and hexamethylene-diisocyanate trimer, and (2) polyurethane prepolymers obtained by polycondensation of polyisocyanates in excess such as polyisocyanates (1) and polyols comprising (3) at least two free alcohol functions such as polypropoxylated bisphenol A comprising 1-10 propylene oxide unit on both sides of the central bisphenol A group, 1-15 ethylene oxide units on both sides of central bisphenol A group, bifunctional, trifunctional and tetrafunctional polycaprolactone-alcohol; polyols comprising (3) and polyurethane prepolymers obtained by polycondensation of excess polyols such as the polyols (3), where the ratio of the isocyanate function number of the polyisocyanate component to the alcohol function number of the polyol component is 1:1.2; and polystyrene-block-polybutadiene-block-poly(methyl methacrylate) blocks copolymer (5-80 wt.%). Independent claims are included for: (1) a preparation of the composition comprising preparing a first composition comprising mixing the polyisocyanate component with the polystyrene-block-polybutadiene-block-poly(methyl methacrylate) blocks copolymer, where the weight ratio of the polyisocyanate component to the blocks copolymer is 95/5 to 20/80, preparing a second composition comprising mixing the polyol component with polystyrene-block-polybutadiene-block-poly(methyl methacrylate) blocks copolymer, where the weight ratio of the polyol to the copolymer blocks is 95/5 to 20/80, and mixing the first composition with the second composition, or preparing the first composition and mixing the polyol component with the first composition, or preparing the second composition and mixing the second composition with the polyisocyanate component, in respective quantities, where the ratio of the isocyanate function number to the alcohol function number is 1:1.2; (2) a transparent polymerized material obtained by thermal hardening of the polymerizable composition; and (3) a optical article comprising the transparent polymerized material.

公开(公告)号：FR2883880B1

公开(公告)日：2007-05-11

申请号：FR0550847

申请日：2005-03-31

Applicant: ESSILOR INT

Inventor： GUERRET OLIVIER ,  JAFFRENNOU BORIS ,  LESARTRE NOEMIE ,  MECHIN FRANCOISE ,  PASCAULT JEAN PIERRE

IPC: C08L75/04 ,  C08G18/72 ,  C08L53/02 ,  G02B1/04 ,  G02C7/02

Abstract: The invention relates to a polymerisable liquid mixture comprising: (a) a polymerisable thermosetting composition which is a precursor by polymerization of a first thermoset polymer material, said composition containing at least one polythiol and/or one polyol, preferably a polythiol, and at least one polyiso(thio)cyanate; and (b) a second polymer material solubilized in the aforementioned polymerisable thermosetting composition, whereby the second material (i) contains at least one block copolymer comprising at least two polymer blocks A and B, namely an elastomer block A and a hydrophilic block B, and, following polymerization of the polymerisable mixture, (ii) forms domains which are rich in elastomer block A and which are dispersed throughout the first material, said domains being smaller than 80 nanometers and preferably smaller than 50 nanometers. The invention also relates to a transparent article having improved toughness, which is produced by means of polymerization of the above-mentioned polymerisable mixture, comprising an alloy of a first thermoset polymer material forming the matrix of said article and of a second polymer material which is dispersed throughout said first material. The aforementioned articles have improved resistance to impact and to crack propagation. The invention is suitable for use in ophthalmic optics.

公开(公告)号：FR2883880A1

公开(公告)日：2006-10-06

申请号：FR0550847

申请日：2005-03-31

Applicant: ESSILOR INT

Inventor： GUERRET OLIVIER ,  JAFFRENNOU BORIS ,  LESARTRE NOEMIE ,  MECHIN FRANCOISE ,  PASCAULT JEAN PIERRE

IPC: C08L75/04 ,  C08G18/72 ,  C08L53/02 ,  G02B1/04 ,  G02C7/02

Abstract: La présente invention a pour objet un mélange polymérisable liquide comprenant (a) une composition polymérisable thermodurcissable, précurseur par polymérisation d'un premier matériau polymère thermodurci, ladite composition comprenant au moins un polythiol et/ou un polyol, préférentiellement un polythiol, et au moins un polyiso(thio)cyanate, (b) un second matériau polymère solubilisé dans ladite composition polymérisable thermodurcissable, ledit second matériau (i) comprenant au moins un copolymère à blocs comprenant au moins deux blocs polymériques A et B, ledit bloc A étant un bloc élastomère et ledit bloc B étant un bloc hydrophile et (ii) formant, après polymérisation du mélange polymérisable, des domaines riches en bloc élastomère A dispersés au sein du premier matériau, lesdits domaines étant de dimensions inférieures à 80 nanomètres, de préférence inférieures à 50 nanomètres. La présente invention a également pour objet un article transparent à ténacité améliorée fabriqué par polymérisation du mélange polymérisable ci-dessus, comprenant un alliage d'un premier matériau polymère thermodurci constituant la matrice dudit article, et d'un second matériau polymère dispersé au sein dudit premier matériau. Ces articles présentent une meilleure résistance aux chocs et à la propagation de fissures. Application à l'optique ophtalmique.