JPH0710584B2 - Laminated body and manufacturing method thereof - Google Patents

Description

TECHNICAL FIELD The present invention relates to a laminate including a layer of a transparent crosslinkable polyurethane resin sheet having a self-repairing property and a peelable protective material.

[Prior Art] An optically smooth sheet of a transparent cross-linked polyurethane-based resin having a self-healing property is known as a material for producing laminated safety glass. For example, a laminated safety glass obtained by laminating two sheets of inorganic glass sheets on one surface of a laminated glass formed by laminating a polyvinyl butyral resin intermediate film (see Japanese Patent Publication No. 59-48775). Laminated safety glass obtained by laminating one sheet of an inorganic glass sheet or the above-mentioned laminated glass with an adhesive synthetic resin layer such as thermoplastic polyurethane resin on one side (JP-A-53-
27671 and JP-A-60-71252), laminated safety glass in which a transparent hard plastic sheet such as a polycarbonate resin is laminated on one side (see JP-A-60-71252).
No. 53-27671) is known. Especially 1
Laminated safety glass obtained by laminating one sheet of an inorganic glass sheet on one side is highly safe and lightweight, and therefore suitable for use as a window material for automobiles. The self-healing property of the cross-linked polyurethane-based resin means the property that scratches formed on the surface disappear naturally over time (see Japanese Patent Publication No. 55-6657), and deterioration of optical properties due to scratches on the surface. This is a property required to prevent This self-healing property is a property exhibited by a specific type of cross-linked polyurethane resin.

The laminated safety glass requires at least one layer of a relatively soft synthetic resin layer having mechanical properties such as penetration resistance (hereinafter referred to as penetration resistance layer). For example, in laminated glass, the interlayer film is a penetration resistant layer. In the above laminated safety glass using one sheet of inorganic glass, the adhesive synthetic resin layer needs to have penetration resistance. Therefore,
In one using one of the laminated safety glass sheets described in JP-A-53-27671, the adhesive synthetic resin is a thermoplastic synthetic resin having high mechanical properties and high thermoplasticity, and The adhesive synthetic resin layer is used as a penetration resistant layer (called an energy absorption layer) as a thick layer of 0.5 mm or more. On the other hand, recently, a laminated safety glass has been proposed in which the mechanical properties of a crosslinkable polyurethane resin having self-healing property are enhanced, and only the layer has both penetration resistance and surface characteristics (JP-A-60-71253). reference). However, the surface properties such as self-repairing property of the crosslinkable polyurethane-based resin are not always sufficient, and it is considered that it is desirable that the surface layer is composed of the conventional crosslinkable polyurethane-based resin layer (JP-A-60-71252). See the bulletin). Furthermore, the present inventors have found a cross-linked polyurethane resin having excellent surface properties and mechanical properties (Japanese Patent Application No. 60-18692,
And Japanese Patent Application No. 60-19266). However, the adhesiveness of this material to the surface of the inorganic glass may not always be sufficient, and it is desirable to laminate it on the surface of the inorganic glass via a layer of an extremely thin (less than about 0.2 mm) adhesive substance.

The cross-linked polyurethane-based resin is required to have uniform transparency (however, it may be partially or wholly colored), optical resistance such as discoloration resistance, and the like as its material. However, even more than that, high optical performance as a sheet is required. That is, both sides of the sheet need to be extremely smooth and their thickness needs to be uniform. It is desirable that such a sheet be produced by a casting method, and particularly it is desirable that it be produced by a continuous casting method from the viewpoint of productivity. The production of a crosslinked polyurethane-based resin sheet by a continuous casting method is known, for example, JP-A-56-1626.
No. 18 and JP-A-60-48312. The crosslinkable polyurethane resin sheet is produced on a smooth film or sheet having a peelable surface (hereinafter referred to as a peelable substrate), and the peelable substrate may not be peeled until just before the production of laminated safety glass. desirable. This is because it is desirable that the peelable base material be used as it is as a protective material for the surface of the sea. During production of laminated safety glass, if foreign substances such as dust are present on the surface of the sheet (that is, the laminating surface) laminated on the surface of inorganic glass or the like, it is impossible to remove it after laminating. Is. Therefore, it is desirable that the laminated surface of the sheet is protected with a protective material composed of a film or sheet having a peelable surface until just before laminating so that foreign matter and dirt do not adhere.
On the other hand, it was considered that the other surface of the sheet did not need to be protected. This is because that surface will eventually become one surface of the laminated safety glass, so that foreign substances and dirt can be removed after the laminated safety glass is manufactured, and since it has self-repairing properties, it does not cause scratches. is there. In the first place, the fact that irremovable foreign matter or dirt easily adheres to this surface, or that scratches that do not disappear tend to be generated, indicate that the surface itself is unsuitable as the surface of laminated safety glass. A crosslinked polyurethane resin sheet having surface properties is not suitable as a material for laminated safety glass.

[Problems to be Solved by the Invention] Although the surface characteristics of the cross-linked polyurethane resin sheet are extremely excellent, the surface not protected by the protective material is apt to cause optical defects for a certain period of time. The present inventor has found that The certain period of time is about several days when the sheet is short after being manufactured. At this time, if the exposed surface of the sheet is scratched, it is difficult to be self-repaired, and if stain is generated, it becomes difficult to remove the stain after that.
Furthermore, when something touches the surface, a contact mark that is difficult to be repaired may occur. It is expected that the cause of this is that the surface properties of the crosslinked polyurethane-based resin immediately after production have not been fully exhibited because the reaction has not been completely completed. Therefore, it is expected that the occurrence of the above-mentioned defects can be prevented by performing sufficient after-curing at the time of producing the sheet to make the reaction more complete, but in reality, this did not solve the problem. It was thought that the cause was that the unreacted part did not react sufficiently by simple heating, and it took a certain amount of time or more to complete the reaction. For example, it is believed that unreacted isocyanate groups do not react even under heating unless there are reactive groups nearby. But,
In continuous sheet production, it is almost impossible to heat the sheet for a long time or keep it at room temperature in a continuous process. It is also difficult to keep a long sheet so that the exposed surface does not have defects.

Conventionally, although the above-mentioned problems have not been recognized, the sheet produced by the casting method has been wound up together with the releasable base material in view of its handling. Therefore, in the wound state, the exposed surface of the sheet was protected by the back surface of the peelable substrate. However, the back surface of the releasable substrate was liable to be scratched when sliding on the substrate therebelow, and foreign matter such as dust was also likely to adhere to the back surface. Further, depending on the releasable base material, the back surface of the releasable base material may not have sufficient smoothness or may have stains. Therefore, if the back surface of the releasable base material is protected by the exposed surface of the sheet, there is not a small possibility that optical defects will occur.

[Means for Solving Problems] The present invention has been made to solve the above problems, and there is a possibility that at least the above-mentioned optical defects may occur on the exposed surface of the crosslinked polyurethane-based resin sheet. The point is to protect with a protective material until it disappears. Of course,
In the case where the other surface of the sheet or the sheet provided with the adhesive synthetic resin layer, the surface of the layer needs to be protected by a protective material.
Protective materials are usually used on each side of the sheet (ie,
One side of the protective material protects one surface of the sheet). However, in some cases, one side of the sheet may be protected by one sheet of protective material without using both sides of the one sheet of protective material as described above. For example, one sheet of protective material is folded in two in the width direction or the length direction, and the sheet is sandwiched therebetween, so that both sides of the sheet can be protected by only one surface of one protective material.

The present invention relates to a laminate comprising a sheet protected by the protective material as described above, and a method for producing the laminate described later, that is, the laminate is the following invention.

An optically smooth sheet of transparent crosslinkable polyurethane resin having self-repairing property, or a sheet of the crosslinkable polyurethane resin having an adhesive synthetic resin layer provided on one surface thereof A layered product that is protected on one side.

Two examples of the laminate of the present invention are shown in FIGS. 1 and 2 as schematic partial sectional views. FIG. 1 shows a laminate of a cross-linked polyurethane resin sheet (1), a first protective material (2), and a second protective material (3). The cross-linking polyurethane resin sheet (1) contact surface of each protective material (2), (3) is a peelable surface, and the protective materials (2), (3) are removed when necessary.
FIG. 2 shows a laminate comprising a cross-linked polyurethane resin sheet (1), an adhesive synthetic resin layer (4), a first protective material (5), and a second protective material (6). The adhesive synthetic resin layer (4) is adhered to one surface of the crosslinked polyurethane-based resin sheet (1), and the other surface is protected by the first protective material (5). The other surface of the crosslinked polyurethane-based resin sheet (1) is protected by the second protective material (6). The surface of each protective material (5), (6) that contacts the surface of the adhesive synthetic resin layer and the surface of the cross-linked polyurethane-based resin sheet is a peelable surface.

The laminated body shown in FIG. 1 has a continuous reactive raw material mixture capable of forming a crosslinked polyurethane-based resin on the surface of the first protective material (2) which can also serve as a peelable substrate having a smooth surface. It is manufactured by covering the upper surface with the second protective material (3) after the cross-linked polyurethane-based resin is almost completely cured by being cast and cured (that is, by performing the continuous casting method).
In addition, before or after covering the second protective material (3),
The surface exposed by peeling off the first protective material used as the peelable base material can be covered with another first protective material. This is because the protective material used as the releasable substrate is often a thick material having relatively high rigidity, which may cause inconvenience in winding and subsequent handling. The laminated body shown in FIG. 2 can also be manufactured by various methods. For example, an adhesive synthetic resin layer (4) is first formed by a casting method on a first protective material (5) which can also be used as a peelable substrate, and then a cross-linkable polyurethane resin is formed on that layer in the same manner as above. The sheet (1) is continuously formed by a casting method (for the two-stage casting method, see, for example, JP-A-56-162618).
(Described in Japanese Unexamined Patent Publication (Kokai)), the cross-linked polyurethane-based resin is almost completely cured, and then the upper surface is covered with a second protective material (6).
It is manufactured by covering with. It is also possible to obtain the same laminate by performing the two-stage casting in the reverse order. further,
After the cross-linking polyurethane-based resin sheet (1) is manufactured on the first protective material (5) by a casting method, the protective material (5) is prepared.
To form an adhesive synthetic resin layer (4) on the surface exposed by the peeling, and thereafter or at the same time, cover the other surface of the adhesive synthetic resin layer with a protective material to form the adhesive synthetic resin layer. The top surface of the seat is
It is manufactured by covering with the protective material (6). As a method of covering the surface with an adhesive synthetic resin layer at the same time with a protective material,
First, there is a method in which an adhesive synthetic resin layer is provided on the surface of the protective material, and the exposed surface of this layer is laminated on the surface of the sheet (1) by pressing or heating. Because of its ease of manufacture, the preferred method is to provide an adhesive synthetic resin layer on the exposed surface of the sheet produced on a releasable substrate, and at the same time as or after the formation of this layer, protect the surface of that layer with a protective material. It is a method of covering with.

The surface of the protective material that comes into contact with the surface of the crosslinked polyurethane-based resin sheet is preferably a smooth surface. But,
The surface of the protective material that contacts the surface of the adhesive synthetic resin layer does not necessarily have to be smooth. Because the adhesive synthetic resin has plasticity, even if there is some unevenness on the surface, when laminated with inorganic glass etc., the surface is pressed against the surface of inorganic glass etc. Because it becomes a face. Rather, when stacking under reduced pressure to prevent air bubbles and the like from remaining between the stacking surfaces, fine unevenness is formed on the surface of the adhesive synthetic resin layer in order to secure a passage for removing air from between the stacking surfaces. It is preferable to form (so-called emboss). The fine irregularities are preferably formed by using a protective material having a fine irregular surface and transferring the irregularities on the surface of the protective material to the surface of the adhesive synthetic resin layer.
For example, a method of transferring a protective material having fine irregularities on the surface of the adhesive synthetic resin layer by pressing or heating and pressing, and after forming the adhesive synthetic resin layer on the surface of the protective material, this is crosslinked polyurethane-based. An adhesive synthetic resin layer having fine irregularities and protected by a protective material is formed by a method such as laminating on a resin sheet.

The surface of the cross-linked polyurethane-based resin sheet, which is the exposed surface of the laminated safety glass, is preferably surface-modified. The surface modification is performed in order to improve other surface properties such as stain resistance and touch without losing the self-repairing property. This surface modification is carried out by impregnating the surface of the cross-linked polyurethane-based resin sheet with a compound having an addition-polymerizable unsaturated group such as an acryloyloxy group or a methacryloyloxy group (hereinafter referred to as a polymerizable compound), and applying ultraviolet rays or electron beams. It is done by polymerizing it with energy rays and heat. Representative examples of the polymerizable compound include polyfunctional compounds such as polyacrylates of polyhydric alcohols, monofunctional compounds such as alkyl acrylates, and other acrylate compounds and methacrylate compounds. The polymerization is preferably performed by energy rays such as ultraviolet rays. It is not preferable that a layer substantially consisting of the polymer of the polymerizable compound is formed on the surface of the cross-linked polyurethane resin sheet. This layer is not self-healing. The polymerizable compound is polymerized inside the surface of the crosslinkable polyurethane resin sheet, and the crosslinkable polyurethane resin must be present on the surface substantially to some extent. For example, as a result of the ATR spectrum measurement of the surface modified surface, it is necessary that the absorption of the cross-linked polyurethane resin be clearly recognized, and the absorption of the polymer of the polymerizable compound is hardly or slightly recognized. It is preferably about This surface modification is performed by impregnating the polymerizable compound with the solution of the polymerizable compound on the surface of the crosslinked polyurethane-based resin sheet by dipping, spraying, coating or the like to remove the solution remaining on the surface, and then removing the solution. It is preferable to perform the polymerization by irradiating an energy ray such as ultraviolet rays. In the solution of the polymerizable compound, a polymerization initiator such as a photopolymerization initiator, a photosensitizer, a leveling agent, a colorant,
Other additives can be arbitrarily blended. As the polymerizable compound, ethylene glycol, propylene glycol, 1.4-butanediol, neopentyl glycol, 1.6-hexanediol, diethylene glycol, glycerin, trimethylolpropane, pentaerythritol, other polyhydric alcohols and acrylic acid or methacrylic acid Polyester is the most preferable, and acrylic acid or methacrylic acid ester of monohydric alcohol can be used together with these.

The surface modification can be performed at any stage after the production of the crosslinked polyurethane-based resin sheet. For example, in the laminate shown in FIG. 1, the exposed surface of the sheet (1) manufactured by the casting method is secondly surface-modified before being covered with the protective material (3), and then the second protection is performed. The target laminate can be manufactured by covering with the material (3). In the laminate shown in FIG. 2, the adhesive synthetic resin layer (4) is provided on one surface of the manufactured sheet (1) as described above, and the surface thereof is covered with the first protective material (5). It can be produced by covering and then surface-modifying the other surface of the sheet (1) and covering that surface with the second protective material (6). Of course, conversely, one surface of the sheet (1) may be first surface-modified and then the adhesive synthetic resin layer may be provided. Further, the surface modification can be carried out continuously following the continuous production of the sheet (1) or the like, and after the production of the sheet (1) etc. is once completed, the surface modification operation can be performed next. it can. The surface may be modified on both sides of the sheet (1) depending on the case. For example, in the layered product of FIG. 2, even if the surface of the sheet (1) that contacts the adhesive synthetic resin layer (4) is surface-modified and the adhesiveness is somewhat reduced, there is little possibility of causing a problem.

The laminate of the present invention can be manufactured by various methods as described above. However, it is preferably produced by the following two methods. The former relates to a method for producing a laminate having or not having the adhesive synthetic resin layer as shown in FIG. 1 or 2, and the latter relates to a method for producing a laminate having the layer as shown in FIG. .

On the smooth surface of the adhesive synthetic resin layer formed on the releasable substrate or on the releasable substrate having a smooth surface, the reactive raw material mixture capable of forming the crosslinked polyurethane resin is cast and cured. To produce an optically smooth sheet of transparent cross-linked polyurethane resin having self-repairing property, if necessary, the exposed surface of the sheet is surface-modified, and then the sheet is surface-modified or not. A method for producing a laminated body, characterized in that the exposed surface of is covered with a protective material having a peelable surface.

An optically smooth sheet of a transparent cross-linkable polyurethane resin having self-repairing property by casting a reactive raw material mixture capable of forming a cross-linkable polyurethane resin on a peelable substrate having a smooth surface and curing the mixture. Is formed, an adhesive synthetic resin layer is formed on the exposed surface of the sheet or the surface formed by peeling the peelable base material, and the surface of the layer is covered with a protective material having a peelable surface. When the flexible substrate is peeled off, the exposed surface of the sheet is covered with a second protective material having a peelable surface at any stage after the production of the sheet, and, if necessary, the second protective material. The surface is modified by applying surface modification to the surface to be covered before being covered with, or to the surface generated by peeling the releasable substrate and where the formation of the adhesive synthetic resin layer is not planned. The second protective material or other exfoliation Be covered with a protective material having a surface, preparation of a laminate characterized by.

A laminate including a sheet having a surface modification and having an adhesive synthetic resin layer as shown in FIG. 2 is preferably manufactured by the following method. That is, an optically smooth sheet as described above is produced on a peelable substrate having a smooth surface, an adhesive synthetic resin layer is formed on the exposed surface of the sheet, and the surface of the layer is treated with a protective material. It is manufactured by a method of protecting and then peeling off the peelable base material, surface-modifying the surface of the resulting sheet, and covering the surface-modified surface with a protective material different from the peelable base material. In this method, it is preferable that the formation of the adhesive synthetic resin layer and the protection of the layer are continuously performed following the continuous production of the sheet. On the other hand, the surface modification may be performed in another step. For example, the time required for the surface modification treatment can be shorter than the time required for producing the sheet, and it is often preferable to perform this step separately from the viewpoint of productivity.

FIG. 3 is a flow sheet showing an outline of the manufacturing process of the laminated body. A reactive raw material mixture (11) capable of forming a cross-linked polyurethane resin on a moving releasable substrate (10) is supplied from a linear nozzle (12) and cast to form a doctor knife (1).
After the surface is made uniform in 3), it is cured in a curing furnace (14) to produce a cross-linked polyurethane resin sheet (15). On the other hand, adhesive synthetic resin solution (17) on the protective material (16)
Is applied, the solvent is removed in a heating furnace (18), and the adhesive synthetic resin layer on the protective material (16) is pressure-laminated on the exposed surface of the sheet (15) with a roll (19). (If it is heated at the same time), the obtained laminated body (20) is wound on a winding roll (21). In this laminate (20), one surface of the crosslinked polyurethane-based resin sheet (15) is protected by the peelable base material (10), an adhesive synthetic resin layer is formed on the other surface, and the surface of the layer is protected. A laminated body protected by a material (16). Further, the surface modification is carried out as follows. The laminate (20) is pulled out from the winding roll (21), the peelable base material (10) is peeled and removed, and this is immersed in a solution (22) containing a polymerizable compound, a photopolymerization initiator or the like. After impregnating them and removing the solvent in the heating furnace (23), the light irradiation device (24) irradiates them with ultraviolet rays to polymerize the polymerizable compound, and then the surface is modified with the second protective material (25). The obtained laminated body (26) is wound on a winding roll (27) while protecting the formed surface. The obtained laminate (28) has a sheet (15) having a surface-modified surface protected by the second protective material (25) and an adhesive synthetic resin layer protected by the protective material (16) on the other surface. Is a laminated body.

The protective material having a peelable surface used in the present invention,
Films and sheets made of plastic, metal and other materials can be used. When the material itself of the protective material has releasability, the film or sheet can be used as it is. As the material having a low releasability, a film or sheet whose surface is subjected to a releasability treatment can be used. For example, a polyolefin resin such as polyethylene or polypropylene or a fluororesin has a releasable material itself, and the film or sheet can be used as it is as a protective material. On the other hand, as a film or sheet made of thermoplastic polyester resin, polyamide resin, or other resin or metal having low releasability, at least the surface is treated with an organosilicon compound, a polyorganosiloxane, a fluorine compound, or another release treatment agent. The processed one is used. In addition,
For a protective material for protecting the surface of the adhesive synthetic resin layer, it is desirable that the release treatment agent is difficult to migrate to the surface of this layer. Further, as described above, the protective material for protecting the surface of this layer preferably has fine irregularities on the surface. As the protective material, a film or sheet of polyolefin resin, particularly polypropylene, is preferable. Furthermore, a film or sheet made of the above-mentioned material or having a release property can be used as a release base material that can also be used as a protective material. However, it is desirable that the releasable substrate has high surface smoothness and little deformation such as elongation. Therefore, a metal film or sheet or a synthetic resin film or sheet having low extensibility is preferable. A particularly preferable releasable substrate is a film or sheet of polyethylene terephthalate resin whose surface has been treated for releasability.

It is necessary that the material of the adhesive synthetic resin layer is a synthetic resin that is capable of adhering to the surface of the inorganic glass or the like even after the laminate of the present invention is manufactured and has plasticity. The synthetic resin may be a solid uncured thermosetting resin or adhesive resin that can be cured when laminated with an inorganic glass or the like, but is preferably a linear or thermoplastic resin having thermoplasticity. A synthetic resin that is crosslinked to such an extent that it is not damaged is preferable. Examples of such synthetic resins include linear polyurethane resins and slightly crosslinked polyurethane resins (see, for example, JP-A-60-71252), polyvinyl butyral resin, ethylene-vinyl acetate copolymer. There is system resin (so-called EVA resin). When the adhesive synthetic resin layer is required to have the performance as a penetration resistant layer, the thickness of the layer is preferably about 0.2 mm or more, particularly about 0.3 to 1.5 mm. On the other hand, if the performance as a penetration resistant layer is not required, it may be less than about 0.2 mm,
0.01-0.1mm is adopted.

As the cross-linked polyurethane resin in the present invention, various resins can be adopted as long as they have self-repairing property and are transparent. For example, those having high mechanical properties or those having low mechanical properties described in the above-mentioned known examples can be used. In the latter case, it is preferable to provide a relatively thick adhesive synthetic resin layer as described above.

However, the cross-linkable polyurethane resin particularly preferable in the present invention is a cross-linkable polyurethane resin having both mechanical properties and self-healing property. This cross-linked polyurethane resin has an elongation of at least about 200% and a breaking strength of about 300 kg / cm ² or more, and usually has an elongation of about 300% or more and about 600 kg.
/ Cm ² or more at break strength (however, physical properties before surface modification). Details of such a cross-linkable polyurethane-based resin are described in the prior applications of the present inventors (Japanese Patent Application No. 60-18692 and Japanese Patent Application No. 60-192).
No. 66), but the outline is explained below.

The cross-linked polyurethane resin is manufactured using the following raw materials.

1. It is necessary to use both a polyol with a relatively high molecular weight and a chain extender, and high mechanical properties cannot be obtained without using a chain extender.

2. It is necessary to use a diol and a polyol having a valence of 3 or more in combination with the above-mentioned polyol, and the average hydroxyl value thereof is about 70-
The equivalence ratio of 150, (polyhydric polyol having a valence of 3 or more) / (diol) should be in the range of about 0.1 to 0.6. If the average hydroxyl value and the equivalent ratio are higher than this, the mechanical properties are deteriorated, and if it is low, the self-repairing property is deteriorated.

3. The chain extender must be a substantially divalent compound having a functionality of about 2.3 or less, particularly about 2.1 or less, and the polyisocyanate compound must also have a functionality of about 2.3 or less, particularly about 2.1 or less. Must be a polyisocyanate compound of. If the number of functional groups is higher than this, the mechanical properties will deteriorate.

4. The amount of chain extender per equivalent of polyol is about 0.4 to 1.8.
Must be equivalent. If it is higher than this, the self-repairing property is lowered, and if it is lower than this, the mechanical properties are lowered.

5. The polyol preferably contains polyester polyol and / or polycarbonate polyol as a main component.

More preferable conditions are as follows.

1) The hydroxyl value of the diol is about 40 to 250, especially about 60 to 150
It may be a mixture of two or more kinds. Especially about hydroxyl value
With 90 to 100 as a boundary, a combination of a diol having an upper limit (hydroxyl value of 100) and a diol having an upper limit or less, or a combination of a diol having a lower limit (hydroxyl value of 90) and a diol having a lower limit or more is preferable.

2) Triol is preferred as the trivalent or higher valent polyol, and its hydroxyl value is preferably about 150 to 250.

3) The average hydroxyl value of the diol and the polyol having 3 or more valences is preferably about 80 to 140, and the equivalent ratio thereof is about 0.15 to
0.35 is preferable.

4) As a chain extender, a polyol is preferable to a polyamine, and a diol having a molecular weight of about 160 or less is particularly preferable. The amount used is about 0 for 1 equivalent of polyol.
7 to 1.3 equivalents are preferred.

5) As the polyisocyanate compound, non-yellowing diisocyanate is used, and particularly methylene bis (cyclohexyl isocyanate) or isophorone diisocyanate is preferable.

6) As the polyol, a combination of polyester-based polyol and polycarbonate-based polyol is preferable.
In particular, a polyester-based polyol having a polyol residue having 6 or less carbon atoms and an aliphatic dicarboxylic acid residue having 8 or less carbon atoms (for example, polybutylene adipate diol),
A combination of a polycaprolactone-based polyester polyol and a polycarbonate-based polyol is preferable.

The laminate of the present invention is preferably used as a material for producing laminated safety glass. The present invention can also be used as a material for manufacturing optical elements such as laminated lenses. Laminated lenses having a cross-linked polyurethane resin layer having self-healing property are known. In addition, the laminate used for the application of laminated safety glass for construction may not be partially transparent in some cases. Further, the laminate of the present invention can be used as a sheet for surface protection of metals, plastics and other materials. For example, it is known that the crosslinkable polyurethane resin having self-repairing property as described above is used for surface protection of plastics, and the laminate of the present invention can be used for the same purpose.

The present invention will be described below with reference to examples and the like, but the present invention is not limited to these examples.

Example 1 43.86 parts of poly (1,6-hexanecarbonate) diol having a hydroxyl value of about 122 [parts by weight, the same applies hereinafter], hydroxyl value of about 90.5
68.93 parts of a poly (caprolactone) diol of, and a poly (caprolactone) triol having a hydroxyl value of about 195.2 12.
After 54 parts were heated and melted at 100 ° C., they were stirred and mixed while dehydration and deaeration under reduced pressure. After lowering the temperature of this polyol mixture to 80 ° C, dibutyltin dilaurate [hereinafter referred to as catalyst]
6.0 x 10 ^-3 parts, 1,4-butanediol 10.02 parts, and 4,
4'-methylenebis (cyclohexyl isocyanate)
64.5 parts of [hereinafter referred to as H ₁₂ MDI] were sequentially added and mixed with stirring to prepare a reactive raw material mixture.

On the other hand, a continuous film of polyethylene terephthalate resin with a peelable surface treatment was transferred onto a flat substrate at a continuous film speed of 10 cm / min, and the above reactive raw material mixture was cast immediately after its production under an ambient temperature of 25 ° C. A 0.7 mm thick layer was formed through a doctor knife. This was introduced into a 140 ° C. curing oven and allowed to pass for 80 minutes. A 0.02 mm thick thermoplastic polyurethane resin layer supported on a polypropylene film is laid on the exposed surface of the cross-linked polyurethane resin sheet that has come out of the curing oven, and the mixture is heated and pressed with a roll, and the resulting laminate is rolled. I wound up. Hereinafter, this laminated body is referred to as a laminated body A. The thermoplastic polyurethane-based resin layer-supported polypropylene film is produced by applying a thermoplastic polyurethane-based resin solution to an embossed polypropylene film (thickness: 0.05 mm, embossing height: about 4 μm) in advance and drying.

Next, the above laminate was pulled out from the roll, the polyethylene terephthalate resin film was peeled off, and continuously dipped in the following solution at a rate of 70 cm / min so that the residence time was 15 seconds. Subsequently, the resultant was passed through a heating furnace at 60 ° C. for 3 minutes to be dried, and then passed through a high pressure mercury lamp irradiation device to be surface-modified.

Neopentyl glycol diacurate 1200 parts Benzophenone 60 parts Acetonitrile 1800 parts Defoamer 15 parts Immediately after surface modification, the surface was covered with a polypropylene film having a smooth surface, and the obtained laminate was wound up on a roll. Hereinafter, this laminated body is referred to as a laminated body B.

Example 2 A sheet (thickness: 1 mm) was produced by the continuous casting method in the same manner as in Example 1, using the following cross-linked polyurethane resin.
Subsequently, an ethanol solution of polyvinyl butyral resin was applied to the exposed surface and dried to form an adhesive layer having a thickness of 0.02 mm. On the surface of this adhesive layer, the same embossed polypropylene film as in Example 1 was laminated by roll pressure with the embossed surface as the lamination surface. Hereinafter, this laminated body is referred to as a laminated body C.

Poly (1,6-hexane carbonate) diol with a hydroxyl value of 57 63.07 parts Poly (caprolactone) diol with a hydroxyl value of 90.5 99.1
2 parts Poly (caprolactone) triol with a hydroxyl value of about 195.2 1
8.02 parts Catalyst 8.25 × 10 ^-3 parts 1,4-Butanediol 14.42 parts H ₁₂ MDI 80.37 parts Next, using the following solution, surface modification was performed in the same manner as in Example 1 to obtain a smooth surface. Was covered with a prepylene film having This laminated body is hereinafter referred to as a laminated body D.

1,6-Hexanediol diacrylate 1200 parts Benzophenone 60 parts Acetone 1800 parts Leveling agent 15 parts [Surface performance test] Test pieces are cut from the laminates A to D and stored for 1 week at room temperature, then have a smooth surface The polypropylene film was peeled off, and its surface performance was measured by the following method. On the other hand, at the time of manufacturing the laminates A to D, a test piece was cut out before being covered with a polypropylene film having a smooth surface, and its surface performance was measured in the same manner. The results are shown in Table 1. The physical properties of only the cross-linked polyurethane resin sheet before surface treatment after being stored for 1 week were as follows (physical property measurement method is according to JIS K6301).

Elongation Break strength Laminate A sheet 390 650 Laminate C sheet 400 750 [Surface performance test method] Self-healing property: Scratch the cross-linked polyurethane resin surface with a 10 μmφ diamond tip under load, at 10 ° C at 25 ° C.
It is expressed as the maximum load at which scratches that occur within minutes can disappear. The disappearance of the scratch was performed visually. In the case of non-self-healing inorganic glass, scratches were generated by this method at a load of about 5 g.

Contamination resistance: Marked when a cross-linked polyurethane resin layer surface is marked with a felt pen and wiped with ethanol 24 hours later.

Contact trace resistance: A smooth film (polyethylene terephthalate film) is placed by enclosing an air trap on the surface of the cross-linked polyurethane resin, left for 24 hours, and then the smooth film is removed to remove air trap marks on the urethane resin surface. I saw how much it remained.

[Brief description of drawings]

1 and 2 are cross-sectional views showing two examples of the laminated body of the present invention. FIG. 3 is a flow sheet showing a method for producing the laminate of the present invention. 1 ... Cross-linked polyurethane resin sheet 2,5 ... First protective material 3,6 ... Second protective material 4 ... Adhesive synthetic resin layer 10 ... Releasable base material (protective material) 14,18, 23 …… Heating furnace 15 …… Crosslinked polyurethane resin sheet 16,25 …… Protective material 20,21 …… Layered body 22 …… Surface modification solution 24 …… Ultraviolet irradiation device

Claims (7)

[Claims] 1. An optically smooth sheet of a transparent crosslinkable polyurethane resin having a self-repairing property, or a sheet of the crosslinkable polyurethane resin having an adhesive synthetic resin layer provided on one side thereof, which has releasability on both sides. A laminate formed by protecting one surface of a protective material having a surface. 2. The surface of the crosslinked polyurethane-based resin sheet that comes into contact with the protective material is a surface that has been surface-modified by impregnating and polymerizing a polymerizable compound in advance.
Item stack. 3. The laminate according to claim 1, wherein the adhesive synthetic resin layer is made of a synthetic resin having a heat fusion property. 4. The laminate according to claim 1, wherein the protective material is a film or sheet having a peelable surface. 5. The surface of a protective material in contact with the adhesive synthetic resin layer has fine irregularities, and the surface of the adhesive synthetic resin layer in contact with the surface of the protective material is formed by transferring the surface of the protective material. The laminate according to claim 1, which has fine irregularities. 6. A reactive raw material mixture capable of forming a crosslinked polyurethane resin on the smooth surface of an adhesive synthetic resin layer formed on a peelable substrate or on a peelable substrate having a smooth surface. Is cast and cured to produce an optically smooth sheet of a transparent cross-linking polyurethane resin having self-repairing property. If necessary, the exposed surface is surface-modified, and then the surface-modified A method for producing a laminate, which comprises covering the exposed surface of the sheet not covered with a protective material having a peelable surface. 7. Optical of transparent cross-linkable polyurethane resin having self-repairing property by casting and curing a reactive raw material mixture capable of forming cross-linkable polyurethane resin on a peelable substrate having a smooth surface. Of an adhesive synthetic resin layer on the exposed surface of the sheet or on the surface formed by peeling off the peelable base material, and the surface of the layer has a peelable surface. When the releasable substrate is peeled off, the exposed surface of the sheet is covered with a second protective material having a releasable surface at any stage after the production of the sheet, and if necessary, The surface to be covered before being covered with the second protective material, or to the surface generated by peeling off the peelable base material and where the adhesive synthetic resin layer is not planned to be formed, is subjected to surface modification. Use the modified surface as a second protective material or other Be covered with a protective material having a release surface, the preparation of a laminate characterized by.