Laminate and method for its preparation

Claim 2

A transparent laminate made of a transparent hard material having a soft synthetic resin layer on its surface, wherein the soft synthetic resin layer has, at its exposed surface side, a surface of a cross-linked polyurethane type resin having a self-healing property with the surface reformed by impregnating an addition-polymerizable unsaturated compound into the cross-linked polyurethane resin surface and polymerizing the impregnated compound.

Claim 3

The laminate according to Claim 1, which comprises a layer of the transparent hard material, a layer of the cross-linked polyurethane type resin formed on one side thereof, and a layer of an adhesive material located between them and bonding them.

Claim 4

The laminate according to Claim 1 or 2, wherein the transparent hard material is a sheet of inorganic glass.

Claim 5

The laminate according to Claim 2 or 3, wherein the adhesive material is a thermoplastic synthetic resin.

Claim 6

The laminate according to Claims 1 to 4, wherein the addition-polymerizable unsaturated compound is at least one compound selected from the group consisting of acrylates and methacrylates.

Claim 7

6 . The laminate according to Claimsl to 5, wherein the cross-linked polyurethane type resin prior to the surface-reforming is a cross-linked polyurethane type resin having a self-healing property and having an elongation of at least about 250% and a breaking strength of at least about 300 kg/cm 2 .

Claim 8

The laminate according to Claimsl to 6, wherein the cross-linked polyurethane type resin is a cross-linked polyurethane type resin obtained by reacting (a) a relatively high molecular weight polyol comprising at least one diol and at least one tri- or higher valent polyol and having,an equivalent ratio of the tri- or higher valent polyol to the diol of from about 0.1 to about 0.6 and an average hydroxyl value of from about 70 to about 150, (b) a substantially bivalent chain extender in an amount of from about 0.4 to about 1.8 equivalent relative to one equivalent of the above polyol, and (c) a substantially bivalent polyisocyanate compound in an amount of from about 0.8 to about 1.2 equivalent relative to one equivalent of the total of the above polyol and chain extender.

Claim 9

The laminate according to Claim 7, wherein the relatively high molecular weight polyol is a relatively high molecular weight polyol comprising at least one diol having a hydroxyl value of from about 60 to about 130 and at least one tri- or higher valent polyol having a hydroxyl value of from about 150 to about 250, which has an average hydroxyl value of from about 80 to about 140, whereby preferably at least a part of the relatively high molecular weight polyol is a polycarbonate type polyol.

Claim 10

-9. The laminate according to claim 8, wherein the relatively high molecular weight polyol comprises the polycarbonate type polyol and a polyester type polyol.

Claim 11

The laminate according to Claim 9, wherien the diol comprises a polycarbonate type diol and a polyester type diol whereby preferably the diol contains at least about 15% by weight of the polycarbonate type diol.

Claim 12

The laminate according to Claim 9 , wherein the tri-or higher valent polyol is a tri- or higher valent polyester type polyol.

Claim 13

The laminate according to Claim 7, wherein the surface reformed cross-linked polyurethane type resin layer is a layer of a sheet obtained by surface-reforming one side of a cross-linked polyurethane type resin sheet obtained by cast molding a material of the cross-linked polyurethane type resin as defined in Claim 7 by a one-shot method.

Claim 15

The method according to Claim 13, wherein the addition-polymerizable unsaturated compound is polymerized by irradiation of energy rays, preferably ultraviolet rays.

Claim 16

15 . A pre-laminated sheet of a cross-linked polyurethane type resin having, at one side, a surface reformed by the impregnation and polymerization of an addition-polymerizable unsaturated compound and having a self-healing property and, at the other side, a layer of an adhesive material, said components being preferably as defined in one of claims 4 to 12.

Claim 17

A method for preparating a pre-laminated sheet according to claim 15, which comprises forming a layer of an adhesive material on one side of a sheet of a cross-linked polyurethane type resin having a self-healing property, protecting the surface of the adhesive material layer with a removable protective film or sheet, and then impregnating an addition-polymerizable unsaturated compound into the exposed side of the cross-linked polyurethane resin sheet and polymerizing the impregnated compound.

Claim 18

The method according to Claim 16, wherein the addition-polymerizable unsaturated compound is polymerized by irradiation of energy rays, preferably ultraviolet rays.

Claim 19

18 . The method according to Claims 16 or 17, wherein the removable protective film or sheet is made of a polyolefin type resin.

Claim 21

A sheet of a cross-linked polyurethane type resin having a self-healing property and having an elongation of at least about 250% and a breaking strength of at least about 300 kg/cm 2 , wherein the cross-linked polyurethane type resin is a cross-linked polyurethane type resin obtained by reacting (a) a relatively high molecular weight polyol comprising at least one diol and at least one tri- or higher valent polyol and having an equivalent ratio of the tri- or higher valent polyol to the diol of from about 0.1 to about 0.6 and an average hydroxyl value of from about 70 to about 150, wherein at least a part of the relatively high molecular weight polyol is a polycarbonate type polyol, (b) a substantially bivalent chain extender in an amount of from about 0.4 to about 1.8 equivalent relative to one equivalent of the above polyol, and (c) a substantially bivalent polyisocyanate compound in an amount of from about 0.8 to about 1.2 equivalent relative to one equivalent of the total of the above polyol and chain extender said components being preferably as defined in one of claims 8 to 11.

Claim 22

The sheet according to Claim 20, which is obtained by a one-shot method.