JPH1178515A - Vehicular window material and manufacture of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a surface having high wear resistance nearly equal to that of an inorganic glass plate by forming silica layers made of a transparent resin plate and an outermost layer stacked on the transparent resin plate, which includes polysilazane and forming an inner layer contacted with the outermost layer as a wear resistance layer. SOLUTION: In both surfaces of a transparent resin plate 10, a first coated layer and a second hard coated layer 2 are respectively stacked. Of these, the first coated layer 1 has a two layer composition, i.e., of an outer layer 11 forming an outermost layer and an inner layer 12 directed contacted therewith. For forming the outer layer 11, there is available polysilazane or the like forming silica which includes no substantial organic base. By forming more minute structure silica with this polysilazane, an outer layer having a better surface characteristic is obtained. Between the transparent resin plate 10 and the inner layer 12, a third layer made of a transparent hard material layer identical or different from that of the inner layer 12 or the outer layer 11 or other transparent synthetic resin may be provided.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a vehicle window material using a transparent resin plate and a method for manufacturing the same.

[0002]

2. Description of the Related Art A glass plate is provided at a window opening of a vehicle such as an automobile to form a window material. In recent years, in order to reduce the weight of vehicles such as automobiles, it has been proposed to use a transparent resin plate instead of a glass plate as a window material. Above all, the transparent resin plate of the aromatic polycarbonate system is resistant to fracture, transparency,
It is a promising material as a window material for vehicles because of its excellent lightness and easy processability.

On the other hand, since vehicles are exposed to the outdoors, vehicle window materials are required to have durability against various external factors.
In particular, as represented by vehicle washing, external forces such as various rubs are applied to the surface of the vehicle window material. Therefore, high wear resistance performance is required for window materials for vehicles. A transparent resin plate has insufficient surface hardness to be used in place of a glass plate, and is apt to be damaged and easily worn, so that transparency is easily lost. Therefore, there is a limit in using a transparent resin plate as a vehicle window material.

Therefore, in a transparent resin plate proposed for a vehicle window, an abrasion-resistant hard coat layer is usually laminated on the surface of the transparent resin plate. As a result, a window material having a certain degree of wear resistance can be obtained. By the way, since the vehicle window material usually has a curved shape, the transparent resin plate is often bent. For this purpose, the hard coat layer laminated on the transparent resin plate is required to be formed from a material that can withstand the above-described bending. As described above, a window material using a transparent resin plate for a vehicle is subject to severe restrictions such as abrasion resistance and ease of bending.

[0005]

Heretofore, many attempts have been made to improve the scratch resistance and abrasion resistance of an aromatic polycarbonate transparent resin plate. One of the most common methods is to add a polymerizable functional group such as an acryloyl group in the molecule.
There is a method of applying a polymer-curable compound having at least one resin-cured compound to a resin plate and curing it with active energy rays such as heat or ultraviolet rays to obtain a resin plate having a transparent cured product layer having excellent scratch resistance. In this method, the composition for coating is relatively stable, and is particularly excellent in productivity because it can be cured by ultraviolet rays. Even when a resin plate is bent, cracks do not occur in the cured film and the surface has scratch resistance. And abrasion resistance can be improved. However, since the cured film is made of only an organic substance, there is a limit to the level of expression of scratch resistance on the surface.

On the other hand, as a method for imparting a higher surface hardness to a substrate, there is a method in which a metal alkoxide is applied to a resin plate and cured by heat. Silicon-based compounds are widely used as metal alkoxides, and can form cured films having excellent abrasion resistance. However, since the adhesion between the cured film and the substrate is poor, there are disadvantages such as easy peeling and cracking of the cured film.

As a method for remedying the disadvantages of these techniques, a mixture of an acryloyl group-containing compound and colloidal silica is applied to a resin plate and cured with an active energy ray such as ultraviolet rays to obtain a transparent cured material having excellent scratch resistance. There is a method of forming a material layer (JP-A-61-181809). By using the colloidal silica and the polymerization-curable compound in combination, it is possible to achieve both high surface hardness and high productivity. However, it was still inferior to the method of applying the above-mentioned metal alkoxide to a substrate and curing by heat at the level of the surface scratch resistance.

There is also known a method in which polysilazane is used in place of the silicon-based metal alkoxide compound, that is, a method in which polysilazane is applied to a substrate and cured by heat or the like (Japanese Patent Laid-Open No. 8-143689). It is thought that polysilazane undergoes condensation reaction and oxidation reaction in the presence of oxygen and changes to silica (silicon dioxide) that may contain nitrogen atoms. Is formed. The silica coating derived from polysilazane has a high surface hardness. However, this coating has poor adhesion between the coating and the resin plate as in the case of the metal alkoxide, and thus has disadvantages such as easy peeling and cracking of the coating.

Furthermore, a method of forming a protective film on a plastic film and applying a polysilazane solution to the surface to form a silica surface layer (Japanese Patent Application Laid-Open No. 9-39161)
Has also been proposed. The protective coating is provided to prevent the plastic film from being attacked by the solvent of the polysilazane solution.

It is known that the surface of a silica layer formed of polysilazane or the like has abrasion resistance. However, the present inventor has found that surface characteristics such as abrasion resistance and scratch resistance of the surface of the silica layer vary depending on the material of the lower layer. It is considered that this is due to the influence of the adhesion between the silica layer and the lower layer and the abrasion resistance of the surface in contact with the lower silica layer.

As described above, various hard coat layers laminated on the surface of the transparent resin plate have been proposed in order to meet the requirements of wear resistance and easy processability, etc., which have been conventionally imposed on the transparent resin plate. However, there is no known window material having the performance required for vehicle use.

[0012]

The present inventors have studied the material of the lower layer which gives the silica layer surface with higher surface characteristics, and as a result, have found a lower material having a specific material and surface characteristics. The material of this lower layer has high adhesion to the silica layer and also has sufficient adhesion to the transparent resin plate.
In other words, despite the fact that the outermost layer is an inorganic coating, it is sufficiently adhered to the inner layer, and consequently to the transparent resin plate, and has a surface abrasion resistance equal to or close to that of glass. A transparent synthetic resin molded article having a cured product layer was found. The present invention is the following invention relating to a vehicle window material using the molded article and a method for manufacturing the same.

A transparent resin plate and a first hard coat layer laminated on the transparent resin plate, wherein the first hard coat layer is formed of two or more transparent cured material layers, The window material for vehicles, wherein the outermost layer is a silica layer which is a cured product of a coating composition containing polysilazane, and the inner layer in contact with the outermost layer is a wear-resistant layer.

In a vehicle window material having a transparent resin plate and a first hard coat layer laminated on the transparent resin plate,
The first hard coat layer is formed of two or more transparent cured material layers, and the inner layer that is in contact with the outermost layer of the two or more transparent cured material layers has two or more active energy ray-curable polymerizable functional groups. A coating composition which is a hardened product of a coating composition (A) containing a multifunctional compound (a) having at least one abrasion-resistant layer, wherein the outermost layer can form silica substantially containing no organic group. A vehicle window material comprising a silica layer which is a cured product of (B).

In a vehicle window material having a transparent resin plate and first and second hard coat layers laminated on both surfaces of the transparent resin plate, the first hard coat layer is formed of two or more transparent hardened layers. Of the two or more transparent cured product layers, the inner layer in contact with the outermost layer is JIS-R32
When the number of rotations of the specimen in the wear resistance test specified in 12 is 100, the haze value (%) after abrasion and the haze value (%) before abrasion of the inner layer side surface of the transparent resin plate on which the inner layer is formed are shown. Is 15% or less, and the surface of the vehicle window material on the first hard coat layer side is JIS-R321.
2. A vehicle window material having abrasion resistance in which a difference between a haze value (%) after abrasion and a haze value (%) before abrasion according to the abrasion resistance test specified in 2 is 10 (%) or less. .

An uncured, partially cured or cured layer of the coating composition (A) containing the polyfunctional compound (a) having two or more active energy ray-curable polymerizable functional groups is formed on a transparent resin plate. After forming a layer of an uncured material or a partially cured material of the coating composition (B) capable of forming silica containing substantially no organic groups on the surface of the layer, these layers were formed. The transparent resin plate is heated and bent, and then the uncured or partially cured product of the coating composition (B) and, if any, the uncured or partially cured product of the coating composition (A) are present. Curing, and forming a cured product of the coating composition (B) on the outermost layer and an abrasion-resistant layer which is a cured product of the coating composition (A) on the inner layer in contact with the outermost layer. Laminate a hard coat layer formed from a transparent cured product layer on a transparent resin plate, exhibiting a curved shape Method of manufacturing a vehicle window material.

In the present invention, the first hard coat layer (hereinafter, simply referred to as the first coat layer) is composed of two or more transparent cured layers, and the outermost layer, which is a silica coating, is a relatively soft transparent resin plate. Instead of being directly laminated on the inner layer of a hard transparent cured product having high abrasion resistance. For this reason, it is considered that the displacement of the outermost layer due to an external force applied to the window material to damage the window material is reduced, so that surface characteristics higher than those provided by a normal inorganic coating can be obtained.

In the present invention, the outermost layer of the first coat layer preferably has a thickness of 0.05 to 10 μm, and the inner layer in contact with the outermost layer has a thickness of 1 to 50 μm. preferable.

[0019]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in more detail with reference to the drawings. FIG. 1 is a schematic sectional view showing an example of the vehicle window material of the present invention. On both sides of the transparent resin plate 10,
A first coat layer 1 and a second hard coat layer (hereinafter, simply referred to as a second coat layer) 2 are respectively laminated. The first coat layer 1 includes a transparent cured material layer (hereinafter, simply referred to as an outer layer) 11 that forms the outermost layer and an outer layer 11.
Transparent cured material layer (hereinafter simply referred to as inner layer) 1 which is in direct contact with
And 2 transparent cured material layers.

Between the transparent resin plate (hereinafter simply referred to as a resin plate) and the inner layer, there is provided a third layer made of a transparent hardened material layer of the same or different type as the inner layer or the outer layer or another transparent synthetic resin. May be present. For example, a layer of a thermoplastic resin such as a thermoplastic acrylic resin or an adhesive layer may be present.

The inner layer 12 has sufficient abrasion resistance. This inner layer is in the same manner as in the abrasion resistance test in JIS-R3212, and has a haze value (%) after 100 rotations of the test piece (in this case, a laminate in which the inner layer is exposed) and a haze before the abrasion test. It is preferable to have abrasion resistance with a difference from the value (%) of 15 (%) or less. The abrasion resistance test can be performed using a specimen in which a transparent cured product layer forming an inner layer is laminated on a resin plate (not necessarily a resin plate). In the present invention, the abrasion resistance is measured in the same manner as in the abrasion resistance test in JIS-R3212, and the number of rotations of the specimen is 100, 500, or 1000 times (in the case of 1,000 times, the JIS-R3212 is used). Haze value before wear (%) from haze value after wear (%)
And expressed as a value (%) after subtracting. Hereinafter, the abrasion resistance of the specimen is represented by “value (%)” obtained by subtracting the haze value (%) before abrasion from the haze value (%) after the abrasion.

Since the vehicle window material of the present invention has an outer layer formed on the cured product layer, it is difficult to subject the vehicle window material itself to an inner layer wear resistance test. The more preferable wear resistance of the inner layer is 10% or less, particularly 5% or less at 100 rotations of the test piece.

As a specific example for obtaining the inner layer 12 having sufficient abrasion resistance, a layer of a cured product of the coating composition (A) is used for the inner layer 12. The layer of the cured product of the coating composition (A) has high adhesion to the outer layer 11. In addition, it has high adhesion to the resin plate 10. When the third layer exists between the inner layer and the resin plate, the third layer preferably has sufficient adhesion to the inner layer and the resin plate.

In order to obtain an inner layer having high adhesion and abrasion resistance, a polyfunctional compound (a) is used as the active energy ray-curable coating composition (A). It is preferable to use a specific polyfunctional compound (a) in order to obtain a cured product having higher abrasion resistance. Preferred specific polyfunctional compound (a) will be described later as preferred polyfunctional compound (a). Similarly, in order to form a cured product having high abrasion resistance, it is also preferable to mix colloidal silica having an average particle diameter of 200 nm or less with the coating composition (A) to form a cured product containing colloidal silica. . In order to efficiently cure the polyfunctional compound (a) with active energy rays (especially ultraviolet rays), the coating composition (A) usually contains a photopolymerization initiator.

The polyfunctional compound (a) having two or more active energy ray-curable polymerizable functional groups in the coating composition (A) may be one kind of polyfunctional compound,
Further, a plurality of types of compounds may be used. In the case of a plurality of compounds, they may be different compounds in the same category, or may be compounds in different categories. For example, a combination of different compounds each of which is acrylic urethane may be used, or one of which may be acrylic urethane and the other may be an acrylic ester compound having no urethane bond.

In the present specification, an acryloyl group and a methacryloyl group are collectively referred to as a (meth) acryloyl group. The same applies to (meth) acryloyloxy group, (meth) acrylic acid, (meth) acrylate and the like.

The active energy ray-curable polymerizable functional group in the polyfunctional compound (a) is an α, β-unsaturated group such as a (meth) acryloyl group, a vinyl group, an allyl group or a group having the same. And it is preferably a (meth) acryloyl group or a (meth) acryloyloxy group. Among them, an acryloyl group or an acryloyloxy group, which is more easily polymerized by ultraviolet rays, is preferable. The polyfunctional compound (a) may be a compound having two or more polymerizable functional groups in one molecule in total, or a compound having two or more polymerizable functional groups in total in one molecule. There may be. The number of polymerizable functional groups in one molecule of the polyfunctional compound (a) is two or more, and the upper limit is not particularly limited. Usually, 2 to 50 pieces are appropriate,
Particularly, 3 to 30 pieces are preferable.

Preferred compounds as the polyfunctional compound (a) are compounds having two or more (meth) acryloyl groups. Among them, (meth) acryloyloxy group is 2
Compounds having two or more, such as polyhydric alcohols
A polyester of a compound having at least two hydroxyl groups and (meth) acrylic acid is preferred.

In the coating composition (A), two or more polyfunctional compounds (a) may be contained as the polyfunctional compound (a). Further, together with the polyfunctional compound (a), a monofunctional compound having one polymerizable functional group that can be polymerized by an active energy ray may be contained. As the monofunctional compound, a compound having a (meth) acryloyl group is preferable, and a compound having an acryloyl group is particularly preferable.

When the monofunctional compound is used in the coating composition (A), the ratio of the monofunctional compound to the total of the polyfunctional compound (a) and the monofunctional compound is not particularly limited. 0-60% by weight is suitable.
If the proportion of the monofunctional compound is too large, the hardness of the cured coating film may decrease and the abrasion resistance may be insufficient. A more preferable ratio of the monofunctional compound to the total of the polyfunctional compound (a) and the monofunctional compound is 0 to 30% by weight.

The polyfunctional compound (a) may be a compound having various functional groups or bonds other than the polymerizable functional group. For example, it may have a hydroxyl group, a carboxyl group, a halogen atom, a urethane bond, an ether bond, an ester bond, a thioether bond, an amide bond, a diorganosiloxane bond, and the like. In particular, a (meth) acryloyl group-containing compound having a urethane bond (so-called acryl urethane) and a (meth) acrylate compound having no urethane bond are preferable. Hereinafter, these two types of polyfunctional compounds (a) will be described.

The (meth) acryloyl group-containing compound having a urethane bond (hereinafter referred to as acryl urethane) includes:
For example: (1) A reaction product of a compound (X1) having a (meth) acryloyl group and a hydroxyl group and a compound having two or more isocyanate groups (hereinafter, referred to as polyisocyanate). (2) A reaction product of the compound (X1), the compound (X2) having two or more hydroxyl groups, and a polyisocyanate. (3) A reaction product of the compound (X3) having a (meth) acryloyl group and an isocyanate and the compound (X2).

It is preferable that these reaction products have no isocyanate group. However, hydroxyl groups may be present. Therefore, in the production of these reaction products, it is preferable that the total number of moles of hydroxyl groups of all reaction raw materials is equal to or larger than the total number of moles of isocyanate groups.

The compound (X1) may be a compound having one (meth) acryloyl group and one hydroxyl group, a compound having two or more (meth) acryloyl groups and one hydroxyl group, and (meth) acryloyl It may be a compound having one group and two or more hydroxyl groups, or a compound having two or more (meth) acryloyl groups and two or more hydroxyl groups. Specific examples include, in the above order, 2-hydroxyethyl (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane mono (meth) acrylate, pentaerythritol di (meth) acrylate, and the like. These are monoesters of a compound having two or more hydroxyl groups and (meth) acrylic acid or polyesters having one or more hydroxyl groups.

Further, the compound (X1) may be a ring-opening reaction product of a compound having at least one epoxy group with (meth) acrylic acid. The reaction between the epoxy group and the (meth) acrylic acid causes the ring opening of the epoxy group to form an ester bond and a hydroxyl group, resulting in a compound having a (meth) acryloyl group and a hydroxyl group. Alternatively, the compound having one or more epoxy groups may be ring-opened to form a hydroxyl group-containing compound, which may be converted to a (meth) acrylate.

As the compound having one or more epoxy groups, a polyepoxide which is a so-called epoxy resin is preferable. As the polyepoxide, for example, a compound having two or more glycidyl groups such as a polyhydric phenol-polyglycidyl ether (for example, bisphenol A-diglycidyl ether) or an alicyclic epoxy compound is preferable. Further, a reaction product of a (meth) acrylate having an epoxy group and a compound having a hydroxyl group or a carboxyl group can also be used as the compound (X1). Examples of the (meth) acrylate having an epoxy group include glycidyl (meth) acrylate.

Other specific examples of the compound (X1) include the following compounds. 2-hydroxypropyl (meth) acrylate, 1,3-propanediol mono (meth) acrylate, 1,4-butanediol mono (meth) acrylate, 2-butene-1,4-diol mono (meth) acrylate, 1, 6-hexanediol mono (meth) acrylate, glycidol di (meth)
Acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol mono (or penta) (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, bisphenol A-diglycidyl ether and (meth) acryl Reaction product with acid.

The polyisocyanate may be an ordinary monomeric polyisocyanate, a multipolymer or modified polyisocyanate, or a prepolymer compound such as an isocyanate group-containing urethane prepolymer. Examples of the polymer include a trimer (isocyanurate-modified), a dimer, and a carbodiimide-modified. Examples of the modified include urethane-modified and buret-modified products obtained by denaturation with a polyhydric alcohol such as trimethylolpropane. , Alohanate modified products, urea modified products and the like. Examples of prepolymers include isocyanate group-containing urethane prepolymers obtained by reacting polyols such as polyether polyols and polyester polyols described below with polyisocyanates. These polyisocyanates can be used in combination of two or more.

Specific examples of the monomeric polyisocyanate include the following polyisocyanates (the names in [] are abbreviated). 2,6-tolylene diisocyanate, 2,4-tolylene diisocyanate, methylene bis (4-phenyl isocyanate) [MDI], 1,5-
Naphthalene diisocyanate, tolidine diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, p-phenylene diisocyanate, trans-cyclohexane-1,4-diisocyanate, xylylene diisocyanate [XDI], hydrogenated XDI, hydrogenated MDI, lysine diisocyanate, tetramethyl xylene diisocyanate , Trimethylhexamethylene diisocyanate, lysine triisocyanate, 1,6,1
1-undecane triisocyanate, 1,8-diisocyanate-4-isocyanatomethyloctane, 1,
3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate.

As the polyisocyanate, non-yellowing polyisocyanate (polyisocyanate having no isocyanate group directly bonded to an aromatic nucleus) is particularly preferable. Specific examples include aliphatic polyisocyanates such as hexamethylene diisocyanate, alicyclic polyisocyanates such as isophorone diisocyanate, and aromatic polyisocyanates such as xylylene diisocyanate. As described above, polymers and modified products of these polyisocyanates are also preferable.

Examples of the compound (X2) include polyhydric alcohols and polyols having a higher molecular weight than polyhydric alcohols. As the polyhydric alcohol, a polyhydric alcohol having 2 to 20 hydroxyl groups is preferable, and a polyhydric alcohol having 2 to 15 hydroxyl groups is particularly preferable. The polyhydric alcohol may be an aliphatic polyhydric alcohol, an alicyclic polyhydric alcohol or a polyhydric alcohol having an aromatic nucleus.

Examples of the polyhydric alcohol having an aromatic nucleus include an alkylene oxide adduct of a polyhydric phenol and a ring-opened polyepoxide having an aromatic nucleus such as polyhydric phenol-polyglycidyl ether. Examples of the high molecular weight polyol include a polyether polyol, a polyester polyol, a polyether ester polyol, and a polycarbonate polyol. Further, a hydroxyl group-containing vinyl polymer can also be used as the polyol. These polyhydric alcohols and polyols can be used in combination of two or more.

Specific examples of the polyhydric alcohol include the following polyhydric alcohols. ethylene glycol,
1,2-propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, dipropylene glycol, neopentyl glycol, 2,2,4 -Trimethyl-1,3-pentanediol, cyclohexanediol, dimethylolcyclohexane, trimethylolpropane, glycerin, pentaerythritol, ditrimethylolpropane, dipentaerythritol, tris (2-hydroxyethyl) isocyanurate, tris (2-hydroxypropyl ) Isocyanurate, 3,9-bis (hydroxymethyl) -2,
4,8,10-tetraoxaspiro [5.5] undecane, 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5.5] Undecane, ring-opened product of bisphenol A-diglycidyl ether, and ring-opened product of vinylcyclohexene dioxide.

Specific examples of the polyol include the following polyols. Polyether polyols such as polyethylene glycol, polypropylene glycol, bisphenol A-alkylene oxide adduct, and polytetramethylene glycol. Aliphatic polyols such as polybutadiene diol and hydrogenated polybutadiene diol; Poly ε-
Caprolactone polyol. Adipic acid, sebacic acid,
A polyester polyol obtained by reacting a polybasic acid such as phthalic acid, maleic acid, fumaric acid, azelaic acid, glutaric acid and the above polyhydric alcohol. A polycarbonate diol obtained by reacting 1,6-hexanediol with phosgene.

Examples of the hydroxyl group-containing vinyl polymer include a copolymer of a hydroxyl group-containing monomer such as allyl alcohol, vinyl alcohol, hydroxyalkyl vinyl ether and hydroxyalkyl (meth) acrylate and a hydroxyl-free monomer such as olefin. .

Compound (X3) includes 2-isocyanatoethyl (meth) acrylate, methacryloyl isocyanate, 3- or 4-isopropenyl-α, α-
And dimethylbenzyl isocyanate.

Next, the (meth) acrylate compound having no urethane bond will be described. As the (meth) acrylate compound having no urethane bond, which is preferable as the polyfunctional compound (a), a compound (X)
Polyester of the same compound having two or more hydroxyl groups as in 2) and (meth) acrylic acid is preferable. As the compound having two or more hydroxyl groups, the above-mentioned polyhydric alcohols and polyols are preferable. Further, a (meth) acrylate compound which is a reaction product of a compound having two or more epoxy groups and (meth) acrylic acid is also preferable.

As a compound having two or more epoxy groups, there is a polyepoxide called an epoxy resin. For example, glycidyl ether type polyepoxide,
A commercially available epoxy resin such as an alicyclic polyepoxide can be used.

Specifically, there are the following polyepoxides, for example. Bisphenol A-diglycidyl ether, bisphenol F-diglycidyl ether, tetrabromobisphenol A-diglycidyl ether, glycerin triglycidyl ether, novolak polyglycidyl ether, vinylcyclohexene dioxide, dicyclopentadiene dioxide.

Specific examples of the polyfunctional compound (a) containing no urethane bond include the following compounds. (Meth) acrylates of the following aliphatic polyhydric alcohols. 1,4-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate,
1,6-hexanediol di (meth) acrylate, di (meth) acrylate of a long-chain aliphatic diol having 14 to 15 carbon atoms, 1,3-butanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, Diethylene glycol di (meth) acrylate, glycerol tri (meth) acrylate, glycerol di (meth) acrylate, triglycerol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tri (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, neopentylglycol Lumpur and di (meth) acrylate of a diol consisting of a condensation product of trimethylol propane.

The following (meth) acrylates of the following polyhydric alcohols or polyphenols having an aromatic nucleus or a triazine ring. Tris (2- (meth) acryloyloxyethyl)
Isocyanurate, bis (2- (meth) acryloyloxyethyl) -2-hydroxyethyl isocyanurate, tris (2- (meth) acryloyloxypropyl) isocyanurate, bis (2- (meth) acryloyloxyethyl) bisphenol A, Bis (2- (meth) acryloyloxyethyl) bisphenol S, bis (2- (meth) acryloyloxyethyl) bisphenol F, tris (2- (meth) acryloyloxyethyl) isocyanurate, bisphenol A dimethacrylate.

The following (meth) acrylates of hydroxyl-containing compounds-alkylene oxide adducts, (meth) acrylates of hydroxyl-containing compounds-caprolactone adducts, and (meth) acrylates of polyoxyalkylene polyols.
Here, EO represents ethylene oxide, PO represents propylene oxide, and [] represents the molecular weight of the polyoxyalkylene polyol. Tri (meth) acrylate of trimethylolpropane-EO adduct, tri (meth) acrylate of trimethylolpropane-PO adduct, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tripropylene glycol di (Meth) acrylate, hexa (meth) acrylate of dipentaerythritol-caprolactone adduct, tri (meth) acrylate of tris (2-hydroxyethyl) isocyanurate-caprolactone adduct, polyethylene glycol [200 to 1000] di (meth) Acrylate, polypropylene glycol [2
00-1000] di (meth) acrylate, tris (2
-(Hydroxyethyl) isocyanurate-caprolactone adduct tri (meth) acrylate.

Carboxylic esters and phosphoric esters having the following (meth) acryloyl groups: Bis (acryloyloxyneopentyl glycol) adipate, di (meth) acrylate of neopentyl glycol hydroxypivalate, di (meth) acrylate of neopentyl glycol hydroxypivalate-caprolactone adduct, bis (2- (meth) acryloyl Oxyethyl) phosphate, tris (2- (meth) acryloyloxyethyl) phosphate.

The following polyepoxide (meth) acrylic acid adduct (provided that one molecule of (meth) acrylic acid is added to each epoxy group of polyepoxide), and glycidyl (meth) acrylate and polyhydric alcohol or polyhydric alcohol Reaction products with carboxylic acids (provided that two or more molecules of glycidyl (meth) acrylate are reacted per molecule of polyhydric alcohol or the like). Bisphenol A-diglycidyl ether (meth) acrylic acid adduct, vinylcyclohexene dioxide- (meth) acrylic acid adduct, dicyclopentadiene dioxide- (meth) acrylic acid adduct, glycidyl (meth) acrylate and ethylene glycol Reaction product of glycidyl (meth) acrylate and propylene glycol; reaction product of glycidyl (meth) acrylate and diethylene glycol; reaction product of glycidyl (meth) acrylate and 1,6-hexanediol; glycidyl (meth) A) reaction products of acrylate and glycerol, reaction products of glycidyl (meth) acrylate and trimethylolpropane, and reaction products of glycidyl (meth) acrylate and phthalic acid.

Alkyl ethers, alkenyl ethers, carboxylic esters and the like of the above-mentioned (meth) acrylates and compounds having an unreacted hydroxyl group (hereinafter also referred to as modified products), Such compounds. Alkyl-modified dipentaerythritol penta (meth) acrylate, alkyl-modified dipentaerythritol tetra (meth) acrylate, alkyl-modified dipentaerythritol tri (meth) acrylate, allyl etherified product of vinylcyclohexene dioxide- (meth) acrylic acid adduct, Vinylcyclohexene dioxide-
Methyl etherified (meth) acrylic acid adduct, stearic acid-modified pentaerythritol di (meth) acrylate.

As the polyfunctional compound (a), at least a part thereof (preferably 30% by weight or more) is used because the cured product of the coating composition (A) can exhibit sufficient abrasion resistance.
Preferably comprises a trifunctional or higher polyfunctional compound (a). Preferably, 50% by weight or more of the polyfunctional compound (a) has three or more functional groups. Further, specific preferred polyfunctional compounds (a) are the following polyfunctional compounds (a) having no urethane bond with acrylic urethane.

In the case of acrylic urethane, acrylic urethane which is a reaction product of pentaerythritol or its multimer, polypentaerythritol, polyisocyanate and hydroxyalkyl (meth) acrylate), or hydroxyl-containing poly (pentaerythritol or polypentaerythritol) Acrylic urethane which is a reaction product of a (meth) acrylate and a polyisocyanate,
A compound having a functionality of 4 or more (preferably 4 to 20) is preferred.

Examples of the polyfunctional compound (a) having no urethane bond include pentaerythritol-based poly (meth)
Acrylates and isocyanurate-based poly (meth) acrylates are preferred. The pentaerythritol-based poly (meth) acrylate refers to pentaerythritol or polyester of polypentaerythritol and (meth) acrylic acid (preferably having a functionality of 4 to 20). The isocyanurate-based poly (meth) acrylate is tris (hydroxyalkyl) isocyanurate or its 1
It refers to a polyester (2 to 3 functional) of an adduct obtained by adding 1 to 6 mol of caprolactone or alkylene oxide to a mol and (meth) acrylic acid.

It is also preferable to use these preferred polyfunctional compounds (a) in combination with other bifunctional or higher polyfunctional compounds (a) (particularly polyhydric alcohol poly (meth) acrylates). These preferred polyfunctional compounds (a) comprise at least 30% by weight, in particular 50% by weight, based on the total polyfunctional compound (a).
% By weight or more is preferred.

As the monofunctional compound that can be used together with the polyfunctional compound (a), for example, a compound having one (meth) acryloyl group in the molecule is preferable. Such a monofunctional compound may have a functional group such as a hydroxyl group and an epoxy group. Preferred monofunctional compounds are (meth) acrylates, ie (meth) acrylates.

Specific examples of the monofunctional compound include the following compounds. Methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) Acrylate, cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate,
2-hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, benzyl (meth) acrylate, 1,4-butylene glycol mono (meth) acrylate, ethoxyethyl (meth) acrylate, phenylglycidyl (Meth) acrylic acid adduct of ether.

In order to enhance the abrasion resistance and hardness of the inner layer, the composition (A) may contain an effective amount of colloidal silica having an average particle size of 200 nm or less. The average particle size of the colloidal silica is preferably from 1 to 100 nm, particularly preferably 1 to 100 nm.
~ 50 nm is preferred. The colloidal silica is preferably the following surface-modified colloidal silica from the viewpoint of improving the dispersion stability of the colloidal silica and the adhesion between the colloidal silica and the polyfunctional compound (a).

When using these colloidal silicas,
In order to sufficiently exert the effect to be used, the amount of the colloidal silica is determined by adjusting the amount of the curable component (polyfunctional compound (a)) in the inner layer.
5 parts by weight or more, and preferably 10 parts by weight or more, based on 100 parts by weight of the compound (a) and the monopolyfunctional compound (a). If this amount is small, it is difficult to obtain sufficient wear resistance. On the other hand, if the amount is too large, fogging (haze) tends to occur in the coating, and the obtained vehicle window material is subjected to heat bending.
When the next processing is performed, problems such as cracks are likely to occur. Therefore, the upper limit of the amount of colloidal silica in the inner layer is preferably 300 parts by weight based on 100 parts by weight of the curable component. A more preferred amount of the colloidal silica is 50 to 250 parts by weight based on 100 parts by weight of the curable component.

As the colloidal silica, a surface-unmodified colloidal silica can be used, but preferably a surface-modified colloidal silica is used. The use of surface-modified colloidal silica improves the dispersion stability of the colloidal silica in the composition. It is considered that the average particle size of the colloidal silica fine particles is not substantially changed or slightly increased by the modification, but the average particle size of the obtained modified colloidal silica is considered to be in the above range. Hereinafter, the surface-modified colloidal silica (hereinafter, simply referred to as modified colloidal silica) will be described.

The unmodified colloidal silica as a raw material of the modified colloidal silica is available in the form of an acidic or basic dispersion. Although any form can be used, when a basic colloidal silica is used, a means such as addition of an organic acid is used so that the cured composition of the inner layer does not gel and the silica does not precipitate from the colloidal dispersion system. To make the dispersion acidic.

Various dispersion media are known as dispersion media of colloidal silica, and the dispersion media of raw material colloidal silica are not particularly limited. If necessary, the modification can be performed by changing the dispersion medium, and the dispersion medium can be changed after the modification. The dispersion medium of the modified colloidal silica is preferably used as a medium (solvent) for the cured composition of the inner layer directly in contact with the resin plate. As the medium of the cured composition of the inner layer which is in direct contact with the resin plate, a solvent having a relatively low boiling point, that is, a usual solvent for a coating material, is preferred from the viewpoint of drying properties and the like.

For reasons such as ease of production, it is preferable that the dispersion medium of the raw material colloidal silica, the dispersion medium of the modified colloidal silica, and the medium of the cured composition of the inner layer are all the same medium (solvent). Such media include:
Organic media widely used as coating solvents are preferred.

As the dispersion medium, for example, the following dispersion medium can be used. water. Lower alcohols such as methanol, ethanol, isopropanol, n-butanol, 2-methylpropanol, 4-hydroxy-4-methyl-2-pentanone and ethylene glycol. Cellosolves such as methyl cellosolve, ethyl cellosolve, and butyl cellosolve. Dimethylacetamide, toluene, xylene, methyl acetate, ethyl acetate, butyl acetate, acetone and the like.

As described above, the dispersion medium is preferably an organic dispersion medium, and among the above-mentioned organic dispersion mediums, alcohols and cellosolves are more preferred. Note that an integrated product of colloidal silica and a dispersion medium in which the colloidal silica is dispersed is referred to as a colloidal silica dispersion.

The modification of the colloidal silica is preferably carried out using a compound having a hydrolyzable silicon group or a silicon group to which a hydroxyl group is bonded (hereinafter, these are referred to as modifiers). It is considered that silanol groups are generated by hydrolysis of the hydrolyzable silicon groups, and these silanol groups react with and bind to silanol groups that are considered to be present on the colloidal silica surface, and the modifier binds to the colloidal silica surface. Two or more modifiers may be used in combination. Further, as described later, a reaction product obtained by previously reacting two types of modifiers having reactive functional groups that are reactive with each other can be used as the modifier.

The modifying agent may have two or more hydrolyzable silicon groups or silanol groups, a partial hydrolysis condensate of a compound having a hydrolyzable silicon group or a partial condensation of a compound having a silanol group. It may be a thing. Preferably, a compound having one hydrolyzable silicon group is used as a modifying agent (a partially hydrolyzed condensate may be generated during the modification treatment). Further, it is preferable that the modifier has an organic group bonded to a silicon atom, and one or more of the organic groups is an organic group having a reactive functional group.

A preferred modifier is a compound represented by the following formula 1. Y _3-n -SiR ¹ _n R ² Formula 1 wherein Y is a hydrolyzable group, R ¹ is a monovalent organic group having no reactive functional group, and R ² is 1 having a reactive functional group. A valent organic group, n represents 0, 1 or 2.

The hydrolyzable group represented by Y includes, for example, a halogen atom, an alkoxy group, an acyloxy group, an amide group, an amino group, an aminoxy group, a ketoximate group, and an alkoxy group is particularly preferable. As the alkoxy group, an alkoxy group having 4 or less carbon atoms is preferable, and a methoxy group and an ethoxy group are particularly preferable. n is 0 or 1
It is preferred that Further, the compound represented in the same manner as in Formula 1 and in which Y is a hydroxyl group is an example of the compound having a silanol group.

[0074] having no reactive functional group represented by R ¹ 1
As the valent organic group, a hydrocarbon group having 18 or less carbon atoms such as an alkyl group, an aryl group, and an aralkyl group is preferable.
As the hydrocarbon group, a hydrocarbon group having 8 or less carbon atoms,
Particularly, an alkyl group having 4 or less carbon atoms is preferable. R ¹ is particularly preferably a methyl group and an ethyl group. Here, the monovalent organic group refers to an organic group bonded to a silicon atom by a carbon atom (the same applies to R ² ).

The monovalent organic group having a reactive functional group represented by R ² includes an alkyl group having a reactive functional group,
A hydrocarbon group having 18 or less carbon atoms such as an aryl group and an aralkyl group is preferred. This organic group may have two or more reactive functional groups. Examples of the reactive functional group include an amino group, a mercapto group, an epoxy group, an isocyanate group, and a polymerizable unsaturated group. As the polymerizable unsaturated group, R ²
It may be itself (for example, a vinyl group) or a polymerizable unsaturated group which becomes R ² by bonding to an organic group such as a (meth) acryloyloxy group or a vinyloxy group. The amino group may be a primary or secondary amino group. In the case of a secondary amino group, the organic group bonded to the nitrogen atom is an alkyl group, an aminoalkyl group, an aryl group, etc. Alkyl group of 4 or less, carbon number 4
The following aminoalkyl groups and phenyl groups are preferred.

Preferred reactive functional groups are amino, mercapto, epoxy and (meth) acryloyloxy. The organic group to which the reactive functional group binds is preferably an alkylene group having 8 or less carbon atoms or a phenylene group, excluding the reactive functional group, and particularly preferably an alkylene group having 2 to 4 carbon atoms (particularly, a polymethylene group). Specific examples of the modifying agent include the following compounds when classified according to the type of the reactive functional group.

(Meth) acryloyloxy group-containing silanes; γ- (meth) acryloyloxypropyltrimethoxysilane, γ- (meth) acryloyloxypropyltriethoxysilane, γ- (meth) acryloyloxypropylmethyldimethoxysilane and the like.

Amino group-containing silanes; γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltriethoxysilane,
γ-ureidopropyltriethoxysilane, N- (N-
Vinylbenzyl-β-aminoethyl) -γ-aminopropyltrimethoxysilane, γ-anilinopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane and the like.

Mercapto group-containing silanes; γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane and the like. Epoxy group-containing silanes; γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyltriethoxysilane and the like. Isocyanate group-containing silanes; γ-isocyanatepropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropylmethyldiethoxysilane and the like.

The reaction products obtained by previously reacting two types of modifiers having reactive functional groups reactive with each other include, for example, a reaction product of an amino group-containing silane and an epoxy group-containing silane, Reaction products of group-containing silanes and (meth) acryloyloxy group-containing silanes, reaction products of epoxy group-containing silanes and mercapto group-containing silanes, mercapto group-containing silanes 2
There are reaction products of molecules.

The modification of colloidal silica is usually carried out by bringing a modifier having a hydrolyzable group into contact with colloidal silica and hydrolyzing it. For example, it can be modified by adding a modifier to the colloidal silica dispersion and hydrolyzing the modifier in the colloidal silica dispersion. In this case, it is considered that the hydrolyzate of the modifier chemically or physically binds to the surface of the fine particles of colloidal silica to modify the surface. In particular, since silanol groups are usually present on the colloidal silica surface, it is considered that the silanol groups condense with the silanol groups generated by hydrolysis of the modifier to form a surface to which the hydrolysis residues of the modifier are bonded. . It is also considered that the hydrolyzate itself that has undergone a condensation reaction may similarly bind to the surface. Also,
In the present invention, modification can be performed by adding a modifying agent to a colloidal silica dispersion liquid after performing hydrolysis to some extent.

In the case of modifying the surface of colloidal silica with a modifier having a hydrolyzable group, the modifier is added to and mixed with the colloidal silica dispersion and hydrolyzed with water in the system or newly added water. As a result, a modified colloidal silica whose surface is modified with this hydrolyzate is obtained. A catalyst is preferably present in order to effectively promote the hydrolysis reaction of the modifying agent and the reaction between the silanol group on the colloidal silica surface and the modifying agent or its partially hydrolyzed condensate. When modifying with a modifier having a silanol group, a catalyst is preferably present to promote the reaction between the silanol groups.

The catalyst includes an acid and an alkali.
Preferably, an acid selected from inorganic acids and organic acids is used. As the inorganic acid, for example, hydrohalic acid such as hydrochloric acid, hydrofluoric acid and hydrobromic acid, sulfuric acid, nitric acid, phosphoric acid and the like can be used. As the organic acid, formic acid, acetic acid, oxalic acid, (meth) acrylic acid and the like can be used.

The reaction is usually carried out in a solvent in order to make the hydrolysis reaction proceed uniformly. Usually, this solvent is a dispersion medium for the raw colloidal silica dispersion. However, a solvent other than this dispersion medium or a mixed solvent of this dispersion medium and another solvent may be used. The conditions of this solvent include dissolving the modifier,
It is preferably one that is compatible with water and a catalyst and hardly causes aggregation of colloidal silica.

Specifically, water; lower alcohols such as methanol, ethanol, isopropanol and n-butanol; ketones such as acetone, methyl isobutyl ketone and methyl ethyl ketone; ethers such as tetrahydrofuran and dioxane; methyl cellosolve And cellosolves such as ethyl cellosolve and butyl cellosolve; dimethylacetamide and the like.

As these solvents, the above-mentioned dispersion medium of colloidal silica may be used as it is, or may be used by substituting a solvent other than the dispersion medium. Further, a necessary amount of a solvent other than the dispersion medium may be newly added to the dispersion and used. The reaction temperature is preferably from room temperature to the boiling point of the solvent used, and the reaction time is preferably in the range of 0.5 to 24 hours, depending on the temperature.

In the modification of the colloidal silica, the amount of the modifier used is not particularly limited, but the modifiers 1 to 10 are added to 100 parts by weight of the colloidal silica (solid content in the dispersion).
0 parts by weight is suitable. If the amount of the modifier is less than 1 part by weight, it is difficult to obtain the effect of surface modification. If the amount exceeds 100 parts by weight, a large amount of hydrolyzate to condensate of the unreacted modifier or the modifier not supported on the surface of the colloidal silica is generated, and these are chained during curing of the cured composition of the transparent coating layer. It acts as a transfer agent or as a plasticizer of the cured film, which may lower the hardness of the cured film.

In order to cure the polyfunctional compound (a) as described above, the coating composition (A) usually contains a photopolymerization initiator. Known or known photopolymerization initiators can be used. Particularly, commercially available products that are easily available are preferable.
A plurality of photopolymerization initiators may be used in the inner layer. Examples of the photopolymerization initiator include arylketone photopolymerization initiators (for example, acetophenones, benzophenones, alkylaminobenzophenones, benzyls, benzoins, benzoin ethers, benzyldimethyl ketals, benzoylbenzoates, α-acylo) Oxime esters), sulfur-containing photopolymerization initiators (eg, sulfides, thioxanthones, etc.), acylphosphine oxide photopolymerization initiators, and other photopolymerization initiators. In particular, the use of an acylphosphine oxide-based photopolymerization initiator is preferred. Further, the photopolymerization initiator can be used in combination with a photosensitizer such as an amine. Specific examples of the photopolymerization initiator include the following compounds.

4-phenoxydichloroacetophenone,
4-t-butyl-dichloroacetophenone, 4-t-butyl-trichloroacetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl)
-2-hydroxy-2-methylpropan-1-one, 1
-(4-dodecylphenyl) -2-methylpropane-1
-One, 4- (2-hydroxyethoxy) -phenyl (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenylketone, 2-methyl-1-
{4- (Methylthio) phenyl} -2-morpholinopropan-1-one.

Benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 3,3'-dimethyl-4-methoxybenzophenone, 3,3 ', 4,4'-tetrakis (t-
Butylperoxycarbonyl) benzophenone, 9.1
0-phenanthrenequinone, camphorquinone, dibenzosuberone, 2-ethylanthraquinone, 4 ', 4 "-
Diethyl isophthalophenone, α-acyloxime ester, methylphenylglyoxylate.

4-benzoyl-4'-methyldiphenyl sulfide, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone. 2,4
6-trimethylbenzoyldiphenylphosphine oxide, benzoyldiphenylphosphine oxide, 2,6
-Dimethylbenzoyldiphenylphosphine oxide,
Bis (2,6-dimethoxybenzoyl) -2,4,4-
Trimethylpentyl phosphine oxide.

The amount of the photopolymerization initiator in the coating composition (A) is 0.01 to 20 parts by weight based on 100 parts by weight of the curable component (the total of the polyfunctional compound (a) and the monofunctional compound). Particularly, 0.1 to 10 parts by weight is preferable.

The coating composition (A) may contain a solvent and various additives in addition to the above basic components. The solvent is usually an essential component, and a solvent is used unless the polyfunctional compound (a) is a liquid having a particularly low viscosity. As the solvent, a solvent usually used for a coating composition containing the polyfunctional compound (a) as a curing component can be used. The dispersion medium of the raw material colloidal silica can be used as a solvent as it is. Further, it is preferable to select and use an appropriate solvent depending on the type of the resin plate.

The amount of the solvent can be appropriately changed depending on the required viscosity of the composition, the desired thickness of the cured film, the drying temperature conditions, and the like. Usually 100% for the curable component in the composition
It is used up to twice the weight, preferably 0.1 to 50 times the weight. Examples of the solvent include solvents such as lower alcohols, ketones, ethers, and cellosolves, which are mentioned as the solvent used for the hydrolysis for modifying the colloidal silica. Other examples include esters such as n-butyl acetate and diethylene glycol monoacetate, halogenated hydrocarbons, hydrocarbons, and the like. For coating of an aromatic polycarbonate resin having low solvent resistance, lower alcohols, cellosolves, esters, a mixture thereof and the like are suitable.

The coating composition (A) may contain, if necessary, stabilizers such as an ultraviolet absorber, a light stabilizer, an antioxidant, and a thermal polymerization inhibitor, a leveling agent, an antifoaming agent, a thickener, and an anti-settling agent. Agent,
A surfactant such as a pigment, a dispersant, an antistatic agent, and an anti-fogging agent, and a curing catalyst selected from acids, alkalis, and salts may be appropriately blended and used.

The coating composition (A) preferably contains an ultraviolet absorber or a light stabilizer. As the ultraviolet absorber, a benzotriazole-based ultraviolet absorber, a benzophenone-based ultraviolet absorber, a salicylic acid-based ultraviolet absorber, and the like which are generally used as an ultraviolet absorber for a synthetic resin are preferable. As the light stabilizer, a hindered amine-based light stabilizer (such as a 2,2,4,4-tetraalkylpiperidine derivative) which is also commonly used as a light stabilizer for a synthetic resin is also preferable.

Ultraviolet rays are particularly preferred as the active energy rays for curing such a coating composition (A). However, it is not limited to ultraviolet rays, and electron beams and other active energy rays can be used. Xenon lamps, pulsed xenon lamps, low-pressure mercury lamps, high-pressure mercury lamps,
Ultra-high pressure mercury lamps, metal halide lamps, carbon arc lamps, tungsten lamps and the like can be used.

The layer thickness of the cured product formed using the coating composition (A) is preferably 1 to 50 μm. If the thickness is more than 50 μm, curing by active energy rays becomes insufficient, and the adhesion to the resin plate tends to be impaired, which is not preferable. If the thickness is less than 1 μm, the abrasion resistance of this layer may be insufficient, and the abrasion resistance and abrasion resistance of the outer layer on this layer may not be sufficiently exhibited. A more preferred layer thickness is 2 to 30 μm.

A cured product of the coating composition (B) capable of forming a silica layer substantially free of an organic group as an outer layer for obtaining high wear resistance as a window material for vehicles. A silica layer. The coating composition (B) comprises a soluble compound capable of forming silica and usually a solvent.
Examples of the soluble compound capable of forming silica containing substantially no organic group include a tetrafunctional hydrolyzable silane compound, a partially hydrolyzed condensate thereof, and polysilazane. Examples of the tetrafunctional hydrolyzable silane compound and its partially hydrolyzed condensate include tetraalkoxysilane and its partially hydrolyzed condensate. However, polysilazane is preferably used. Since polysilazane forms silica having a more dense structure, an outer layer having more excellent surface characteristics can be obtained.

Examples of the polysilazane include polysilazane (perhydropolysilazane) substantially free of an organic group, polysilazane in which a hydrolyzable group such as an alkoxy group is bonded to a silicon atom, and an organic group such as an alkyl group bonded to a nitrogen atom. There are polysilazanes. Even if such polysilazane has an organic group, silica substantially containing no organic group is formed by a hydrolysis reaction at the time of curing. In particular, perhydropolysilazane is preferable from the viewpoint of low firing temperature and denseness of a cured film after firing. The cured product obtained by sufficiently curing the polysilazane becomes silica containing almost no nitrogen atoms.

The polysilazane is composed of a polymer having a chain, cyclic or crosslinked structure, or a mixture of a plurality of these structures in the molecule. The molecular weight of polysilazane is preferably 200 to 50,000 in number average molecular weight. If the number average molecular weight is less than 200, it is difficult to obtain a uniform cured film even when firing. On the other hand, if the number average molecular weight is more than 50,000, it is not preferable because it is difficult to dissolve in a solvent and the coating composition (B) may become viscous.

Solvents for dissolving polysilazane include hydrocarbon solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons and aromatic hydrocarbons, halogenated hydrocarbon solvents, aliphatic ethers, and the like.
Ethers such as alicyclic ethers can be used. Specifically, pentane, hexane, isohexane, methylpentane, heptane, isoheptane, octane, isooctane, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, benzene, toluene,
Hydrocarbons such as xylene and ethylbenzene, halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, bromoform, ethylene chloride, ethylidene chloride, trichloroethane and tetrachloroethane, ethyl ether,
Examples include ethers such as isopropyl ether, ethyl butyl ether, butyl ether, dioxane, dimethyl dioxane, tetrahydrofuran, and tetrahydropyran.

When these solvents are used, plural kinds of solvents may be mixed in order to adjust the solubility of polysilazane and the evaporation rate of the solvent. The amount of the solvent to be used varies depending on the coating method employed, the structure of polysilazane, the average molecular weight, and the like, but is preferably adjusted to a solid concentration of 0.5 to 80% by weight.

In order to cure the polysilazane into silica, heating which is usually called calcination is required. But,
In the present invention, the firing temperature is limited because the resin plate is a synthetic resin. That is, it is difficult to heat and cure the resin plate at a temperature higher than the heat resistance temperature. Generally, the heat resistance of the cured product of the coating composition (A) is higher than that of the resin plate. However, in some cases, the heat resistance of the cured product may be lower than the heat resistance of the resin plate. In such a case, it may be necessary to cure the polysilazane at a temperature lower than the heat resistance temperature of the cured product. Therefore, when a resin plate made of a general synthetic resin such as an aromatic polycarbonate resin is used in the present invention, the firing temperature of polysilazane is preferably 180 ° C. or less.

In order to lower the firing temperature of polysilazane, a catalyst is usually used. Depending on the type and amount of the catalyst, it can be calcined at a low temperature, and in some cases, can be cured at room temperature. Further, it is preferable that the atmosphere in which the firing is performed is an atmosphere in which oxygen is present, such as in air. By firing polysilazane, its nitrogen atoms are replaced by oxygen atoms to produce silica. By firing in an atmosphere in which sufficient oxygen exists, a dense silica layer is formed.

It is preferable to use a catalyst capable of curing polysilazane at lower temperature. Such catalysts include, for example, gold, silver, palladium, platinum,
There is a metal catalyst composed of fine particles of a metal such as nickel.
The particle size of these metal fine particles is preferably smaller than 0.1 μm, and more preferably smaller than 0.05 μm in order to ensure transparency of the cured product. In addition, as the particle size decreases, the specific surface area increases, and the catalytic ability increases. Therefore, it is preferable to use a catalyst having a smaller particle size in terms of improving the catalytic performance. The amount of the catalyst is 0.01 to 10 parts by weight, more preferably 0.05 to 5 parts by weight, based on 100 parts by weight of the polysilazane. The blending amount is 0.
If the amount is less than 01 parts by weight, a sufficient catalytic effect cannot be expected, and
If the amount is more than part by weight, agglomeration of the catalysts tends to occur, and the transparency may be impaired.

The coating composition (B) may contain, if necessary, stabilizers such as an ultraviolet absorber, a light stabilizer and an antioxidant, a leveling agent, an antifoaming agent, a thickener, an antisettling agent, a pigment, Surfactants such as a dispersant, an antistatic agent and an antifogging agent may be appropriately blended and used. In the following, polysilazane refers to perhydropolysilazane unless otherwise specified.

The thickness of the cured product layer formed using the coating composition (B) is preferably 0.05 to 10 μm. If the thickness of the outer layer is more than 10 μm, further improvement in surface properties such as scratch resistance cannot be expected, and the layer becomes brittle, and cracks and the like are liable to occur in this layer even by slight deformation of the coated molded product. On the other hand, if the thickness is less than 0.05 μm, the outer layer may not sufficiently exhibit wear resistance and scratch resistance. A more preferred layer thickness is 0.1 to 3 μm.

The two kinds of coating compositions (A) as described above,
As a method of forming two transparent cured layers formed using (B), a usual coating method can be adopted. For example, first, a coating composition (A) is applied and cured on a resin plate, and then the coating composition (B) is applied and cured on the surface of the cured product to obtain a target vehicle window. Wood is obtained.

The means for applying these coating compositions is not particularly limited, and a known or well-known method can be employed.
For example, dipping, flow coating, spraying, bar coating, gravure coating, roll coating, blade coating, air knife coating, spin coating, slit coating, micro gravure coating, etc. it can. After coating, if the coating composition contains a solvent, the coating composition is dried to remove the solvent, and then, in the case of a layer using the coating composition (A), the coating composition is cured by irradiating ultraviolet rays or the like, and the coating composition (B In the case of a layer using ()), the layer is cured by heating or left at room temperature.

The combination (timing) of the curing of the coating composition (A) and the coating and curing of the coating composition (B) includes the following three methods. 1) A method of applying the coating composition (A), irradiating a sufficient amount of active energy rays after the coating to sufficiently complete the curing, and then coating the composition (B) thereon (the method described above). ).

2) After coating the coating composition (A) to form an uncured layer of the coating composition (A), the coating composition (B) was coated on the uncured layer. Forming a layer of the uncured material of the coating composition (B) by irradiating a sufficient amount of active energy rays to terminate the curing of the uncured material of the coating composition (A). In this case, the uncured material of the coating composition (B) cures almost simultaneously with the uncured material of the coating composition (A),
The uncured coating composition (A) is cured by heating or the like after curing.

3) The minimum amount of active energy rays (usually about 30
(Irradiation amount up to 0 mJ / cm ² ) to form a partially cured layer of the coating composition (A), and then apply the coating composition (B) on the partially cured layer to form a coating. Composition (B)
A method of forming a layer of the uncured material, and thereafter irradiating a sufficient amount of active energy rays to terminate the curing of the uncured material of the coating composition (A). The curing of the uncured material of the coating composition (B) is the same as in the above 2).

In order to increase the adhesion between the two cured product layers, the above method 2) or 3) is more preferable. However, in the case of the method 2), when the dipping method is used as a method of applying the coating composition (B), the coating composition (A)
However, there is a possibility that the uncured component may contaminate the dipping solution of the coating composition (B), and thus there is a restriction that the coating by such a dipping method is not suitable.

The window material for a vehicle usually has a curved shape.
When manufacturing the bent window material for a vehicle of the present invention, the bent window resin plate can be used as the vehicle window material of the present invention. However, when a bent resin plate is used, it is often difficult to form each layer by coating and curing. On the other hand, according to conventional studies by the present inventors, a resin plate having a cured product layer of the coating composition (A) formed thereon can be bent by hot bending or the like. However, when a layer of the cured product of the coating composition (B) is formed, the cured product is hard, so that bending is difficult.

The inventor of the present invention has proposed a resin sheet having such a layer (a layer of a cured product of the coating composition (A)) if the layer is an uncured or partially cured product of the coating composition (B). ) Can be bent. Further, as in the methods 2) and 3), an uncured or partially cured layer of the coating composition (B) is formed on the uncured or partially cured layer of the coating composition (A). It can also be bent in a state where it has been bent. By curing the uncured or partially cured product of the coating composition (B) after or almost simultaneously with the bending, the intended bent coated article can be obtained. The bending is usually performed in a heated state. Therefore, the uncured material or the partially cured material of the coating composition (B) is cured by heating for bending, but the uncured material of the coating composition (B) or the uncured material of the coating composition (B) is usually compared with the time required for bending. Since the time required for curing the partially cured product is long, there is little possibility that bending processing becomes difficult due to the curing of the coating composition (B).

Accordingly, the bent window material of the present invention can be obtained by coating the coating composition (A) on a resin plate with an uncured product, a partially cured product or a cured product, and a coating composition (B) on the surface of the layer. )) After forming the uncured or partially cured layer
The resin plate having these layers is bent, and then the uncured or partially cured product of the coating composition (B) and the uncured or partially cured product of the coating composition (A), if any, are present. Can be produced by curing.

Specifically, for example, the coating composition (B)
After forming a layer of an uncured or partially cured material, the resin plate is heated to a heat softening temperature of the resin plate for about 5 minutes, followed by bending.
Thereafter, the resin composition is cured at a temperature lower than the thermal softening temperature of the resin plate and at a temperature at which the uncured or partially cured product of the coating composition (B) can be cured, whereby the bent window material of the present invention is obtained. can get. According to such a method, the resin plate is deformed before the coating composition (B) is sufficiently cured, and a hard silica layer is formed thereafter, so that problems such as cracks do not occur in the silica layer.

As the material of the resin plate in the present invention, various transparent synthetic resins can be used. For example, a transparent synthetic resin such as an aromatic polycarbonate resin, a polymethyl methacrylate resin (acrylic resin), or a polystyrene resin can be used as a material for the resin plate. Particularly, a resin plate made of an aromatic polycarbonate resin is preferable. The thickness of the resin plate is appropriately determined according to the compatible portion of the window material.
0 mm.

External force such as rubbing is applied to the vehicle window material particularly from the outside of the vehicle. Therefore, the window material of the present invention is preferably attached to the vehicle body such that the surface on which the first coat layer is provided is disposed outside the vehicle. In this case, the abrasion resistance of the window material of the present invention on the first coat layer side is JIS.
-Wear test specified in R3212 (10
(00 times) is preferably 10% or less. In particular, when the window material of the present invention is attached to the front side window of the vehicle, the wear resistance is preferably 4% or less in order to secure the driver's view.

Since an external force such as rubbing is also applied to the inner side surface of the window material, it is preferable that the window material of the present invention has a second coating layer provided on a resin plate as shown in FIG. FIG.
The second coat layer 2 is the same kind as the first coat layer and a different composition even if a transparent cured material layer obtained by curing the same composition as the first coat layer 1 is formed in the same laminated configuration. May be formed in the same layered structure. Further, a coating layer using a different layer configuration from the first coating layer or a different conventionally known material may be used.

In the case where the second coat layer is formed of a coat layer using a conventionally known material different from the first coat layer, for example, there are the following cases. In general,
Vehicle window materials include fixed windows such as front windows, side windows, and rear windows, and sliding windows that slide like door windows. Since the fixing window is bonded and fixed to the vehicle body through an adhesive such as urethane, it is necessary to select a coating layer provided on the resin plate that has a sufficient adhesive fixing force to the vehicle body. The first coat layer in the present invention can have a surface performance equivalent to the surface of quartz glass if the outer layer is completely cured, and can sufficiently express the adhesive fixing force to the vehicle body.

On the other hand, as a coat layer having excellent adhesion to a vehicle body, an acrylic coat layer has been conventionally known. Therefore, in order to obtain especially high adhesion to the vehicle body,
As the second coat layer, a layer different from the first coat layer, such as a conventionally known acrylic coat layer, can be used.

When the second coat layer is different from the first coat layer, the number of coating steps on the resin plate increases.
The number of steps required for bending the window material of the present invention increases, and the abrasion resistance is slightly inferior to the first coat layer. In particular, since window materials for vehicles often have a curved shape, the window material of the present invention using a material suitable for bending is effective. Therefore, it is preferable to form the second coat layer from the same type of transparent cured product as the first coat layer.

Further, the window material used for the sliding window opens and closes while being in contact with a run channel or a belt line molding provided on the periphery of the window opening of the vehicle body. Therefore, when the window material of the present invention is used for a sliding window, in order to make both surfaces of the resin plate have high abrasion resistance, the second coating layer is formed of the same kind of transparent hardening as the first coating layer. It is particularly preferred to form from an object.

When the second coat layer is formed of a material different from the first coat layer, the resin plate provided with these layers is bent, for example, as follows.
That is, after forming the layer of the uncured material or the partially cured material of the coating composition (B) as described above, when heating to the thermal softening temperature of the resin plate, the second coat layer is formed before heating. And heat-bending. In this case, unlike the cured product of the coating composition (B) of the first coat layer, a material that does not cause cracks or the like at the time of bending is used, and a material that is easily bent can be used for the second coat layer forming material. Desired. Such a second coat layer may be inferior in abrasion resistance as compared with the first coat layer because it is easy to bend. If the second coat layer is disposed on the inside of the vehicle where external force such as rubbing is unlikely to occur, even if the second coat layer has a lower abrasion resistance than the first coat layer, it may be used. The window material of the present invention can be sufficiently applied to vehicle windows.

By the way, as a window material for a vehicle, a laminated glass in which two or more glass plates are bonded via an intermediate film is conventionally known. The resin plate with a hard coat according to the present invention can be used as one of the glass plates of the laminated glass. In this case, one surface of the resin plate is disposed opposite to the glass plate surface and is not exposed, so that the second coat layer may not be provided. Further, in consideration of the adhesiveness to the intermediate film, an appropriate layer can be provided instead of the hard coat layer instead of the second coat layer. Furthermore, the resin plate with a hard coat layer in the present invention can be used as a laminated resin plate in which two or more resin plates are laminated via an intermediate film or an intermediate adhesive layer. In this case, it is preferable that the vehicle window material of the present invention is configured such that the first coat layer is disposed on the vehicle exterior surface of the laminated resin plate.

In the window material of the present invention, a dark-colored layer provided on a peripheral portion of the window material for concealing an adhesive for bonding and fixing to the vehicle body from the outside of the vehicle, and a predetermined portion of the window material are provided. A linear antenna conductor, a hot wire conductor, or the like can be provided. Specifically, a dark paint is applied between the inner layer and the resin plate, between the resin plate and the second coat layer, on the second coat layer, or the like, by providing a ceramic conductor print, or the like. sell. A coloring agent may be added to the composition itself forming each layer constituting the window material, and the window material itself may be a colored transparent window. Using a third layer that can be formed between the first coat layer and the resin plate, the coloring, conductor print, and the like can be provided in the window material of the present invention.

[0129]

The present invention will be described below with reference to Synthesis Examples (Examples 1 to 5), Examples (Examples 6 to 16), and Comparative Examples (Examples 17 to 20), but the present invention is not limited thereto. Examples 6 to 15,
The measurement and evaluation of various physical properties of Nos. 18 to 20 were performed by the following methods, and the results are shown in Table 1. Table 1 also shows the results of measurement and evaluation of physical properties using a normal vehicle window glass plate.

[Initial haze value, abrasion resistance] JIS-R321
According to the abrasion resistance test method in No. 2, the haze value was measured with a haze meter when a 500 g weight was combined with each of the two CS-10F abrasion wheels, and the haze meter was used to evaluate the abrasion resistance. The haze was measured at four points on the wear cycle orbit, and the average value was calculated.

The abrasion resistance test of the inner layer before forming the outer layer was performed by using a sample obtained by applying the curable coating composition (A) to a resin plate and curing the resin layer in the same manner as described above. The abrasion resistance was evaluated by measuring the haze value before the abrasion test and the haze value after 100 rotations.

[Adhesion] The sample was cut 11 times in each of the vertical and horizontal directions at intervals of 1 mm with a razor blade to make 100 grids. Then, when a commercially available cellophane tape is closely adhered and then rapidly peeled in the forward direction by 90 degrees, the number (m) of the grids remaining without peeling off the coating is represented by m / 100.

[Weather Resistance] The appearance was evaluated using a sunshine weather meter at a black panel temperature of 63 ° C. and a cycle of rainfall of 12 minutes and drying of 48 minutes for 3000 hours.

[Example 1] Ethyl cellosolve dispersed colloidal silica (silica content: 30% by weight, average particle size: 11 nm)
5 parts by weight of 3-mercaptopropyltrimethoxysilane and 3.0 parts by weight of 0.1N hydrochloric acid were added to 100 parts by weight, and 10 parts by weight were added.
After heating and stirring at 0 ° C. for 6 hours, the mixture was aged at room temperature for 12 hours to obtain a mercaptosilane-modified colloidal silica dispersion.

Example 2 Dispersion of acrylsilane-modified colloidal silica was carried out in the same manner as in Example 1, except that 5 parts by weight of γ-acryloyloxypropyltrimethoxysilane was used instead of 5 parts by weight of 3-mercaptopropyltrimethoxysilane. A liquid was obtained.

Example 3 An aminosilane-modified colloid was prepared in the same manner as in Example 1 except that 5 parts by weight of N-phenyl-3-aminopropyltrimethoxysilane was used instead of 5 parts by weight of 3-mercaptopropyltrimethoxysilane. A silica dispersion was obtained.

[Example 4] Epoxysilane-modified colloidal silica was prepared in the same manner as in Example 1 except that 5 parts by weight of 3-glycidoxypropyltrimethoxysilane was used instead of 5 parts by weight of 3-mercaptopropyltrimethoxysilane. A dispersion was obtained.

Example 5 Isopropanol-dispersed colloidal silica (silica content: 30% by weight, average particle size: 11 nm) instead of ethyl cellosolve-dispersed colloidal silica
A mercaptosilane-modified colloidal silica dispersion was obtained in the same manner as in Example 1 except that 00 parts by weight and the reaction temperature was 83 ° C.

[Example 6] 1 equipped with a stirrer and a cooling pipe
In a 00 mL four-necked flask, add isopropanol 15
g, butyl acetate 15 g, ethyl cellosolve 7.5 g,
2,4,6-trimethylbenzoyldiphenylphosphine oxide 150 mg, 2- (3,5-di-t-amyl-2-hydroxyphenyl) benzotriazole 100
0 mg, and bis (1-octyloxy-2,2,2)
200 mg of 6,6-tetramethyl-4-piperidinyl) sebacate is added and dissolved, and then urethane acrylate (an average of 15 acrylates per molecule) is a reaction product of dipentaerythritol polyacrylate having a hydroxyl group and partially nullated hexamethylene diisocyanate. Was added and the mixture was stirred at room temperature for 1 hour to obtain a coating composition (hereinafter, referred to as coating liquid 1).

This coating liquid 1 was applied (wet thickness 16 μm) to a transparent aromatic polycarbonate resin plate (150 mm × 300 mm) having a thickness of 3 mm using a bar coater, and was then placed in a hot air circulating oven at 80 ° C. for 5 minutes. Held. This was put in an air atmosphere using a high-pressure mercury lamp at 3000 mJ /
Ultraviolet rays of cm ² (integrated amount of ultraviolet energy in a wavelength range of 300 to 390 nm) were irradiated to form an inner layer having a thickness of 5 μm.

Next, a xylene solution of perhydropolysilazane (solids: 20% by weight, trade name: L110, manufactured by Tonen Co., Ltd.) (hereinafter referred to as a coating liquid 2) (which is hereinafter referred to as a coating liquid 2) was further applied using a bar coater. Coat (wet thickness 6 μm) and hold in a hot air circulating oven at 80 ° C. for 10 minutes followed by 120 ° C. in a hot air circulating oven at 100 ° C.
A sufficiently cured outer layer was obtained by holding for minutes. And it was confirmed by IR analysis that the outer layer was a complete silica coating. Thus, a first coat layer having a total film thickness of 6.2 μm was formed on the aromatic polycarbonate resin plate. Various physical properties were measured and evaluated using this sample.

On the other hand, another sample of an aromatic polycarbonate resin plate having an inner layer sufficiently cured by using the above-mentioned coating liquid 1 was evaluated for the abrasion resistance of the inner layer surface. 1
The abrasion resistance after 00 rotations was 2.8%.

[Example 7] The sample preparation method in Example 6 was changed as follows. After the coating solution 1 was applied, the coating solution was kept in a hot air circulating oven at 80 ° C. for 5 minutes, and was kept in an air atmosphere at 150 mJ / cm ² (wavelength 30
Ultraviolet rays in the range of 0 to 390 nm in ultraviolet energy) were applied to form a 5 μm-thick partially cured product layer. Then, the coating liquid 2 was applied thereon again using a bar coater (wet thickness: 6 μm), and kept in a hot air circulating oven at 80 ° C. for 10 minutes.
3000 mJ / cm ² (wavelength 300) using a high pressure mercury lamp
(Integrated energy of ultraviolet light in the range of ３390 nm). Finally, the sample was kept in a hot air circulating oven at 100 ° C. for 120 minutes, and then various physical properties were measured and evaluated.

[Example 8] The sample preparation method in Example 7 was changed as follows. Finally, instead of holding in a hot air circulating oven at 100 ° C. for 120 minutes, curing was performed at room temperature for one day, and various physical properties were measured.

[Example 9] The sample preparation method in Example 6 was changed as follows. After coating the coating liquid 1, the coating liquid 2 was kept in a hot air circulating oven at 80 ° C. for 5 minutes, and then the coating liquid 2 was again coated thereon using a bar coater (wet thickness 6 μm). Was held in a hot-air circulation oven for 10 minutes, and this was irradiated with 3000 mJ / cm ² (ultraviolet integrated energy in a wavelength range of 300 to 390 nm) using a high-pressure mercury lamp in an air atmosphere. Finally, the sample is placed in a hot air circulating oven at 100 ° C. for 120 minutes.
After holding for 5 minutes, various physical properties were measured and evaluated.

[Example 10] Isopropanol 15 was added to a 100 mL four-necked flask equipped with a stirrer and a condenser.
g, butyl acetate 15 g, 2,4,6-trimethylbenzoyldiphenylphosphine oxide 150 mg, 2-
(3,5-di-t-amyl-2-hydroxyphenyl)
1000 mg of benzotriazole and 200 mg of bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate were added and dissolved.
Subsequently, 10.0 g of tris (2-acryloyloxyethyl) isocyanurate was added, and the mixture was stirred at room temperature for 1 hour. Subsequently, 30.3 g of the mercaptosilane-modified colloidal silica dispersion synthesized in Example 1 was added, and the mixture was further stirred at room temperature for 15 minutes to obtain a coating composition (hereinafter, referred to as coating liquid 3).

Next, this coating liquid 3 was applied to a transparent aromatic polycarbonate resin plate (150 mm × 300 mm) having a thickness of 3 mm using a bar coater (wet thickness 16 μm).
m) and kept in a hot air circulating oven at 80 ° C. for 5 minutes. It is 150m in an air atmosphere using a high pressure mercury lamp.
Ultraviolet rays of J / cm ² (integrated energy of ultraviolet rays in a wavelength range of 300 to 390 nm) were applied to form a partially cured layer having a thickness of 5 μm. Then, the coating liquid 2 was applied thereon again using a bar coater (wet thickness: 6 μm), and kept in a hot air circulating oven at 80 ° C. for 10 minutes. 3000
Ultraviolet rays of mJ / cm ² (integrated energy of ultraviolet rays in a wavelength range of 300 to 390 nm) were applied. Finally, the sample was kept in a hot air circulating oven at 100 ° C. for 120 minutes, and then various physical properties were measured and evaluated.

On the other hand, a sample of an aromatic polycarbonate resin plate having an inner layer sufficiently cured by using the above-mentioned coating liquid 3 was evaluated for abrasion resistance on the surface of the transparent cured layer. The abrasion resistance after 100 rotations was 0.9%.

[Example 11] The sample preparation method in Example 10 was changed as follows. Finally, instead of holding in a hot air circulating oven at 100 ° C. for 120 minutes,
After curing, various physical properties were measured.

Example 12 The procedure of Example 10 was repeated except that 30.3 g of the acrylsilane-modified colloidal silica dispersion synthesized in Example 2 was used instead of 30.3 g of the mercaptosilane-modified colloidal silica dispersion synthesized in Example 1. In the same manner, various physical properties were measured and evaluated using this sample.
In addition, 100% of the inner layer sufficiently cured using a coating liquid using this acrylic silane-modified colloidal silica dispersion liquid.
The abrasion resistance after rotation was 1.1%.

Example 13 Same as Example 10 except that 30.3 g of the aminosilane-modified colloidal silica dispersion synthesized in Example 3 was used instead of 30.3 g of the mercaptosilane-modified colloidal silica dispersion synthesized in Example 1. Using this sample, various physical properties were measured and evaluated. The abrasion resistance after 100 rotations of the inner layer sufficiently cured by using the coating liquid using the aminosilane-modified colloidal silica dispersion was 1.3%.

Example 14 The procedure of Example 10 was repeated except that 30.3 g of the epoxysilane-modified colloidal silica dispersion synthesized in Example 4 was used instead of 30.3 g of the mercaptosilane-modified colloidal silica dispersion synthesized in Example 1. In the same manner, various physical properties were measured and evaluated using this sample.
In addition, 100% of the inner layer sufficiently cured using a coating liquid using the epoxysilane-modified colloidal silica dispersion liquid was used.
The abrasion resistance after rotation was 1.2%.

Example 15 Example 10 was repeated except that 30.3 g of the mercaptosilane-modified colloidal silica dispersion synthesized in Example 5 was used instead of 30.3 g of the mercaptosilane-modified colloidal silica dispersion synthesized in Example 1. In the same manner, various physical properties were measured and evaluated using this sample. The abrasion resistance after 100 rotations of the inner layer sufficiently cured by using the coating liquid using the mercaptosilane-modified colloidal silica dispersion was 1.4%.

[Example 16] The sample adjustment method in Example 10 was changed as follows. The coating liquid 3 is applied to a transparent aromatic polycarbonate resin plate (150 mm × 30 mm) having a thickness of 3 mm.
0 mm) using a bar coater (wet thickness 16)
μm) and kept in a hot air circulating oven at 80 ° C. for 5 minutes. This was placed in an air atmosphere using a high-pressure mercury lamp for 150
Ultraviolet rays of mJ / cm ² (integrated energy of ultraviolet rays in a wavelength range of 300 to 390 nm) were irradiated to form a partially cured layer having a thickness of 5 μm. Then, the coating liquid 2 was applied thereon again using a bar coater (wet thickness: 6 μm), and kept in a hot air circulating oven at 80 ° C. for 5 minutes.
This is 3,000 mJ in an air atmosphere using a high-pressure mercury lamp.
/ Cm ² (integrated amount of ultraviolet light in a wavelength range of 300 to 390 nm), and then kept in a hot air circulating oven at 170 ° C. for 5 minutes. In this manner, the mold was pressed against a mold having a curvature of 180 mmR and subjected to bending. And
As a result of observing the appearance of the cured product at room temperature for one day, it was found that the cured product had no cracks or wrinkles.

[Example 17] A sample having two fully cured layers finally obtained in Example 10 was kept in a hot air circulating oven at 170 ° C for 5 minutes, and immediately after being taken out, a transparent cured layer was applied. It was pressed against a mold having a curvature of 180 mmR so that the worked surface was on the convex side, and subjected to bending. As a result of observing the appearance of the obtained sample, cracks and wrinkles were found in the cured product layer.

[Example 18] A coating liquid 1 was coated on a transparent aromatic polycarbonate resin plate having a thickness of 3 mm (150 mm x 300 m).
m) using a bar coater (wet thickness 20μ)
m) and kept in a hot air circulating oven at 80 ° C. for 5 minutes. This is 3,000 in an air atmosphere using a high-pressure mercury lamp.
The transparent cured material layer having a thickness of 6 μm was cured by irradiating ultraviolet rays of mJ / cm ² (integrated amount of ultraviolet light in a wavelength range of 300 to 390 nm), and various physical properties were measured and evaluated using the sample.

[Example 19] A coating liquid 2 was coated with a transparent aromatic polycarbonate resin plate having a thickness of 3 mm (150 mm x 300 m).
m) using a bar coater (wet thickness 30μ)
m) and kept in a hot air circulating oven at 80 ° C. for 10 minutes. Subsequently, it was kept in a hot air circulating oven at 100 ° C. for 120 minutes to cure a transparent cured product layer having a thickness of 6 μm, and various physical properties were measured and evaluated using this sample.

Example 20 A coating liquid 3 was coated on a transparent aromatic polycarbonate resin plate having a thickness of 3 mm (150 mm × 300 m).
m) using a bar coater (wet thickness 20μ)
m) and kept in a hot air circulating oven at 80 ° C. for 5 minutes. This is 3,000 in an air atmosphere using a high-pressure mercury lamp.
The transparent cured material layer having a thickness of 6 μm was cured by irradiating ultraviolet rays of mJ / cm ² (integrated amount of ultraviolet light in a wavelength range of 300 to 390 nm), and various physical properties were measured and evaluated using the sample.

[0159]

[Table 1]

[0160]

According to the present invention, it is possible to obtain a vehicle window material having a surface having a high abrasion resistance almost equivalent to an inorganic glass plate used for a vehicle window and having excellent surface characteristics.
Furthermore, even if it has a predetermined curved shape required for a vehicle window, a vehicle window material having sufficient wear resistance can be obtained.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view showing an example of a vehicle window material of the present invention.

[Explanation of symbols]

 1: first coat layer 2: second coat layer 10: resin plate 11: outer layer 12: inner layer

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Hiroshi Yamamoto 1150 Hazawa-cho, Kanagawa-ku, Yokohama-shi

Claims (10)

[Claims] 1. A transparent resin plate and a first hard coat layer laminated on the transparent resin plate, wherein the first hard coat layer is formed of two or more transparent cured product layers, A window material for a vehicle, wherein the outermost layer is a silica layer which is a cured product of a coating composition containing polysilazane, and the inner layer in contact with the outermost layer is a wear-resistant layer. 2. A vehicle window material having a transparent resin plate and a first hard coat layer laminated on the transparent resin plate,
The first hard coat layer is formed of two or more transparent cured material layers, and the inner layer that is in contact with the outermost layer of the two or more transparent cured material layers has two or more active energy ray-curable polymerizable functional groups. A coating composition which is a hardened product of a coating composition (A) containing a multifunctional compound (a) having at least one abrasion-resistant layer, wherein the outermost layer can form silica substantially containing no organic group. A vehicle window material comprising a silica layer which is a cured product of (B). 3. The coating composition (A) further has an average particle size of 20.
The vehicle window material according to claim 2, comprising colloidal silica having a diameter of 0 nm or less. 4. The vehicle window material according to claim 2, wherein the coating composition (B) is a coating composition containing polysilazane. 5. The wear resistance of the inner layer of the transparent resin plate on which the inner layer is formed after the inner layer is formed when the number of rotations of the specimen in the wear test specified in JIS-R3212 is 100. The difference between the haze value (%) and the haze value (%) before abrasion is 1
The vehicle window material according to claim 1, 2, 3 or 4, wherein the content is 5% or less. 6. The first hard coat layer is disposed on the outside of the vehicle, and the abrasion resistance of the surface of the vehicle window material on the first hard coat layer side is defined by JIS-R3212. The difference between the haze value (%) after abrasion and the haze value (%) before abrasion according to an abrasion test is 10% or less.
The vehicle window material according to 3, 4, or 5. 7. A second hard coat layer is laminated on a surface of the transparent resin plate opposite to the first hard coat layer side,
The vehicle window material according to claim 1, 2, 3, 4, 5, or 6, wherein the first hard coat layer side is disposed outside the vehicle. 8. A vehicle window material having a transparent resin plate and first and second hard coat layers respectively laminated on both surfaces of the transparent resin plate, wherein the first hard coat layer has two or more layers. An inner layer formed of a transparent cured product layer and in contact with the outermost layer of the two or more transparent cured product layers is JIS-R32
When the number of rotations of the specimen in the wear resistance test specified in 12 is 100, the haze value (%) after abrasion and the haze value (%) before abrasion of the inner layer side surface of the transparent resin plate on which the inner layer is formed are shown. Is 15% or less, and the surface of the vehicle window material on the first hard coat layer side is JIS-R321.
2. A vehicle window material having abrasion resistance in which a difference between a haze value (%) after abrasion and a haze value (%) before abrasion according to the abrasion resistance test specified in 2 is 10 (%) or less. . 9. The vehicle window material according to claim 8, wherein the outermost layer is a silica layer which is a cured product of a coating composition containing polysilazane. 10. An uncured, partially cured or cured layer of a coating composition (A) containing a polyfunctional compound (a) having two or more active energy ray-curable polymerizable functional groups is transparent. After forming a layer of an uncured material or a partially cured material of the coating composition (B) which can be formed on a resin plate and form silica containing substantially no organic groups on the surface of the layer, these layers are formed. The cured transparent resin plate is heated and bent, and then the uncured or partially cured product of the coating composition (B) and the uncured or partially cured product of the coating composition (A) are present. It is cured, and a cured product of the coating composition (B) is formed on the outermost layer, and an abrasion-resistant layer, which is a cured product of the coating composition (A), is formed on the inner layer in contact with the outermost layer. A hard coat layer formed from the above transparent cured material layer is laminated on a transparent resin plate, and has a curved shape. Method of manufacturing a vehicle window material that.