JP2014000802A - Transparent laminate and method for manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a transparent laminate which achieves load resistance required as a window material for a vehicle, and has a transparent protective film in which the cracks and peeling are hardly caused and that is superior in scratch resistance.SOLUTION: A transparent laminate 1 comprises: a transparent resin substrate 2; a transparent protective film 3 provided on at least one face thereof; and a transparent primer layer 4 interposed between the substrate 2 and the protective film 3. The substrate 2 has heat resistance to a temperature of 70°C or higher, substantially uniform thickness of 1 mm or more, and an elastic modulus of 1 GPa or more and Vickers hardness of 10 kgf/mmor more at room temperature. The protective film 3 contains silicone resin composition as a main component, which contains a cage silsesquioxane resin of 15 wt.% or more, and has a thickness of 5 μm or more but 80 μm less. The primer layer 4 includes an acrylic resin, and has a thickness of 5 μm or more.

Description

  The present invention relates to a transparent laminate. Specifically, it is related with the transparent laminated body provided with the transparent protective film which was hard to produce a crack and peeling and was excellent in damage resistance, and the manufacturing method of this transparent laminated body.

  For the purpose of improving fuel efficiency, there is a demand for lighter vehicles. Therefore, conventionally, development of a vehicle window material based on a resin having a specific gravity smaller than that of glass has been attempted. However, in the case of such a resin window material, since the resin has poor scratch resistance and is also weak against ultraviolet rays, there is a problem that the transparency of the window material cannot be sufficiently secured.

  In order to solve such a problem, for example, Patent Document 1 discloses a transparent structure in which a film laminate is bonded to the surface of glass via an adhesive layer. The film laminate comprises a layer containing a cage silsesquioxane resin having photocurability and a transparent plastic film layer on the layer.

  For example, Patent Document 2 discloses a transparent organic glass including a resin base material and a protective film containing a cage silsesquioxane resin on the resin base material.

  According to these techniques, the effect of maintaining the transparency of the resin window material can be expected by applying the cage silsesquioxane to the transparent protective film that protects the transparent resin substrate.

JP 2010-125719 A JP 2009-29881 A

  By the way, the window material for vehicles provided with the base material and the protective film is required to have a load resistance against an impact and a load assumed during use in an actual use environment. In order to satisfy this requirement, it is necessary to consider the thickness and elastic modulus of the base material of the window material. In addition, in order to improve the scratch resistance while preventing the protective film from cracking and peeling, it is necessary to increase the thickness of the protective film itself and to consider the heat resistance of the substrate. However, if the thickness of the protective film is too large, the protective film may be cracked, peeled off or damaged due to volume shrinkage during the manufacture of the window material. Therefore, when the cage-type silsesquioxane is applied to the protective film, it is necessary to set the thickness of the protective film while taking these into consideration.

  However, in Patent Documents 1 and 2, the elastic modulus and thickness of the base material are not considered in consideration of the load resistance of the vehicle window material, and the protective film is cracked, peeled off, damaged, etc. There have not been sufficient studies on the heat resistance of the base material, the thickness of the protective film, etc. to make it difficult to occur.

  Then, this invention makes it a subject to provide the transparent laminated body provided with the transparent protective film which achieved the load resistance requested | required as a window material for vehicles, was hard to produce a crack and peeling, and was excellent in damage resistance. .

In order to solve the above-mentioned problem, the invention according to claim 1 of the present application includes a transparent resin base material, a transparent protective film provided on at least one surface of the transparent resin base material, and a transparent resin base material and a transparent protective film. A transparent laminate having a transparent primer layer interposed therebetween, wherein the transparent resin base material has a heat resistance of 70 ° C. or higher, a substantially uniform thickness of 1 mm or higher, and a temperature of 1 GPa or higher at room temperature. It has an elastic modulus and a Vickers hardness of 10 kgf / mm ² or more, and the transparent protective film is mainly composed of a silicone resin composition containing 15% by weight or more of a cage silsesquioxane resin, and is 5 μm or more and 80 μm or less. The transparent primer layer has a thickness, and includes an acrylic resin and has a thickness of 5 μm or more.

  The invention according to claim 2 is characterized in that, in the invention according to claim 1, the transparent resin base material contains a polycarbonate resin or an acrylic resin as a main component.

  In addition, the invention according to claim 3 is the ladder type according to the invention according to claim 1 or 2, wherein the transparent protective film includes a ladder type when the silicone resin composition contains a material other than a cage silsesquioxane resin. It contains at least one of silsesquioxane resin and random type silsesquioxane resin.

  By the way, when the window material for vehicles is used for a long period of time or depending on the usage mode, the window material may undergo color change or gloss change. For this, it is conceivable that the transparent protective film contains an ultraviolet absorber or the like, but problems such as softening of the protective film and inhibition of curing during photocuring may occur.

  In this regard, Patent Document 1 only discloses that the protective film can contain a filler-based additive when curing is not inhibited during photocuring. The protective film in the case of containing an ultraviolet absorber is disclosed. Sufficient studies have not been made on the inhibition of softening and photocuring.

  Accordingly, an invention according to claim 4 is the invention according to any one of claims 1 to 3, wherein at least one of the transparent protective film and the transparent primer layer contains an ultraviolet absorber.

で表され（但し、Ｒは水素原子又はメチル基）、前記一般式（１）におけるＺは、下記式（２）又は（３）

で表される脂環式不飽和化合物を１０重量％以上１００重量％以下の割合で含むことを特徴とする。 The invention according to claim 5 is the invention according to any one of claims 1 to 4, wherein the transparent primer layer is an acrylic that can be radically polymerized with a silicone resin composition that is a main component of the transparent protective film. The acrylic copolymer composition has a copolymer composition, and the acrylic copolymer composition has the following general formula (1)

(Wherein R is a hydrogen atom or a methyl group), Z in the general formula (1) represents the following formula (2) or (3)

The alicyclic unsaturated compound represented by these is included in the ratio of 10 weight% or more and 100 weight% or less.

  The invention according to claim 6 is the invention according to any one of claims 1 to 5, wherein the transparent laminate is a window material of a moving body.

Furthermore, the invention according to claim 7 is a transparent resin substrate, a transparent protective film provided on at least one surface of the transparent resin substrate, and a transparent interposed between the transparent resin substrate and the transparent protective film. A method for producing a transparent laminate provided with a primer layer, having a heat resistance of 70 ° C. or higher, a substantially uniform thickness of 1 mm or more, an elastic modulus of 1 GPa or more and a Vickers hardness of 10 kgf / mm ² or more at room temperature. A base material preparing step for preparing a transparent resin base material, a first coating step for applying a first paint composition containing an acrylic resin on the transparent resin base material, and a second paint composition containing a silicone resin composition A second coating step of coating the first coating composition on the first coating composition, and light curing the first coating composition and the second coating composition by irradiating light at an atmospheric temperature lower than the heat-resistant temperature of the transparent resin substrate. A transparent plastic on the transparent resin substrate. In the second coating step, a cage silsesquioxane resin, a cage silsesquioxane resin, and a ladder silsesquioxane resin are used as the silicone resin composition. It is characterized by using a mixture with at least one of an oxan resin and a random type silsesquioxane resin.

The invention according to claim 8 is the invention according to claim 7, wherein, in the photocuring step, light having a wavelength region of 200 nm or more and 400 nm or less is emitted with an illuminance of 1 × 10 ⁻² mW / cm ² or more and 1 × 10 10 It is characterized by being irradiated and photocured under conditions of ⁴ mW / cm ² or less and an integrated light quantity in the wavelength range of 5 × 10 ² mJ / cm ² or more and 3 × 10 ⁴ mJ / cm ² or less.

Further, the invention according to claim 9 is a transparent resin substrate, a transparent protective film provided on at least one surface of the transparent resin substrate, and a transparent interposed between the transparent resin substrate and the transparent protective film. A method for producing a transparent laminate provided with a primer layer, having a heat resistance of 70 ° C. or higher, a substantially uniform thickness of 1 mm or more, an elastic modulus of 1 GPa or more and a Vickers hardness of 10 kgf / mm ² or more at room temperature. A base material preparing step for preparing a transparent resin base material, a first coating step for applying a first paint composition containing an acrylic resin on the transparent resin base material, and a second paint composition containing a silicone resin composition A second application step of applying an object on the first coating composition, and heating and curing the first coating composition and the second coating composition at an atmospheric temperature lower than the heat-resistant temperature of the transparent resin substrate, Transparent primer on the transparent resin substrate A thermosetting step of providing a layer and a transparent protective film, and in the second coating step, a cage silsesquioxane resin, or a cage silsesquioxane resin and a ladder silsesquioxane resin are used as the silicone resin composition. A mixture of at least one of a sun resin and a random type silsesquioxane resin is used.

  The invention according to claim 10 is the invention according to any one of claims 7 to 9, wherein at least one of the first paint composition in the first application step and the second paint composition in the second application step. One is characterized by containing an ultraviolet absorber.

  With the above configuration, according to the invention of each claim of the present application, the following effects can be obtained.

  First, according to the invention which concerns on Claim 1 of this application, the load resistance required as a window material for vehicles is achieved by making the thickness and elastic modulus of a transparent resin base material into the said range. In addition, when the ratio of the cage silsesquioxane resin in the silicone resin composition is 15% or more, the heat resistance of the transparent resin substrate and the thickness of the transparent protective film are within the above ranges, so that cracking or peeling Thus, a transparent laminate including a transparent protective film that is less likely to cause scratching and excellent in scratch resistance is realized.

  Here, when the heat resistance of the transparent resin base material is improved, the deformation of the base material is suppressed, and the indication surface of the transparent protective film is stabilized, so that the protective film is prevented from being cracked, peeled off, or damaged. It will be. In addition, by setting the Vickers hardness of the transparent resin base material within the above range, combined with setting the heat resistance of the base material within the above range, the scratch resistance of the transparent protective film is improved.

  Moreover, according to the invention which concerns on Claim 2, when a transparent resin base material contains a polycarbonate resin or an acrylic resin as a main component, the effect about the load resistance of a transparent resin base material and the damage resistance of a transparent protective film is effective. Specifically achieved.

  According to the invention of claim 3, when the silicone resin composition contains a resin other than the cage silsesquioxane resin in addition to the cage silsesquioxane resin, Since ladder-type silsesquioxane resins and random-type silsesquioxane resins having similar properties are used, the portion of the transparent protective film that undergoes photodegradation is reduced, and the weather resistance of the transparent protective film itself can be improved. .

  According to the fourth aspect of the present invention, at least one of the transparent protective film and the transparent primer layer contains the ultraviolet absorber, so that the ultraviolet absorbing ability, that is, the weather resistance of the transparent laminate can be improved.

  As described above, a part of the ultraviolet absorbing function of the transparent protective film can be distributed to the transparent primer layer by the intervention of the transparent primer layer. That is, since the transparent primer layer can contain an ultraviolet absorber, softening of the transparent protective film, which can occur when only the transparent protective film contains a large amount of ultraviolet absorber, and inhibition of curing during photocuring can be suppressed. . Therefore, it is possible to improve the weather resistance while ensuring the scratch resistance of the transparent protective film.

  Moreover, according to the invention which concerns on Claim 5, peeling of a transparent protective film is carried out because a transparent primer layer contains the acrylic resin composition which can be radically polymerized with the silicone resin composition which is a main component of a transparent protective film. Is prevented.

  According to the invention of claim 6, the load resistance required as a vehicle-resistant window material is achieved, and a window material that is hardly cracked or peeled off and excellent in scratch resistance is realized, and therefore the vehicle is light. There is a possibility of becoming.

  Further, according to the invention of claim 7, a transparent laminate having a transparent protective film that achieves the load resistance required as a window material for vehicles, is less prone to cracking and peeling, and has excellent scratch resistance is manufactured. Is possible. Also, if the process time in the window material manufacturing process is long, impurities are likely to be mixed in, resulting in poor yields and therefore high costs. Therefore, a transparent protective film can be quickly provided by a photocuring process. Therefore, the yield can be improved as compared with the method using the firing step.

  According to the eighth aspect of the invention, the effect of the seventh aspect is specifically achieved by setting the illuminance and integrated light quantity of light in the wavelength range of 200 nm to 400 nm.

  Furthermore, according to the invention according to claim 9, a transparent laminated body provided with a transparent protective film that achieves the load resistance required as a window material for vehicles, is less prone to cracking and peeling, and has excellent scratch resistance. Is possible. Moreover, since the thermosetting process is less susceptible to physical obstacles and the distance from the heat source than the photocuring process, the degree of freedom of shape of the manufactured transparent laminate can be increased.

  According to the invention of claim 10, the transparent laminate including the transparent protective film having excellent weather resistance when at least one of the first coating composition and the second coating composition contains an ultraviolet absorber. It can be manufactured.

It is a schematic diagram of the transparent laminated body by embodiment of this invention. It is explanatory drawing about the range of the heat resistance of a transparent resin base material. It is explanatory drawing about the range of the elasticity modulus of a transparent resin base material. 1 shows a test apparatus for a scratch resistance test. The apparatus for measuring the surface gloss value is shown. The test apparatus of a weather resistance test is shown.

(Transparent laminate)
FIG. 1 is a schematic diagram of a transparent laminate according to an embodiment of the present invention. The transparent laminate 1 includes a transparent resin base material 2 (hereinafter simply referred to as a base material), a transparent protective film 3 (hereinafter simply referred to as a protective film) provided on the base material 2, a base material 2 and a protective film. 3, a primer layer 4 (hereinafter simply referred to as a primer layer) interposed therebetween. In FIG. 1, the protective film 3 is provided on one surface of the substrate 2, but may be provided on both surfaces.

  The base material 2 contains a polycarbonate resin or an acrylic resin as a main component. In the experiment described with reference to FIGS. 2 and 3, polycarbonate (Teijin Kasei Co., Ltd .: L-1250) was used as the substrate 2.

FIG. 2 is an explanatory diagram of the heat resistance of the substrate. The substrate 2 placed in the black box was irradiated with light having an illuminance of 0 to 900 W / m ² assumed in an actual use environment for about 3 hours. The solid line in FIG. 2 shows the experimental results at the highest ambient temperature of 40 ° C. assumed in the actual use environment. For comparison, the experimental results at an atmospheric temperature of 20 ° C. are shown by dotted lines.

    As shown in FIG. 2, the maximum temperature reached at an ambient temperature of 40 ° C. was 70 ° C. Therefore, it is preferable that the base material 2 has a heat resistance of 70 ° C. or higher. This 70 ° C. is the glass transition temperature, and if it exceeds this, the substrate 2 is warped or deformed.

  FIG. 3 is an explanatory diagram of the elastic modulus of the base material. In general, the resin has a specific gravity about half that of glass. Moreover, the thickness of the conventional glass window for vehicles is about 3 mm. Therefore, if the thickness of the resin window is about 6 mm or less, it can be said that the weight can be reduced as compared with the conventional case. In FIG. 3, when four sides of a square-shaped base material 2 having a substantially uniform thickness of 1 mm and a side of 150 mm are fixed, and a center concentrated load of 0.6 N is applied in accordance with the JIS K 7191B method, The relationship between the elastic modulus of the base material 2 at room temperature and the maximum deflection is shown.

  The vehicle window is required to have a maximum deflection amount of about 0.4 mm or less under the above conditions. As shown in FIG. 3, when the maximum deflection amount is 0.34 mm, the elastic modulus is 1 GPa. Therefore, the base material 2 has an elastic modulus of 1 GPa or more at room temperature.

Moreover, if the surface hardness of the base material 2 is not sufficiently high, deformation is likely to occur when a load is applied to the protective film 3, and the damage generated in the protective film 3 in accordance with the deformation of the base material 2 may increase. There is. Therefore, the base material 2 preferably has a Vickers hardness of 10 kgf / mm ² or more at room temperature in order to ensure the scratch resistance required as a vehicle window material of the transparent laminate 1.

The protective film 3 has a silicone resin composition as a main component. The silicone resin composition is a cage silsesquioxane resin represented by the following general formula (4), or the cage silsesquioxane resin, a ladder silsesquioxane resin, and a random type. And at least one silsesquioxane resin having an incomplete cage structure in which a portion of the cage is open.
[RSiO _3/2 ] _n (4)
(However, R is a (meth) acryloyl group, a glycidyl group or a vinyl group, or an organic functional group having any one of the following general formulas (5) to (7), and n is 8, 10, 12 or 14) .)
However, the cage-type silsesquioxane resin is not limited to these, and those having other structures can be used, and each may be used alone or in combination of two or more. .

  As the silicone resin composition, in addition to the cage silsesquioxane resin, a ladder type, a random type, and a siloxane resin having an incomplete cage type structure in which a part of the cage is opened are used. As a result, the portion of the protective film 3 that is photodegraded is reduced, and the weather resistance of the protective film 3 itself can be improved.

Furthermore, the silicone resin composition may contain an unsaturated compound in addition to the silsesquioxane resin.
Specifically, as the unsaturated compound, tricyclo [5.2.1.02,6] decane diacrylate (or dicyclopentanyl diacrylate), tricyclo [5.2.1.02,6] de Candiacrylate, tricyclo [5.2.1.02,6] decanedimethacrylate, tricyclo [5.2.1.02,6] decanedimethacrylate, tricyclo [5.2.1.02,6] decaneacrylate methacrylate , Tricyclo [5.2.1.02,6] decane acrylate methacrylate, pentacyclo [6.5.1.13, 6.02, 7.09,13] pentadecane diacrylate, pentacyclo [6.5.1.13 , 6.02, 7.09, 13] pentadecane diacrylate, pentacyclo [6.5.1.13, 6.02, 7.09]. 13] pentadecane dimethacrylate, pentacyclo [6.5.1.13, 6.02, 7.09, 13] pentadecane dimethacrylate, pentacyclo [6.5.1.13, 6.02, 7.09, 13] Pentadecane acrylate methacrylate, pentacyclo [6.5.1.13,6.02,7.09,13] pentadecane acrylate methacrylate, epoxy acrylate, epoxidized oil acrylate, urethane acrylate, unsaturated polyester, polyester acrylate, polyether acrylate, Vinyl acrylate, polyene / thiol, silicone acrylate, polybutadiene, polystyryl ethyl methacrylate, styrene, vinyl acetate, N-vinyl pyrrolidone, butyl acrylate, 2-ethylhexyl acrylic , N-hexyl acrylate, cyclohexyl acrylate, n-decyl acrylate, isobornyl acrylate, dicyclopentenyloxyethyl acrylate, phenoxyethyl acrylate, trifluoroethyl methacrylate, tripropylene glycol diacrylate, 1,6-hexanediol Acrylate, bisphenol A diglycidyl ether diacrylate, tetraethylene glycol diacrylate, hydroxypivalate neopentyl glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, or others These reactive oligomers and monomers can be used. These reactive oligomers and monomers may be used alone or in combination of two or more.

  Generally, in order to obtain the protective film 3 having excellent scratch resistance, it is preferable to increase the thickness of the protective film 3. However, when intermolecular crosslinking (curing) does not occur uniformly in the entire protective film 3 in the photocuring step or thermosetting step for producing the transparent laminate 1, there is a position where volume shrinkage due to intermolecular crosslinking is increased. Arise. Thereby, there is a problem that the protective film 3 is easily cracked. In addition, even if no cracking occurs immediately after production, the protective film 3 is likely to be cracked, peeled off or scratched at a position where volume shrinkage has occurred due to use in an actual use environment. This problem can be solved by including a cage-type silsesquioxane resin at a certain ratio (for example, 15% or more) in the silicone resin composition, but if the protective film 3 is too thick, cracks will occur. It becomes difficult to suppress peeling and scratches.

  From the viewpoint of scratch resistance, the thickness of the protective film 3 is preferably 10 μm or more. Further, in order to prevent cracking or peeling in an actual use environment, the thickness of the protective film 3 is preferably 80 μm or less.

  The primer layer 4 may include an acrylic copolymer composition. The acrylic copolymer composition contains 10% by weight or more and 100% by weight or less of an alicyclic unsaturated compound. The alicyclic unsaturated compound is, for example, a diacrylate represented by the following general formula (8). Such an acrylic copolymer composition can be radically polymerized with the silicone resin composition that is the main component of the protective film 3.

  In the general formula (8), R is a hydrogen atom or a methyl group, and Z is represented by the following formula (9) or (10).

  Specifically, examples of the alicyclic unsaturated compound include tricyclo [5.2.1.02,6] decane diacrylate (or dicyclopentanyl diacrylate) and tricyclo [5.2.1. .02,6] decanediacrylate, tricyclo [5.2.1.02,6] decanedimethacrylate, tricyclo [5.2.1.02,6] decanedimethacrylate, tricyclo [5.2.1.02 , 6] decane acrylate methacrylate, tricyclo [5.2.1.02,6] decane acrylate methacrylate, pentacyclo [6.5.1.13,6.02,7.09,13] pentadecane diacrylate, pentacyclo [6 5.1.13, 6.02, 7.09, 13] pentadecane diacrylate, pentacyclo [6.5.1.13, 6.0 , 7.09,13] pentadecane dimethacrylate, pentacyclo [6.5.1.13, 6.02, 7.09,13] pentadecane dimethacrylate, pentacyclo [6.5.1.13, 6.02, 7 .09,13] pentadecane acrylate methacrylate, pentacyclo [6.5.1.13,6.02,7.09,13] pentadecane acrylate methacrylate, and the like. These alicyclic unsaturated compounds may be used alone or in admixture of two or more.

  Here, the acrylic copolymer composition may contain an acyclic unsaturated compound in addition to the alicyclic unsaturated compound. In general, unsaturated compounds are broadly classified into reactive oligomers, which are polymers having a structural unit having about 2 to 20 repeating units, and low molecular weight, low viscosity reactive monomers. There are monofunctional unsaturated compounds having one and polyfunctional unsaturated compounds having a plurality of unsaturated groups.

  In this embodiment, as the reactive oligomer, epoxy acrylate, epoxidized oil acrylate, urethane acrylate, unsaturated polyester, polyester acrylate, polyether acrylate, vinyl acrylate, polyene / thiol, silicone acrylate, polybutadiene, polystyrylethyl methacrylate, etc. Can be used. Further, as reactive monofunctional monomers, styrene, vinyl acetate, N-vinylpyrrolidone, butyl acrylate, 2-ethylhexyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, n-decyl acrylate, isobornyl acrylate, dicyclopentenyloxy Ethyl acrylate, phenoxyethyl acrylate, trifluoroethyl methacrylate, or the like can be used. On the other hand, reactive polyfunctional monomers include tripropylene glycol diacrylate, 1,6-hexanediol diacrylate, bisphenol A diglycidyl ether diacrylate, tetraethylene glycol, which are unsaturated compounds other than the general formula (4). Diacrylate, hydroxypivalic acid neopentyl glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, and the like can be used. Further, as the unsaturated compound used in the present embodiment, other reactive oligomers and reactive monomers can be used. Moreover, these reactive oligomers and reactive monomers may be used alone or in combination of two or more.

  Further, the primer layer 4 may contain, for example, a compound such as an acetophenone-based, benzoin-based, benzophenone-based, thioxanthone-based, or acylphosphine oxide-based compound as a photocuring catalyst. The photocuring catalyst acts as a polymerization initiator in the photocuring step included in the method for producing the transparent laminate 1 described later. Further, the primer layer 4 may contain a photoinitiator auxiliary agent or a sharpening agent that exhibits an effect in combination with a photocuring catalyst that acts as a polymerization initiator.

  Specifically, the photocuring catalyst includes trichloroacetophenone, diethoxyacetophenone, 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- ( 4-methylthiophenyl) -2-morpholinopropan-1-one, benzoin methyl ether, benzyldimethyl ketal, benzophenone, thioxanthone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, methylphenylglyoxylate, camphorquinone, benzyl, Anthraquinone, Michler's ketone, etc. can be used.

  Furthermore, at least one of the protective film 3 and the primer layer 4 may contain an ultraviolet absorber, a light stabilizer, a heat ray absorber, or the like. The ultraviolet absorber can be, for example, a hydroxyphenyltriazine-based organic ultraviolet absorber. The light stabilizer can be, for example, a hindered amine light stabilizer.

  Specifically, examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 2,2'-dihydroxy-4,4 '. -Benzophenones such as dimethoxybenzophenone, or 2- (5'-methyl-2'-hydroxyphenyl) benzotriazole, 2- (3'-t-butyl-5'-methyl-2'-hydroxyphenyl) benzotriazole Benzotriazoles such as 2- (3 ′, 5′-di-t-butyl-2′-hydroxyphenyl) -5-chlorobenzotriazole, or ethyl-2-cyano-3,3-diphenyl acrylate, 2 -Cyanoacrylates such as ethylhexyl-2-cyano-3,3-diphenylacrylate Or salicylates such as phenyl salicylate and p-octylphenyl salicylate, or benzylidene malonates such as diethyl-p-methoxybenzylidene malonate and bis (2-ethylhexyl) benzylidene malonate, or 2- (4, 6-Diphenyl-1,3,5-triazin-2-yl) -5-[(methyl) oxy] -phenol, 2- (4,6-diphenyl-1,3,5-triazin-2-yl)- 5-[(ethyl) oxy] -phenol, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(propyl) oxy] -phenol, 2- (4,6 -Diphenyl-1,3,5-triazin-2-yl) -5-[(butyl) oxy] -phenol, 2- (4,6-diphenyl-1,3,5-tria N-2-yl) -5-[(hexyl) oxy] -phenol and other triazines or 2- (2′-hydroxy-5-methacryloxyethylphenyl) -2H-benzotriazole and copolymerized with the monomer Copolymer with possible vinyl monomer, copolymer of 2- (2′-hydroxy-5-acryloxyethylphenyl) -2H-benzotriazole and vinyl monomer copolymerizable with the monomer, titanium oxide Metal oxide fine particles such as cerium oxide, zinc oxide, tin oxide, tungsten oxide, zinc sulfide, and cadmium sulfide can be used. These ultraviolet absorbers may be used alone or in combination of two or more.

  Examples of the light stabilizer include bis (2,2,6,6-tetramethyl-4-piperidyl) carbonate, bis (2,2,6,6-tetramethyl-4-piperidyl) succinate, and bis (2 , 2,6,6-tetramethyl-4-piperidyl) sebacate, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 4-octanoyloxy-2,2,6,6-tetramethylpiperidine Bis (2,2,6,6-tetramethyl-4-piperidyl) diphenylmethane-p, p'-dicarbamate, bis (2,2,6,6-tetramethyl-4-piperidyl) benzene-1,3 Hindered amines such as disulfonate, bis (2,2,6,6-tetramethyl-4-piperidyl) phenyl phosphite, or nickel bis (octylphenyl) Nickel complexes such as Rufide, nickel complex-3,5-di-t-butyl-4-hydroxybenzyl phosphate monoethylate, nickel dibutyldithiocarbamate, etc. can be used. Alternatively, two or more kinds may be mixed and used.

  As described above, by making the thickness and elastic modulus of the base material 2 within a predetermined range, it is possible to obtain an advantage of weight reduction by using a resin for the material of the base material 2 and as a vehicle window material. The required load capacity is achieved. Moreover, the crack in a manufacturing process is prevented by making the heat resistance of the base material 2, Vickers hardness, the thickness of the protective film 3, and the ratio of the cage silsesquioxane resin in the silicone resin composition within a predetermined range. In addition, the transparent laminated body 1 including the protective film 3 that is hardly cracked or peeled off in an actual use environment and has excellent scratch resistance is realized.

  In addition, since the primer layer 4 including the acrylic layer is interposed between the base material 2 and the protective film 3, a part of the ultraviolet and heat ray absorbing function of the protective film 3 can be distributed to the primer layer 4. Further, since the primer layer 4 can contain an ultraviolet absorber or a heat ray absorber, softening of the protective film 3 which can occur when only the protective film 3 contains a large amount of an ultraviolet absorber or a heat ray absorber, Curing inhibition during photocuring can be suppressed. Thus, the weather resistance of the protective film 3 can be improved, and the transparent laminate 1 suitable for use in a vehicle window material that can withstand long-term use is obtained.

  In addition, the primer layer 4 includes an acrylic copolymer composition that can be radically polymerized with a silicone resin composition that is a main component of the protective film 3. By such an acrylic copolymer composition, the primer layer 4 and the protective film 3 and the base material 2 are strongly bonded to each other, so that the protective film 3 is prevented from being peeled off.

(Method for producing transparent laminate)
The manufacturing method of the transparent laminate 1 includes a base material preparing step for preparing the base material 2, a first coating step for applying the first coating composition constituting the primer layer 4 on the base material 2, and a protective film. A first coating composition by irradiating light at an ambient temperature lower than the heat resistance temperature (glass transition temperature) of the base material 2 and a second coating step of coating the second coating composition constituting 3 on the first coating composition A photocuring step of photocuring the product and the second coating composition, and providing the primer layer 4 and the protective film 3 on the substrate 2.

  In the first coating step, a first coating composition containing an acrylic resin such as the acrylic copolymer composition is cast on the substrate 2. In the second coating step, a second coating composition containing a silicone resin composition, a nonpolar solvent, a basic catalyst, and a photopolymerization initiator is cast on the first coating composition. As the silicone resin composition, the cage silsesquioxane resin represented by the general formula (4), or the cage silsesquioxane resin, a ladder silsesquioxane resin, and a random silsesquioxane resin. A mixture of an oxan resin and at least one of a silsesquioxane resin with an incomplete cage structure in which a portion of the cage is open is used.

  The nonpolar solvent is preferably a low-boiling poorly water-soluble solvent. The basic catalyst can be an alkali metal hydroxide or an ammonium hydroxide salt such as tetramethylammonium hydroxide, and is preferably a catalyst that is soluble in a nonpolar solvent.

  Specifically, nonpolar solvents include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and other ketones, tetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane and other ethers, ethyl acetate, ethyl acetate Esters such as ethyl, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, 2-ethoxyethanol, 1-methoxy Alcohols such as 2-propanol and 2-butoxyethanol, hydrocarbons such as n-hexane, n-heptane, isooctane, benzene, toluene, xylene, gasoline, light oil, kerosene, acetonitrile, nitromethane, water, etc. are possible. is there. These nonpolar solvents may be used alone or in combination of two or more.

  Here, at least one of the first coating step and the second coating step uses a coating composition containing an ultraviolet absorber or a light stabilizer, so that at least one of the protective film 3 and the primer layer 4 has an ultraviolet absorber or light. The transparent laminated body 1 containing a stabilizer can be created.

  In the first and second coating steps, organic / inorganic fillers, plasticizers, flame retardants, thermal stabilizers, antioxidants, lubricants, antistatic agents, mold release agents, foaming agents, nucleating agents, colorants, and crosslinks It is also possible to use a coating composition containing at least one of an additive, a dispersion aid, a resin component and the like as an additive.

  Moreover, you may include the process of adhere | attaching a spacer on the base material 2 so that the primer layer 4 may become predetermined thickness before a 1st application | coating process. Further, after the first coating step, heating at a temperature sufficiently lower than the heat resistance temperature of the base material 2 (for example, when the base material 2 is polycarbonate having a heat resistance temperature of 140 ° C. or polymethyl methacrylate having a heat resistance temperature of about 100 ° C.) And a step of removing excess first coating composition with a film or the like from above. These steps can be performed on the second coating composition constituting the protective film 3 also in the second coating step.

  Further, for example, so-called wet-on-wet coating may be performed in which the heating at 80 ° C. is performed only for a short time and the second coating composition is applied in a state where the first coating composition is not dried. In this case, since the transparent laminated body 1 can be created by only one photocuring process, productivity improves.

In the photocuring step, for example, using a mercury lamp, light having a wavelength range of 200 nm or more and 400 nm or less is emitted with an illuminance of 1 × 10 ⁻² mW / cm ² or more and 1 × 10 ⁴ mW / cm ² or less. Irradiation is performed under the condition that the integrated light quantity is 5 × 10 ² mJ / cm ² or more and 3 × 10 ⁴ mJ / cm ² or less.

  Such a photocuring step may be performed by opening to the atmosphere, and is preferably performed in an atmosphere in which the oxygen partial pressure is reduced by purging with nitrogen. Furthermore, a transparent member, for example, a transparent film, a laminate, glass, or the like may be disposed on the upper portion to perform the photocuring step.

  By the method described above, the load resistance required as a vehicle window material can be achieved, and the transparent laminate 1 including the protective film 3 having excellent scratch resistance and weather resistance can be manufactured. It is. Moreover, since the protective film 3 can be quickly provided by a photocuring process, a yield can be improved rather than the method by a baking process.

  Further, the photocuring reaction is a radical reaction and is subjected to oxygen inhibition. As described above, when the photocuring step is performed in an atmosphere in which the oxygen partial pressure is reduced, such oxygen inhibition can be suppressed. Moreover, the smoothness of the surface of the transparent laminated body 1 can be improved by arrange | positioning a transparent member in the upper part and implementing a photocuring process.

  In addition, even when the thermosetting process is carried out instead of the photocuring process, the transparent laminate 1 can be similarly manufactured. In that case, in the second coating step, a second coating composition containing a curing catalyst such as phthalimide DBU is used. In the thermosetting step, heating is performed at a temperature sufficiently lower than the heat resistant temperature of the substrate 2 (for example, about 120 ° C. when the substrate 2 is polycarbonate). Although not essential, after the first coating step, the first coating composition is allowed to stand to evaporate a certain amount of solvent, and at a temperature that is about the same as the temperature in thermosetting and sufficiently shorter than the thermosetting step. Preheating may be performed. According to the above thermosetting process, since it is less susceptible to physical obstacles and distance from the heat source than the photocuring process, there is an advantage that the degree of freedom of shape of the manufactured transparent laminate 1 can be increased. is assumed.

  Although the embodiments of the present invention have been described above, the present invention is not limited to the embodiments, and various improvements and design changes can be made without departing from the scope of the present invention. Needless to say.

    Hereinafter, although the Example of the transparent laminated body 1 is demonstrated with a comparative example, this invention is not limited to a following example. In the examples, parts and% mean parts by weight and% by weight.

  In this example, an acrylic resin composition and a silicone resin synthesized by the following synthesis examples were used.

[Synthesis Example of Acrylic Resin Composition]
With the inside of the flask equipped with a reflux condenser and a stirrer replaced with nitrogen, 80.1 parts methyl methacrylate, 13 parts 2-hydroxyethyl methacrylate, 0.14 parts azobisisobutyronitrile and 1,2-dimethoxy 200 parts of ethane was added and mixed to dissolve. Then, it was made to react under stirring at 70 degreeC in nitrogen stream for 6 hours. The obtained reaction solution was added to n-hexane and purified by reprecipitation. As a result, 80 parts of an acrylic copolymer C was obtained. Methyl ethyl ketone was prepared by using 8.9 parts of this acrylic copolymer C, 2 parts of a hydroxyphenyltriazine ultraviolet absorber (BASF Japan KK: TINUVIN479), 1 part of a hindered amine light stabilizer (BASF Japan KK: TINUVIN123). It is dissolved in a mixed solvent consisting of 20 parts, 30 parts of methyl isobutyl ketone and 30 parts of 2-propanol, and further hexagonal so that the isocyanate group is 1.5 equivalents relative to 1 equivalent of the hydroxy group of the acrylic copolymer C. 1.1 parts of methylene diisocyanate was added and stirred at 25 ° C. for 5 minutes. Thereby, an acrylic resin composition was obtained.

[Synthesis example of silicone resin]
To a reaction vessel equipped with a stirrer, a dropping funnel and a thermometer, 40 ml of 2-propanol (IPA) as a solvent and 5% tetramethylammonium hydroxide aqueous solution (TMAH aqueous solution) as a basic catalyst were added. To the dropping funnel, 15 ml of IPA and 12.69 g of 3-methacryloxypropyltrimethoxysilane (SZ-6030 manufactured by Toray Dow Corning Silicone Co., Ltd.) were added. Subsequently, an IPA solution of 3-methacryloxypropyltrimethoxysilane was dropped over 30 minutes at room temperature while stirring the reaction vessel. After completion of dropping, the mixture was stirred for 2 hours in a non-heated environment. Subsequently, the solvent was removed under reduced pressure and dissolved in 50 ml of toluene. The reaction solution was washed with saturated brine until neutral, and dehydrated over anhydrous magnesium sulfate. Subsequently, anhydrous magnesium sulfate was filtered off and concentrated. As a result, 8.6 g of a hydrolysis product (silsesquioxane) was obtained. Such silsesquioxane was a colorless viscous liquid soluble in various organic solvents. Next, put 20.65 g of the obtained silsesquioxane, 82 ml of toluene, and 3.0 g of 10% TMAH aqueous solution into a reaction vessel equipped with a stirrer, a Din Stark and a cooling tube, and gradually heat to distill off the water. did. Subsequently, this was heated to 130 ° C., and toluene was recondensed at the reflux temperature. The temperature of the reaction solution at this time was 108 ° C. The mixture was stirred for 2 hours after refluxing toluene to complete the reaction. The reaction solution was washed with saturated brine until neutral, and dehydrated over anhydrous magnesium sulfate. Subsequently, anhydrous magnesium sulfate was filtered off and concentrated. As a result, 18.77 g of a cage-type silsesquioxane (mixture) as a target product was obtained. The obtained cage-type silsesquioxane was a colorless viscous liquid soluble in various organic solvents. Gravimetric analysis of the reaction product after the recondensation reaction after liquid chromatography separation was performed, and it was confirmed that the silicone resin contained 60% or more of cage silsesquioxane having an acryloyl group.

(Transparent laminate produced by photocuring)
[Examples 1 to 14, Comparative Example 7]
As the substrate 2, polycarbonate (manufactured by Teijin Chemicals Ltd .: L-1250) or polymethyl methacrylate (manufactured by Kaneka Corporation) was used. A second coating composition constituting protective film 3 mixed with 2.5 parts of 1-hydroxycyclohexyl phenyl ketone as a photopolymerization initiator is cast on a PET film, and the excess second coating composition is removed with a blade. did. Subsequently, a spacer was adhered on the base material 2 so that the primer layer 4 had a predetermined thickness, the first coating composition constituting the primer layer 4 was cast, and heated at 80 ° C. for 3 minutes. Subsequently, using the PET film with the second coating composition attached thereto, the base material 2 with the first coating composition attached was pressed down to remove the second coating composition that would become the extra primer layer 4. . Thereafter, the first coating composition is irradiated with a mercury lamp under the condition that the illuminance in the wavelength region of 200 nm or more and 400 nm or less is 505 mW / cm ² with the PET film covered, and the accumulated exposure amount is 8400 mJ / cm ² . And the second coating composition was cured. Thereby, the transparent laminated body 1 was obtained.

[Comparative Examples 1-6]
As the base material 2, polycarbonate (manufactured by Teijin Chemicals Ltd .: L-1250) was used. First, a spacer was bonded on the substrate 2 having a thickness of 3 mm so that the protective film 3 had a predetermined thickness. Then, the coating composition which comprises the protective film 3 which mixed 2.5 parts of 1-hydroxy cyclohexyl phenyl ketone as a photoinitiator was cast, and it heated at 80 degreeC for 3 minute (s). Subsequently, it was pressed with a PET film to remove excess coating composition. Thereafter, with a PET film covered, light having a wavelength range of 200 nm or more and 400 nm or less is irradiated using a mercury lamp under the condition of an illuminance of 505 mW / cm ² , and a paint composition with an accumulated exposure amount of 8400 mJ / cm ^2. The object was cured. Thereby, the transparent laminated body 1 was obtained.

(Transparent laminate manufactured by thermosetting)
[Examples 15 and 16]
As the base material 2, polycarbonate (manufactured by Teijin Chemicals Ltd .: L-1250) was used. First, a spacer is bonded onto the substrate 2 having a thickness of 3 mm so that the primer layer 4 has a predetermined thickness, the first coating composition constituting the primer layer 4 is cast, and left at 25 ° C. for 20 minutes. Preheating was performed at 120 ° C. for 1 hour. Subsequently, a spacer is adhered on the first coating composition so that the protective film 3 has a predetermined thickness, and 2.5 parts of phthalimide DBU is mixed as a curing catalyst, and the second coating composition constituting the protective film 3 is flowed. And heated at 80 ° C. for 3 minutes. Subsequently, the excess coating composition was removed with a coater blade. Then, it heated at 120 degreeC for 11 hours, and the 1st coating composition and the coating composition were thermosetted. Thereby, the transparent laminated body 1 was obtained.

  Table 1 below shows the material of the substrate 2 used in each of Examples 1 to 16 and Comparative Examples 1 to 7, the composition and film thickness of the protective film 3, and the composition and film thickness of the primer layer 4.

In Table 1, each symbol indicates the following.
Base resin S1: Polycarbonate (PC) (manufactured by Teijin Chemicals Ltd .: L-1250)
S2: Polymethyl methacrylate (PMMA) (manufactured by Kaneka Corporation)
Acrylic resin composition PA: dicyclopentanyl diacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: light acrylate DCP-A)
PB: PEG400 # diacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: Light acrylate 9EG-A)
PC: Acrylic copolymer C (acrylic resin composition obtained in the synthesis example)
Silicone resin composition A: Compound obtained in synthesis example (acryloyl group)
B: Dipentaerythritol hexaacrylate (Kyoeisha Chemical Co., Ltd .: Light acrylate DPE-6A)
C: Dicyclopentanyl diacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: Light acrylate D
CP-A)
D: Octakis [[3- (2,3-epoxypropoxy) propyl] dimethylsiloxy] octasilsesquioxane (manufactured by Mayateries: Q-4)
E: 1,4-cyclohexanedimethanol diglycidyl ether (manufactured by Shin Nippon Chemical Co., Ltd .: Rica Resin DME-100)
F: 1,2,4,5-cyclohexanetetracarboxylic dianhydride (manufactured by Tokyo Chemical Industry Co., Ltd.)
Ultraviolet absorber U1-U3: Hydroxyphenyltriazine type ultraviolet absorber (manufactured by BASF Japan Ltd .: TINUVIN400, TINUVIN477, TINUVIN479)
Light stabilizer H1, H2: Hindered amine light stabilizer (manufactured by BASF Japan Ltd .: TINUVIN123, TINUVIN5100)

The substrate S1 has a heat resistance of about 140 ° C. (JIS K 7191B method), an elastic modulus of about 2.2 GPa and a Vickers hardness of about 13 kgf / mm ² at room temperature. Similarly, the substrate S2 has a heat resistance of about 100 ° C. (JIS K 7191B method), an elastic modulus of about 3.1 GPa and a Vickers hardness of about 20 kgf / mm ² at room temperature.

  Moreover, among AC contained in the silicone resin composition in Table 1, Compound A obtained in Synthesis Example 1 contains a cage silsesquioxane resin. As described above, Compound A obtained in Synthesis Example 1 contains 60% or more of a cage silsesquioxane resin. In consideration of this, “cage-type ratio (% by weight)” in Table 1 indicates the range of the ratio of the cage-type silsesquioxane resin in the silicone resin composition. In addition, the range of the ratio of the cage silsesquioxane resin in the silicone resin composition in Examples 15 and 16 is as shown in Table 1. The compound C is added to the silicone resin composition as an unsaturated compound.

  Further, “PA ratio” in Table 1 indicates the ratio of dicyclopentanyl diacrylate (PA) capable of radical polymerization with the silicone resin composition as the main component of the protective film 3 in the acrylic resin composition. .

Table 1 shows the evaluation results of tests performed on the transparent laminates obtained in Examples and Comparative Examples.
Each test was performed by the following method.
Initial appearance: The appearance of the transparent laminate 1 before each test was visually observed. When the protective film 3 was not cracked or peeled off, it was marked as ◯.
Scratch resistance test: A test was conducted using a scratch resistance test apparatus shown in FIG. The wound child 12 covered with cotton and attached to the weighted arm 11 was moved back and forth in the direction indicated by the arrow (A) in a state where the dust D was present between the wound child 12 and the test piece G. The test was carried out at a load applied by the weight arm 11 of 2 N, the moving distance of the wounded child 12 was 120 mm, the reciprocating speed was 0.5 times / s, and the ambient temperature was 20 ° C. The dust D was a particle group including silica particles and alumina particles having an average particle size of 300 μm or less. The numerical value of scratch resistance shown in Table 1 indicates the surface gloss value after reciprocating a predetermined number of times when the surface gloss value before the start of the test is 100. The surface gloss value was calculated based on the intensity of the reflected light received by the light receiver 22 by irradiating the test piece G with light from the light source 21 using the measuring device shown in FIG. When the gloss retention (= surface gloss value after test / surface gloss value before test) was less than 70%, it was judged that sufficient scratch resistance could not be secured in an actual use environment.
Heat-resistant adhesion test: A scratch having a length of 50 mm was put in a cross, and the appearance of the transparent laminate 1 was visually observed after being left in a 70 ° C. environment for 168 hours. When the protective film 3 was not peeled off, it was marked as ◯.
6. Weather resistance test: As shown in FIG. 6, using a weather resistance test apparatus equipped with a xenon light source 31 and a sprinkler 32, 1) illuminance of 180 W / m ² at a black panel temperature of 73 ° C. and humidity of 35%. Was irradiated for 60 min. Subsequently, 2) light with an illuminance of 180 W / m ² was irradiated for 80 min under the conditions of a black panel temperature of 50 ° C. and a humidity of 95%. This cycle was repeated with 1) and 2) as one cycle. The integrated irradiation light quantity was 200 MJ / m ² and 600 MJ / m ² . The external appearance change of the transparent laminated body 1 was observed visually. If no crack or color change occurred in the protective film 3, it was evaluated as “Good”.

  As shown in Table 1, in each Example and Comparative Example, the test was performed with the ratio of the cage silsesquioxane resin in the silicone resin composition contained in the protective film 3 being 15% to 25%. Even when the ratio is further increased to 100%, for example, it is considered that the same result as the result of Table 1 can be obtained. On the other hand, when the ratio is decreased, it is considered that there is an unfavorable influence on the result of each test. Therefore, in this example, the ratio is set as the value.

  First, in Comparative Examples 1 to 6, the primer layer 4 was not provided and the thickness of the protective film 3 was changed.

Comparing Comparative Example 1 with Comparative Examples 2 to 5, when the protective film 3 has a film thickness of 5 μm (Comparative Example 1), the gloss retention is as low as 23%, while the film thickness is 10 μm to 80 μm or less (Comparative Example 2). In ~ 5), it rises greatly to 80% or more. Therefore, when the primer layer 4 is not provided, it can be seen that the thickness of the protective film 3 is preferably 10 μm or more from the viewpoint of scratch resistance.
Further, when Comparative Example 6 and Comparative Examples 1 to 5 are compared, when the thickness of the protective film 3 is 100 μm (Comparative Example 6), the protective film 3 is peeled off in the heat-resistant adhesion test, and the weather resistance test (200 MJ / m ² ), the protective film 3 was cracked, but was not generated when the protective film 3 had a thickness of 80 μm or less (Examples 1 to 5). The gloss retention was 53% when the thickness of the protective film 3 was 100 μm (Comparative Example 6). Therefore, it can be understood that the thickness of the protective film 3 is preferably 80 μm or less from the viewpoint of prevention of cracking and peeling of the protective film 3 and scratch resistance.

  In Examples 1-14, the primer layer 4 was provided with respect to Comparative Examples 1-5. And the thickness and composition of the primer layer 4 were changed, and the film thickness of the protective film 3 was also changed. In Comparative Example 7, the composition of the primer layer 4 was the same as that of Examples 1 and 2 and the thickness was 1 μm.

First, paying attention to the proportion of dicyclopentanyl diacrylate PA in the acrylic resin composition of the primer layer 4, there was no significant difference in test results due to changing the proportion. However, since PA is an acrylic copolymer composition that can be radically polymerized with the silicone resin composition, it is considered that PA contributes to prevention of peeling of the protective film 3.
Moreover, in Examples 5-13, although the quantity and kind of the ultraviolet absorber and light stabilizer which were contained in the protective film 3 and the primer layer 4 were changed, the big difference about a test result was not recognized.
Next, when Example 1 and Comparative Example 1 are compared, when the film thickness of the protective film 3 is 5 μm and the primer layer 4 is not provided (Comparative Example 1), the gloss retention is significantly lower than 70%. . On the other hand, when the thickness of the protective film 3 was 5 μm and when the primer layer 4 having a thickness of 5 μm was provided (Example 1), the gloss retention exceeded 70%. Therefore, it can be seen that by providing the primer layer 4 having a thickness of 5 μm or more, excellent scratch resistance of the protective film 3 is ensured. In view of the scratch resistance in conjunction with the above examination, when the primer layer 4 is provided, it can be said that the thickness of the protective film 3 is preferably 5 μm or more and 80 μm or less.

Next, focusing on the results of the weather resistance test (600 MJ / m ² ) of each example and comparative example, when the thickness of the primer layer 4 is 0 to 1 μm (comparative examples 1 to 7), both are protected. Although yellowing or cracking occurred in the film 3, it did not occur when the thickness of the primer layer 4 was 5 μm or more (Examples 1 to 14). Therefore, it can be seen that by setting the thickness of the primer layer 4 to 5 μm or more, the protective film 3 can be made more difficult to break and excellent in weather resistance.
In addition, when Comparative Example 2 and Comparative Example 7 are compared, since the protective film 3 is peeled off by providing the primer layer 4 having a thickness of 1 μm, the primer layer 4 can also be prevented from being peeled off easily. It can be seen that the thickness of the film is preferably 5 μm or more.

  In Example 14, other Examples, Comparative Examples, and base resin were changed. There was no significant change in the results of each test.

  In Examples 15 and 16, unlike the other examples, the protective film 3 was provided by thermosetting, but the same results as those obtained by photocuring could be obtained.

  The present invention can be widely applied as a window material for a moving body such as a vehicle window material.

  DESCRIPTION OF SYMBOLS 1 Transparent laminated body, 2 Transparent resin base material, 3 Transparent protective film, 4 Transparent primer layer, 11 Weight arm, 12 Wound child, 21 Light source, 22 Light receiver, 31 Xenon light source, 32 Sprinkler, D dust, G test Fragment

Claims (10)

A transparent laminate comprising a transparent resin substrate, a transparent protective film provided on at least one surface of the transparent resin substrate, and a transparent primer layer interposed between the transparent resin substrate and the transparent protective film. And
The transparent resin substrate has a heat resistance of 70 ° C. or more, a substantially uniform thickness of 1 mm or more, and an elastic modulus of 1 GPa or more and a Vickers hardness of 10 kgf / mm ² or more at room temperature,
The transparent protective film is mainly composed of a silicone resin composition containing 15% by weight or more of a cage silsesquioxane resin, and has a thickness of 5 μm or more and 80 μm or less,
The transparent primer layer includes an acrylic resin and has a thickness of 5 μm or more.   The transparent laminate according to claim 1, wherein the transparent resin base material contains a polycarbonate resin or an acrylic resin as a main component.   The transparent protective film contains at least one of a ladder-type silsesquioxane resin and a random-type silsesquioxane resin when the silicone resin composition contains a material other than a cage-type silsesquioxane resin. The transparent layered product according to claim 1 or 2, characterized in.   4. The transparent laminate according to claim 1, wherein at least one of the transparent protective film and the transparent primer layer contains an ultraviolet absorber. The transparent primer layer is
Having a silicone resin composition that is a main component of the transparent protective film and an acrylic copolymer composition capable of radical polymerization;
The acrylic copolymer composition has the following general formula (1)

(Wherein R is a hydrogen atom or a methyl group), Z in the general formula (1) represents the following formula (2) or (3)

The transparent laminated body of any one of Claims 1-4 characterized by including the alicyclic unsaturated compound represented by these in the ratio of 10 to 100 weight%.   It is a window material of a moving body, The transparent laminated body of any one of Claims 1-5 characterized by the above-mentioned. Production of transparent laminate comprising transparent resin substrate, transparent protective film provided on at least one surface of transparent resin substrate, and transparent primer layer interposed between transparent resin substrate and transparent protective film A method,
A base material preparation step of preparing a transparent resin base material having a heat resistance of 70 ° C. or higher, a substantially uniform thickness of 1 mm or higher, and an elastic modulus of 1 GPa or higher and a Vickers hardness of 10 kgf / mm ² or higher at room temperature;
A first application step of applying a first coating composition containing an acrylic resin on the transparent resin substrate;
A second coating step of coating a second coating composition containing a silicone resin composition on the first coating composition;
The first coating composition and the second coating composition are photocured by irradiating light at an atmospheric temperature lower than the heat resistance temperature of the transparent resin substrate, and a transparent primer layer and a transparent protective film are formed on the transparent resin substrate. Including a photocuring step to be provided,
In the second application step, as the silicone resin composition, a cage silsesquioxane resin, or a cage silsesquioxane resin, a ladder silsesquioxane resin, and a random silsesquioxane resin, and A method for producing a transparent laminate, comprising using a mixture of the above. In the photocuring step, light having a wavelength range of 200 nm or more and 400 nm or less is emitted with an illuminance of 1 × 10 ⁻² mW / cm ² or more and 1 × 10 ⁴ mW / cm ² or less, and an integrated light amount in the wavelength range of 5 × 10 ^The method for producing a transparent laminate according to claim 7, wherein the photocuring is performed by irradiation under conditions of ² mJ / cm ² or more and 3 × 10 ⁴ mJ / cm ² or less. Production of transparent laminate comprising transparent resin substrate, transparent protective film provided on at least one surface of transparent resin substrate, and transparent primer layer interposed between transparent resin substrate and transparent protective film A method,
A base material preparation step of preparing a transparent resin base material having a heat resistance of 70 ° C. or higher, a substantially uniform thickness of 1 mm or higher, and an elastic modulus of 1 GPa or higher and a Vickers hardness of 10 kgf / mm ² or higher at room temperature;
A first application step of applying a first coating composition containing an acrylic resin on the transparent resin substrate;
A second coating step of coating a second coating composition containing a silicone resin composition on the first coating composition;
Heat for providing a transparent primer layer and a transparent protective film on the transparent resin substrate by heating and thermosetting the first coating composition and the second coating composition at an atmospheric temperature lower than the heat-resistant temperature of the transparent resin substrate. A curing process,
In the second application step, as the silicone resin composition, a cage silsesquioxane resin, or a cage silsesquioxane resin, a ladder silsesquioxane resin, and a random silsesquioxane resin, and A method for producing a transparent laminate, comprising using a mixture of the above.   The at least one of the 1st coating composition in the said 1st application process and the 2nd coating composition in the said 2nd application process contains a ultraviolet absorber, The any one of Claims 7-9 characterized by the above-mentioned. The manufacturing method of the transparent laminated body of description.

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