JP6213349B2 - Transparent laminate and method for producing the same - Google Patents

Description

  The present invention relates to a transparent laminate used as a substitute for window glass. Specifically, the present invention relates to a transparent laminate having required strength and transparency, and a method for producing such a transparent laminate.

  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.

  For vehicle window materials, maintaining transparency in the actual usage environment is an important issue. However, in general, resins have poor abrasion resistance and scratch resistance against scratches caused by car wash brushes. Therefore, in the case of the resin window material, there is a problem that sufficient transparency cannot be secured.

  As a technique related to such a problem, for example, Japanese Patent Application Laid-Open No. 2010-202860 (Patent Document 1) describes an organic-inorganic composite that achieves both high surface hardness and antiglare property and anti-Newton ring property. For example, JP2013-108050A (Patent Document 2) describes a film made of a polysiloxane organic-inorganic composite having a surface whose hardness is higher than that of the inside.

  According to these techniques, by applying the organic-inorganic composite to a protective film that protects the transparent resin base material, the surface hardness is improved, and the effect of maintaining the transparency of the resin window material can be expected.

JP 2010-202860 A JP2013-108050A

  By the way, in addition to the above-mentioned transparency, the window material for vehicles has load resistance to withstand impacts and loads assumed during use in an actual use environment and high heat resistance to prevent cracking. Required. In order to replace conventional window glass with resin window materials while satisfying these requirements, heat resistance is set appropriately in addition to the elastic modulus of the transparent resin base material that constitutes the window material, and further improvement of the window material In order to reduce the weight, it is necessary to appropriately set the thickness of the transparent resin substrate.

  Moreover, in order to ensure scratch resistance, it is preferable that the thickness of the transparent protective film is sufficiently large. However, in consideration of thermal shrinkage, the thickness of the transparent resin base material is used to prevent cracking of the protective film. It is necessary to set the elastic modulus to a predetermined value or less.

  However, in Patent Documents 1 and 2, the elastic modulus and thickness of the base material are not determined in consideration of the load resistance and heat resistance of the vehicle window material. Further, the thickness range of the transparent protective film is not determined in consideration of the composition of the protective film, and examination for preventing the protective film from cracking has not been sufficiently performed.

  On the other hand, when silica fine particles are further used in the organic-inorganic composite, it is considered that the shear stress is dispersed by the presence of the silica fine particles, and the wear resistance is further improved.

  However, in this case, by containing silica fine particles having high hardness, cracks are generated in the transparent protective film during brushing and the like, and the protective film is likely to be finely broken, and therefore the scratch resistance is deteriorated. Occurs.

  The above-mentioned problems are not limited to window materials for vehicles, but also include general window materials for glass substitutes that require the same performance as window materials for vehicles, including window materials for other moving objects. It will occur.

  Therefore, the present invention provides a transparent laminate having both excellent wear resistance and scratch resistance as a transparent laminate used as a resin window material for replacing glass, and a method for producing such a transparent laminate. The task is to do.

In order to solve the above problems, the present invention provides the following aspects.
[1]
A transparent laminate comprising a plate-like transparent resin substrate and a transparent protective film provided on at least one surface of the transparent resin substrate,
The transparent resin substrate has a heat resistance of 70 ° C. or higher,
The transparent protective film is a protective film having a thickness of 5 μm or more and 150 μm or less obtained by applying and curing the coating composition;
The coating composition contains a curable resin containing an organic-inorganic composite, and inorganic oxide fine particles having an average particle diameter of 10 nm to 100 nm,
The amount of the inorganic oxide fine particles contained in the coating composition is 5 parts by weight or more and 400 parts by weight or less with respect to 100 parts by weight of the resin component contained in the coating composition.
Transparent laminate.
[2]
The transparent resin base material includes a polycarbonate resin or an acrylic resin, and has 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,
The thickness of the transparent protective film is 10 μm or more and 80 μm or less,
The organic-inorganic composite is a composite prepared using a photosensitive compound, an organosilicon compound, and an ultraviolet curable compound, and the photosensitive compound is selected from the group consisting of titanium, zirconium, and aluminum. Including at least one of
The inorganic oxide fine particles are at least one inorganic oxide fine particle selected from the group consisting of silicon oxide, titanium oxide, tin oxide, zircon oxide, cerium oxide, zinc oxide, antimony oxide, and double oxides thereof. ,
The inorganic oxide fine particles are surface-treated with a silane compound,
The amount of the silane compound is 0.1 to 80 parts by weight with respect to 100 parts by weight of the inorganic oxide fine particles.
Transparent laminate.
[3]
A transparent primer layer interposed between the transparent resin substrate and the transparent protective film,
The transparent primer layer is a layer obtained by coating and curing a primer composition containing a (meth) acrylate compound, and the transparent primer layer has a thickness of 5 μm or more,
The transparent protective film has a thickness of 5 μm or more and 80 μm or less,
Transparent laminate.
[4]
The transparent resin base material includes a polycarbonate resin or an acrylic resin, and has 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,
The organic-inorganic composite is a composite prepared using a photosensitive compound, an organosilicon compound, and an ultraviolet curable compound, and the photosensitive compound is selected from the group consisting of titanium, zirconium, and aluminum. Including at least one of
The inorganic oxide fine particles are at least one inorganic oxide fine particle selected from the group consisting of silicon oxide, titanium oxide, tin oxide, zircon oxide, cerium oxide, zinc oxide, antimony oxide, and double oxides thereof. ,
The inorganic oxide fine particles are surface-treated with a silane compound,
The amount of the silane compound is 0.1 to 80 parts by weight with respect to 100 parts by weight of the inorganic oxide fine particles.
Transparent laminate.
[5]
The transparent laminate as described above, which is a window material for a moving body.
[6]
A preparatory step of preparing a plate-like transparent resin base material having a heat resistance of 70 ° C. or higher, a substantially uniform thickness of 1 mm or more, and an elastic modulus of 1 GPa or more at room temperature;
A coating composition is applied on at least one surface of the transparent resin substrate and then cured to provide a transparent protective film having a thickness of 5 μm or more and 150 μm or less on the transparent resin substrate. Protective film forming step,
A method for producing a transparent laminate, comprising:
The coating composition contains a curable resin containing an organic-inorganic composite, and inorganic oxide fine particles having an average particle diameter of 10 nm to 100 nm,
The amount of the inorganic oxide fine particles is 5 parts by weight or more and 400 parts by weight or less with respect to 100 parts by weight of the curable resin contained in the coating composition.
A method for producing a transparent laminate.
[7]
A preparatory step of preparing a plate-like transparent resin base material having 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; ,
A primer layer forming step of coating a primer composition containing a (meth) acrylate compound on at least one surface of the transparent resin substrate to provide a primer layer having a thickness of 5 μm or more;
Using the coating composition, a film portion composed of the coating composition is formed on the primer layer, and then cured to provide a transparent protective film having a thickness of 5 μm or more and 80 μm or less on the primer layer. A transparent protective film forming step;
A method for producing a transparent laminate, comprising:
The coating composition contains a curable resin containing an organic-inorganic composite, and inorganic oxide fine particles having an average particle diameter of 10 nm to 100 nm,
The amount of the inorganic oxide fine particles is 5 parts by weight or more and 400 parts by weight or less with respect to 100 parts by weight of the curable resin contained in the coating composition.
A method for producing a transparent laminate.
[8]
The curing means in the transparent protective film forming step is a light having a wavelength range of 200 nm or more and 400 nm or less at an ambient temperature lower than the heat resistant temperature of the transparent resin substrate, and an illuminance of 1 × 10 ⁻² mW / cm ² or more 1 X10 ⁴ mW / cm ² or less, and a means for photocuring by irradiating under a condition where the integrated light quantity in the wavelength region is 5 × 10 ² mJ / cm ² or more and 3 × 10 ⁴ mJ / cm ² or less,
A method for producing a transparent laminate.
[9]
The organic-inorganic composite is a composite prepared using a photosensitive compound, an organosilicon compound, and an ultraviolet curable compound, and the photosensitive compound is selected from the group consisting of titanium, zirconium, and aluminum. Including at least one of
The inorganic oxide fine particles are at least one inorganic oxide fine particle selected from the group consisting of silicon oxide, titanium oxide, tin oxide, zircon oxide, cerium oxide, zinc oxide, antimony oxide, and double oxides thereof. ,
The inorganic oxide fine particles are surface-treated with a silane compound,
The amount of the silane compound is 0.1 to 80 parts by weight with respect to 100 parts by weight of the inorganic oxide fine particles.
A method for producing a transparent laminate.

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

  First, according to invention of Claim 1 of this application, the transparent laminated body provided with the transparent protective film which is hard to be cracked is obtained by setting heat resistance in the predetermined range. In addition, by using a curable resin containing an organic-inorganic composite and providing a transparent protective film with a thickness within a predetermined range on the transparent resin base material, it ensures scratch resistance while ensuring excellent scratch resistance. A transparent laminate having a transparent protective film having excellent properties can be obtained. Moreover, when the curable resin contained in the coating composition in the present invention contains an organic-inorganic composite, a protective film having excellent scratch resistance and the like can be obtained.

  The transparent protective film in the present invention further contains inorganic oxide fine particles. Thereby, the shear stress with respect to a transparent protective film is disperse | distributed by the inorganic oxide fine particle with high hardness, and the outstanding abrasion resistance will be exhibited. Furthermore, since the curable resin contained in the coating composition in the present invention contains an organic-inorganic composite, it interacts between the organic-inorganic composite present in the transparent protective film and the inorganic oxide fine particles. Occurs. Thereby, the outstanding damage resistance will be exhibited. Therefore, a transparent laminate including a transparent protective film having both excellent wear resistance and scratch resistance is realized.

  And the abrasion resistance and damage resistance of the whole transparent laminated body will improve by improving the abrasion resistance and damage resistance of a transparent protective film.

  In addition, according to the invention described in claim 2, by setting the thickness and elastic modulus of the transparent resin base material within predetermined ranges, the transparent laminate can be reduced in weight while being used in an actual use environment. It is possible to secure load resistance to withstand an assumed impact or load. In addition, the Vickers hardness of the transparent resin substrate is set within a predetermined range, the thickness of the transparent protective film is further set within a preferable range, and the inorganic oxide fine particles are mixed with silane having a weight ratio within the predetermined range. By surface-treating with a compound, the scratch resistance can be further improved.

  According to the invention of claim 3, the transparent protective film has a transparent primer layer formed of a primer composition between the transparent resin substrate and the transparent protective film. Part of UV and heat ray absorption function and part of scratch protection function can be distributed to the transparent primer layer, so it is possible to prevent yellowing even when the window material is used in harsh environment. The weather resistance of the laminate can be improved.

  Furthermore, when a large amount of UV absorber and heat ray absorber are contained only in the transparent protective film, it is considered that the transparent protective layer softens and inhibits curing during photocuring. Since an agent and a heat ray absorbent can be contained, these can be suppressed. Thereby, the weather resistance of a transparent laminated body can further be improved.

  According to the invention described in claim 4, the Vickers hardness of the transparent resin substrate is set within a predetermined range, the thickness of the transparent protective film is further set within a preferable range, and the inorganic oxidation is further performed. By subjecting the fine particles to a surface treatment with a silane compound having a weight ratio within a predetermined range, the scratch resistance can be further improved.

  Moreover, according to the invention of Claim 5, the window material excellent in both abrasion resistance and scratch resistance is realized.

  According to invention of Claim 6, it is possible to manufacture the transparent laminated body which was excellent in both abrasion resistance and damage resistance.

  Furthermore, according to the invention described in claim 7, it is possible to produce a transparent laminate having the same effect as that of claim 5 and having excellent weather resistance.

  According to invention of Claim 8, it is possible to manufacture the transparent laminated body which was excellent in both abrasion resistance and damage resistance. Furthermore, in this method, since the transparent protective film can be quickly provided by the photocuring step, the yield can be improved.

  According to invention of Claim 9, favorable hardness can be obtained, ensuring the function (transparency etc.) as a window material, when inorganic oxide microparticles | fine-particles are a specific kind.

It is a schematic diagram of the transparent laminated body by 1st Embodiment of this invention. It is an enlarged view of the transparent protective film part of FIG. It is a figure which shows the experimental result 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. It is explanatory drawing about the range of the average particle diameter of inorganic oxide microparticles | fine-particles. FIG. 6 (a) is a diagram (part 1) for explaining the effect of the first embodiment of the present invention, and FIG. 6 (b) is an enlarged view of a square part of FIG. 6 (a). It is a schematic diagram of the transparent laminated body by 2nd Embodiment of this invention. It is an enlarged view of the transparent protective film part of FIG. 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 According to First Embodiment FIG. 1 is a schematic view of a transparent laminate 1 according to the first embodiment of the present invention, and FIG. 2 is an enlarged view of the transparent protective film 3 portion of FIG. A transparent laminate 1 according to the present invention includes a plate-like transparent resin substrate 2 and a transparent protective film 3 provided on the transparent resin substrate 2. The transparent resin base material 2 constitutes a visible light transmitting portion that actually transmits light in a window material such as a moving body. In addition, such a window material may have a visible light non-transmission part as needed. 1 and 2 show the transparent laminate 1 in which the transparent protective film 3 is provided only on one side of the transparent resin base material 2, but the transparent protective film 3 may be provided on both sides. Good.

Transparent resin base material The transparent laminated body of this invention has a plate-shaped transparent resin base material. Examples of the transparent resin base material include resins that can sufficiently transmit visible light, such as polycarbonate resins, acrylic resins (such as acrylate resins and methacrylate resins), and PET resins. As a preferable transparent resin base material, a polycarbonate resin or a methacrylate resin may be mentioned. In the experiment mentioned in the form described below, polycarbonate (Teijin Kasei Co., Ltd .: L-1250) was used as the transparent resin substrate 2.

FIG. 3 shows the experimental results on the heat resistance of the transparent resin substrate 2. A transparent resin substrate 2 covering the surrounding black box, a is the ^{200W / m 2, 400W / m} 2, the light of the illuminance of 900 W / ^{m 2} assumed in real use environment temperature reached was irradiated until saturation. The solid line in FIG. 3 shows the experimental results at the highest ambient temperature of 40 ° C. assumed in the actual use environment. For reference, the experimental results at an atmospheric temperature of 20 ° C. are indicated by dotted lines.

  As shown in FIG. 3, the maximum temperature reached at an ambient temperature of 40 ° C. was 70 ° C. Therefore, the transparent resin substrate 2 preferably has a heat resistance of 70 ° C. or higher.

  FIG. 4 is an explanatory diagram for the elastic modulus of the transparent resin substrate 2. 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, unless the thickness of the resin window material is 6 mm or less, it is not possible to reduce the weight. In FIG. 4, when a load of 0.6 N is applied to the 150 mm square transparent resin base material 2 having a substantially uniform thickness of 1 mm in accordance with the JIS K 7191B method, with four sides fixed. The relationship between the elastic modulus of the transparent resin base material 2 and the maximum deflection amount at room temperature is shown.

  In general, the window material for a vehicle is required to have a maximum deflection amount of 0.34 mm or less under the above conditions. As shown in FIG. 4, when the maximum deflection amount is 0.34 mm, the elastic modulus is 1 GPa. Therefore, the transparent resin substrate 2 preferably has an elastic modulus of 1 GPa or more at room temperature.

If the surface hardness of the transparent resin base material 2 is not sufficiently high, deformation is likely to occur when a load is applied to the transparent protective film 3, and scratches generated in the transparent protective film 3 in accordance with the deformation increase. there is a possibility. Therefore, it is preferable that the transparent resin base material 2 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.

  In addition, the Vickers hardness of a resin base material can be measured based on description of JISZ2244 (2009).

Transparent Protective Film The transparent laminate of the present invention has a transparent protective film 3. And this transparent protective film 3 is a protective film obtained by coating and hardening the coating composition described below.

Coating composition The coating composition in this invention contains curable resin and the inorganic oxide microparticles | fine-particles which have an average particle diameter of 10 nm or more and 100 nm or less. The curable resin includes at least an organic-inorganic composite.

Organic-inorganic composite The organic-inorganic composite contained in the curable resin in the present invention can be prepared using a light-sensitive compound, an organic silicon compound, and an ultraviolet curable compound.

Photosensitive compound The photosensitive compound is selected from the group consisting of metal chelate compounds, metal organic acid salt compounds, metal compounds having two or more hydroxyl groups or hydrolyzable groups, hydrolysates thereof, and condensates thereof. At least one kind. This photosensitive compound is a compound sensitive to light having a wavelength of 350 nm or less.

  The photosensitive compound as used in the present invention is a compound that can remove the carbon component on the surface side by the action of light having a wavelength of 350 nm or less irradiated from the surface side, regardless of the mechanism. Preferably, the carbon content of the surface portion in the depth direction 2 nm from the surface is 80% of the carbon content of the portion where the carbon amount is not reduced (in the case of a film, for example, the back surface portion in the depth direction 10 nm from the film back surface). % Or less, more preferably 2 to 60%, and even more preferably 2 to 40%. Particularly preferably, the carbon component is reduced to a predetermined depth so that the removal amount thereof gradually decreases from the surface side. A compound that can be removed, that is, a compound that can form a film in which the carbon content gradually increases from the surface to a predetermined depth. Specific examples include compounds that absorb and excite light having a wavelength of 350 nm or less.

  Here, the light having a wavelength of 350 nm or less is light using a light source having light of any wavelength of 350 nm or less, preferably a light source having light of any wavelength of 350 nm or less as a main component. That is, light using a light source having a wavelength of 350 nm or less with the largest component amount.

  As the photosensitive compound, at least one selected from the group consisting of metal chelate compounds, metal organic acid salt compounds, metal compounds having two or more hydroxyl groups or hydrolyzable groups, hydrolysates thereof, and condensates thereof. The compound of this is mentioned. These may be hydrolysates and / or condensates, and in particular, hydrolysates and / or condensates of metal chelate compounds are preferred. Examples of the compound derived therefrom include those obtained by further condensing a condensate of a metal chelate compound. Such a photosensitive compound and / or derivative thereof may be chemically bonded to the organosilicon compound, dispersed in a non-bonded state, or in a mixed state thereof.

  The metal chelate compound is preferably a metal chelate compound having a hydroxyl group or a hydrolyzable group, and more preferably a metal chelate compound having two or more hydroxyl groups or hydrolyzable groups. In addition, having two or more hydroxyl groups or hydrolyzable groups means that the sum of hydrolyzable groups and hydroxyl groups is 2 or more. The metal chelate compound is preferably a β-ketocarbonyl compound, a β-ketoester compound, or an α-hydroxyester compound. Specifically, methyl acetoacetate, n-propyl acetoacetate, isopropyl acetoacetate, acetoacetate β-ketoesters such as n-butyl, sec-butyl acetoacetate, t-butyl acetoacetate; acetylacetone, hexane-2,4-dione, heptane-2,4-dione, heptane-3,5-dione, octane Β-diketones such as -2,4-dione, nonane-2,4-dione and 5-methyl-hexane-2,4-dione; hydroxycarboxylic acids such as glycolic acid and lactic acid: etc. coordinated compounds Is mentioned.

  The metal organic acid salt compound is a compound composed of a salt obtained from a metal ion and an organic acid. Examples of the organic acid include carboxylic acids such as acetic acid, oxalic acid, tartaric acid and benzoic acid; sulfonic acid, sulfinic acid and thiophenol. Organic compounds exhibiting acidity such as sulfur-containing organic acids such as: phenol compounds; enol compounds; oxime compounds; imide compounds; aromatic sulfonamides;

  The metal compound having two or more hydroxyl groups or hydrolyzable groups excludes the metal chelate compound and the metal organic acid salt compound, and examples thereof include metal hydroxides and metal alcoholates.

  Examples of the hydrolyzable group in the metal compound, the metal chelate compound, or the metal organic acid salt compound include an alkoxy group, an acyloxy group, a halogen group, and an isocyanate group, and an alkoxy group having 1 to 4 carbon atoms and 1 to 1 carbon atoms. An acyloxy group of 4 is preferred. In addition, having two or more hydroxyl groups or hydrolyzable groups means that the sum of hydrolyzable groups and hydroxyl groups is 2 or more.

  Such a hydrolyzate and / or condensate of a metal compound is obtained by hydrolyzing 0.5 mol or more of water with respect to 1 mol of a metal compound having two or more hydroxyl groups or hydrolyzable groups. It is preferable that it is a thing hydrolyzed using 0.5-2 mol water.

  Further, the hydrolyzate and / or condensate of the metal chelate compound is preferably hydrolyzed using 5 to 100 mol of water with respect to 1 mol of the metal chelate compound, More preferably, it is hydrolyzed with water.

  Further, the hydrolyzate and / or condensate of the metal organic acid salt compound is preferably one hydrolyzed using 5 to 100 mol of water with respect to 1 mol of the metal organic acid salt compound. More preferably, it is hydrolyzed with ˜20 mol of water.

  Examples of the metal in these metal compounds, metal chelate compounds or metal organic acid salt compounds include titanium, zirconium, aluminum, silicon, germanium, indium, tin, tantalum, zinc, tungsten, lead, etc. Among these, titanium Zirconium and aluminum are preferable, and titanium is particularly preferable. These may be used alone or in combination of two or more.

Organosilicon Compound As the organosilicon compound, a compound represented by the formula (I) can be given.
R _n SiX _4-n (I)
R and X are as follows.
R represents an organic group in which a carbon atom is directly bonded to Si in the formula. Examples of the organic group include a hydrocarbon group and a group composed of a hydrocarbon polymer. A hydrocarbon group having 1 to 30 carbon atoms is preferable, an alkyl group having 1 to 10 carbon atoms, and 2 to 10 carbon atoms. Are more preferable, or an epoxyalkyl group having 1 to 10 carbon atoms. The organic group may contain a silicon atom, or may be a group containing a polymer such as polysiloxane, polyvinyl silane, or polyacryl silane. Examples of the substituent include halogen and methacryloxy group. N represents 1 or 2, and n = 1 is particularly preferable. When n is 2, R may be the same or different.

  X represents a hydroxyl group or a hydrolyzable group. When (4-n) of formula (I) is 2 or more, X may be the same or different. The hydrolyzable group is, for example, a group capable of being hydrolyzed to form a silanol group or a siloxane condensate by heating at 25 ° C. to 100 ° C. in the presence of no catalyst and excess water. Specifically, an alkoxy group, an acyloxy group, a halogen group, an isocyanate group and the like can be mentioned, and an alkoxy group having 1 to 4 carbon atoms or an acyloxy group having 1 to 4 carbon atoms is preferable. .

  Specifically, as the organosilicon compound, methyltrichlorosilane, methyltrimethoxysilane, methyltriethoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriisopropoxysilane, ethyltributoxysilane, butyltrimethoxysilane, Pentafluorophenyltrimethoxysilane, phenyltrimethoxysilane, nonafluorobutylethyltrimethoxysilane, trifluoromethyltrimethoxysilane, dimethyldiaminosilane, dimethyldichlorosilane, dimethyldiacetoxysilane, dimethyldimethoxysilane, diphenyldimethoxysilane, dibutyldimethoxy Silane, trimethylchlorosilane, vinyltrimethoxysilane, (meth) acryloxypropyltrimethoxysilane, glycidyloxy Trimethoxysilane, 3- (3-methyl-3-oxetanemethoxy) propyltrimethoxysilane, oxacyclohexyltrimethoxysilane, methyltri (meth) acryloxysilane, methyl [2- (meth) acryloxyethoxy] silane, methyl- And triglycidyloxysilane and methyltris (3-methyl-3-oxetanemethoxy) silane. These may be used alone or in combination of two or more.

  Examples of the organosilicon compound having a hydrocarbon polymer group include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and cyclohexyl. (Meth) acrylate and other (meth) acrylic acid esters; (meth) acrylic acid, itaconic acid, fumaric acid and other carboxylic acids and maleic anhydride and other acid anhydrides; glycidyl (meth) acrylate and other epoxy compounds; diethylaminoethyl Amino compounds such as (meth) acrylate and aminoethyl vinyl ether; amino acids such as (meth) acrylamide, itaconic acid diamide, α-ethylacrylamide, crotonamide, fumaric acid diamide, maleic acid diamide, and N-butoxymethyl (meth) acrylamide Compound: A compound in which a vinyl polymer obtained by copolymerizing a vinyl compound selected from acrylonitrile, styrene, α-methylstyrene, vinyl chloride, vinyl acetate, vinyl propionate and the like is used as the R component of the formula (I) can be mentioned. .

  The photosensitive compound and the organosilicon compound may be condensed in advance. The condensation reaction of the photosensitive compound and the organosilicon compound can be performed by reacting these compounds in an aqueous solvent.

Ultraviolet curable compound An ultraviolet curable compound is a compound or resin having a functional group that undergoes a polymerization reaction upon irradiation with ultraviolet light in the presence of a photopolymerization initiator, and is a (meth) acrylate compound, epoxy resin, acrylate. There are vinyl compounds and the like excluding the compounds based on the base material. The number of functional groups is not particularly limited as long as it is 1 or more.
Examples of acrylate compounds include polyurethane (meth) acrylate, polyester (meth) acrylate, epoxy (meth) acrylate, polyamide (meth) acrylate, polybutadiene (meth) acrylate, polystyryl (meth) acrylate, polycarbonate diacrylate, and tripropylene glycol diacrylate. (Meth) acrylate, hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, siloxane polymer having (meth) acryloyloxy group, and the like, preferably polyester ( (Meth) acrylate, polyurethane (meth) acrylate, and epoxy poly (meth) acrylate, more preferably polyurethane ( (Meth) acrylate.
The molecular weight is usually 500 to 50,000, preferably 1,000 to 10,000 as a weight average molecular weight.

The epoxy (meth) acrylate can be obtained, for example, by an esterification reaction between an oxirane ring of a low molecular weight bisphenol type epoxy resin or a novolak epoxy resin and acrylic acid.
The polyester (meth) acrylate is obtained, for example, by esterifying the hydroxyl group of a polyester oligomer having hydroxyl groups at both ends with acrylic acid, obtained by condensation of a polyvalent carboxylic acid and a polyhydric alcohol. Alternatively, it can be obtained by esterifying the terminal hydroxyl group of an oligomer obtained by adding an alkylene oxide to a polyvalent carboxylic acid with acrylic acid.

  Urethane (meth) acrylate is a reaction product of an isocyanate compound obtained by reacting a polyol with diisocyanate and an acrylate monomer having a hydroxyl group, and examples of the polyol include polyester polyol, polyether polyol, and polycarbonate diol. .

  The urethane (meth) acrylate may be a commercially available product. As a commercial item, for example, Arakawa Chemical Industries, Ltd. product name: Beam set 102, 502H, 505A-6, 510, 550B, 551B, 575, 575CB, EM-90, EM92, Sannopco Corporation product name: Photomer 6008, 6210, manufactured by Shin-Nakamura Chemical Co., Ltd. Trade name: NK Oligo U-2PPA, U-4HA, U-6HA, H-15HA, UA-32PA, U-324A, U-4H, U-6H, Product name: Aronix M-1100, M-1200, M-1210, M-1310, M-1600, M-1960, manufactured by Kyoeisha Chemical Co., Ltd. Product names: AH-600, AT606, UA -306H, manufactured by Nippon Kayaku Co., Ltd. Trade names: Kayarad UX-2201, UX-2301, UX-3204, UX-3301, UX-4101 UX-6101, UX-7101, manufactured by Nippon Synthetic Chemical Industry Co., Ltd. Trade name: Purple light UV-1700B, UV-3000B, UV-6100B, UV-6300B, UV-7000, UV-7600B, UV-2010B, Negami Industrial Product name: Art Resin UN-1255, UN-5200, HDP-4T, HMP-2, UN-901T, UN-3320HA, UN-3320HB, UN-3320HC, UN-3320HS, H-61, HDP -M20, manufactured by Daicel UCB Co., Ltd. Trade names: Ebecryl 6700, 204, 205, 220, 254, 1259, 1290K, 1748, 2002, 2220, 4833, 4842, 4866, 5129, 6602, 8301, etc. it can.

  Examples of vinyl compounds excluding acrylate compounds include N-vinyl pyrrolidone, N-vinyl caprolactam, vinyl acetate, styrene, unsaturated polyester, and epoxy resins include hydrogenated bisphenol A diglycidyl ether, 3,4-epoxy. Cyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-meta-dioxane, bis (3,4-epoxycyclohexylmethyl) Examples include adipate.

Preparation of organic-inorganic composite The organic-inorganic composite contained in the curable resin of the present invention can be prepared using a light-sensitive compound, an organic silicon compound, and an ultraviolet curable compound. Examples of the method for preparing the organic-inorganic composite include a method in which water and a solvent are added as necessary, and the above ultraviolet curable compound, photopolymerization initiator, organosilicon compound, photosensitive compound, and the like are mixed.
Specifically, for example, a photosensitive compound is mixed with a solvent, a predetermined amount of water is added, (partial) hydrolysis is performed, and then an organosilicon compound is added (partial) to be hydrolyzed. Next, the ultraviolet curable compound is dissolved in a solvent and a photopolymerization initiator is added, and then both solutions may be mixed, or these components may be mixed simultaneously. As for the method of mixing the organosilicon compound and the photosensitive compound, after mixing the organosilicon compound and the photosensitive compound, water is added (partially) to hydrolyze the organosilicon compound and the photosensitive compound. A method of mixing separately (partially) hydrolyzed products can be mentioned. Although it is not always necessary to add water and / or a solvent, it is preferable to add (partly) a hydrolyzate by adding water. The amount of the predetermined amount of water depends on the type of the photosensitive compound. For example, when the photosensitive compound is a metal compound having two or more hydroxyl groups or hydrolyzable groups, the amount of water is 1 mol of the metal compound. It is preferable to use 0.5 mol or more of water, and more preferably 0.5 to 2 mol of water. When the photosensitive compound is a metal chelate compound or metal organic acid salt compound, it is preferable to use 5 to 100 mol of water with respect to 1 mol of the metal chelate compound or metal organic acid salt compound. More preferably, the water is used.

  The metal oxide sol can be prepared by dispersing metal oxide particles in a solvent, and can be prepared by blending with other components. For example, the dispersion stability can be improved by treating these metal oxide particles with a silane coupling agent, a titanium coupling agent, or the like.

  The solvent to be used is not particularly limited. For example, aromatic hydrocarbons such as benzene, toluene and xylene; aliphatic hydrocarbons such as hexane and octane; and alicyclic hydrocarbons such as cyclohexane and cyclopentane. Ketones such as acetone, methyl ethyl ketone and cyclohexanone; ethers such as tetrahydrofuran and dioxane; esters such as ethyl acetate and butyl acetate; amides such as N, N-dimethylformamide and N, N-dimethylacetamide; dimethyl sulfoxide And the like; alcohols such as methanol and ethanol; polyhydric alcohol derivatives such as ethylene glycol monomethyl ether and ethylene glycol monomethyl ether acetate; and the like. These solvents may be used alone or in combination of two or more.

  The organic / inorganic composite thus obtained preferably has a solid content of 1 to 75% by weight, more preferably 10 to 60% by weight. The amount of the ultraviolet curable compound is preferably 2 to 98% by weight based on the total weight of the organosilicon compound and / or the condensate thereof, the photosensitive compound, the ultraviolet curable compound and the photopolymerization initiator. More preferably, it is -95 weight%. In addition, although the content of the photosensitive compound depends on the type, generally, metal atoms (for example, titanium, zirconium and / or aluminum) in the photosensitive compound with respect to Si in the organosilicon compound. Etc.) is preferably 0.01 to 0.5 molar equivalent, more preferably 0.05 to 0.2 molar equivalent.

Other unsaturated compounds The curable resin in the present invention may contain other unsaturated compounds in addition to the organic-inorganic composite. Specific examples of the unsaturated compound include, for example, 2-hydroxy-3-acryloyloxypropyl methacrylate, glycerin dimethacrylate, bisphenol A diglycidyl ether diacrylate, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, γ -Methacryloyloxypropyltrimethoxysilane, tricyclo [5.2.1.02,6] decane diacrylate, dicyclopentanyl diacrylate, tricyclo [5.2.1.02,6] decane diacrylate, 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 Methacrylate, 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 Tellurium, polyester acrylate, polyether acrylate, vinyl acrylate, polyene / thiol, silicone acrylate, polybutadiene, polystyrylethyl methacrylate, styrene, vinyl acetate, N-vinylpyrrolidone, butyl acrylate, 2-ethylhexyl acrylate, n-hexyl acrylate, cyclohexyl Acrylate, n-decyl acrylate, isobornyl acrylate, dicyclopentenyloxyethyl acrylate, phenoxyethyl acrylate, trifluoroethyl methacrylate, tripropylene glycol diacrylate, 1,6-hexanediol diacrylate, tetraethylene glycol diacrylate, hydroxy Pivalic acid neopentyl glycol diacrylate, trimethylo Propane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, can be used dipentaerythritol hexaacrylate, diallyl maleate or other reactive monomers or oligomers. These reactive monomers or oligomers may be used alone or in combination of two or more.

As a preferred configuration of the curable resin in the coating composition in the present invention,
Organic-inorganic composite: 5-75 parts by weight
Other unsaturated compounds: 25 to 95 parts by weight,
(The above is a solid content ratio with respect to 100 parts by weight of the curable resin.)
Is mentioned.

  In the present specification, the “curable resin contained in the coating composition” means the solid weight of the curable resin contained in the coating composition.

  In the present invention, the transparent protective film 3 preferably has a thickness of 5 μm or more on the visible light transmitting portion of the transparent resin substrate 2 in order to ensure excellent scratch resistance. In order to prevent cracking and ensure excellent scratch resistance, it is preferable to have a thickness of 150 μm or less. That is, the transparent protective film 3 preferably has a thickness of 5 μm or more and 150 μm or less in order to ensure excellent scratch resistance and prevent cracking. Further, the transparent protective film 3 further preferably has a thickness of 10 μm or more and 80 μm or less in order to ensure better scratch resistance.

Inorganic oxide fine particles The coating composition of the present invention contains inorganic oxide fine particles 4.
FIG. 5 shows the results of a wear resistance test and a scratch resistance test described later, with the average particle diameter of the inorganic oxide fine particles 4 being changed for the transparent laminate 1. In addition, FIG. 5 shows the test result with respect to the transparent laminated body 1 whose thickness is 16 micrometers. Moreover, the weight ratio of the silane compound with respect to the inorganic oxide fine particle 4 mentioned later is 23 weight% (based on the composition of Example 1). Here, when the haze change ΔH is 10% or more, it is easy to perceive a decrease in transmitted image clarity. Therefore, when the haze change ΔH is less than 10%, excellent wear resistance is ensured. Can be determined. Similarly, when the gloss retention is less than 70%, it is easy to perceive a decrease in transmitted image definition. Therefore, when the gloss retention exceeds 70%, excellent scratch resistance is ensured. It can be judged.

  As shown in FIG. 5, when the average particle size of the inorganic oxide fine particles 4 is in the range of 10 nm to 100 nm, the haze value change ΔH is less than 10% and the gloss retention is more than 70%. Therefore, the inorganic oxide fine particles 4 preferably have an average particle diameter of 10 nm to 100 nm in order to ensure both excellent wear resistance and scratch resistance.

  In the present specification, the average particle diameter of the inorganic oxide fine particles means a numerical value of the volume-based average diameter to be measured. The particle size distribution is preferably measured using a laser diffraction / scattering particle size distribution measuring apparatus.

  The inorganic oxide fine particles are at least one inorganic oxide fine particle selected from the group consisting of silicon oxide, titanium oxide, tin oxide, zircon oxide, cerium oxide, zinc oxide, antimony oxide, and double oxides thereof. Is preferred.

  As an example of the case where the inorganic oxide fine particles are silicon oxide, silica fine particles having an average particle diameter in the above range can be mentioned. Specific examples of such silica fine particles include, for example, methanol silica sol, IPA-ST, IPA-ST-ZL, EG-ST, NPC-ST-30, DMAC-ST, which are organosilica sols manufactured by Nissan Chemical Industries, Ltd. , MEK-ST, MIBK-ST, XBA-ST, PMA-ST, PGM-ST and the like.

  Specific examples of the case where the inorganic oxide fine particles are titanium oxide include 1120Z, 2120Z, 6320Z manufactured by JGC Catalysts and Chemicals, TECNADIS-TI-220 manufactured by TECNAN, and the like.

  Specific examples of the case where the inorganic oxide fine particles are tin oxide include CX-S303IP, CX-S301H, CX-S501M, and CX-S505M manufactured by Nissan Chemical Industries, Ltd.

  As specific examples when the inorganic oxide fine particles are zircon oxide, for example, ZR-30AL, ZR-30AH, ZR-20AS, ZR-40BL, ZR-30BS, ZR-30BF, TECNAN manufactured by Nissan Chemical Industries, Ltd. Examples thereof include TECNADIS-ZR-220 manufactured by KK.

  Specific examples of the case where the inorganic oxide fine particles are cerium oxide include, for example, CE-20A manufactured by Nissan Chemical Industries, Ltd., TECNADIS-CE-220 manufactured by TECNAN, and the like.

  Specific examples of the case where the inorganic oxide fine particles are zinc oxide (ZnO) include, for example, F-2 and F-1 manufactured by Hux Itec, ZnO-310, ZnO-410, ZnO-510 manufactured by Sumitomo Osaka Cement, TECNAN Examples thereof include TECNADIS-ZN-220 manufactured by KK.

  As a specific example when the inorganic oxide fine particles are antimony oxide, for example, PATOX-U manufactured by Nippon Seiko Co., Ltd. may be mentioned.

As a specific example when the inorganic oxide fine particles are a double oxide of the above metal oxide, for example, a double oxide of zinc oxide (ZnO) and antimony pentoxide (Sb ₂ O ₅ ) (ZnSb ₂ O ₆ ), etc. Is mentioned. Specific examples of such a double oxide include CX-Z210IP-F2, CX-Z330H, and CX-Z610M-F2 manufactured by Nissan Chemical Industries, Ltd.

  The amount of the inorganic oxide fine particles is preferably contained in the coating composition in an amount of 5 to 400 parts by weight with respect to 100 parts by weight of the curable resin. When the amount of the inorganic oxide fine particles is less than 5 parts by weight, there is a possibility that sufficient wear resistance cannot be ensured. When the amount of inorganic oxide fine particles exceeds 400 parts by weight, the film part may be embrittled. The amount of the inorganic oxide fine particles is more preferably contained in the coating composition in an amount of 5 to 200 parts by weight with respect to 100 parts by weight of the curable resin.

  As the inorganic oxide fine particles, it is more preferable to use inorganic oxide fine particles surface-treated with a silane compound. By using inorganic oxide fine particles surface-treated with a silane compound, the inorganic oxide fine particles can be suitably dispersed in the transparent protective film. Furthermore, the curable resin and the inorganic oxide fine particles contained in the coating composition can be covalently bonded, and this has the advantage that the effects of improving wear resistance and scratch resistance can be enhanced. Furthermore, by selecting a silane compound suitable for the curable resin contained in the coating composition, a hydrogen bond, a π bond, or the like occurs between the silane compound surface-treated on the inorganic oxide fine particles and the curable resin. Intermolecular force can be applied. Thereby, the effect of improving abrasion resistance and scratch resistance can be further enhanced.

As a silane compound used for surface treatment of inorganic oxide fine particles, for example, the following general formula (5)
Y _m SiA _n B _4-mn (5)
It is preferable to use the compound represented by these. Here, Y is an organic functional group having at least one selected from the group consisting of (meth) acryloyl group, glycidyl group, vinyl group, guanyl group and epoxy group, and A is an alkyl group or other organic functional group , B is a hydroxyl group, an alkoxyl group or a halogen atom, m is an integer of 0 to 1, n is an integer of 0 to 3, and m + n satisfies 1 or more and 3 or less.

  Specific examples of such silane compounds include 3-acryloxypropyldimethylmethoxysilane, 3-acryloxypropylmethyldimethoxysilane, 3-acryloxypropyldiethylmethoxysilane, 3-acryloxypropylethyldimethoxysilane, 3-acryloxy. Propyltrimethoxysilane, 3-acryloxypropyldimethylethoxysilane, 3-acryloxypropylmethyldiethoxysilane, 3-acryloxypropyldiethylethoxysilane, 3-acryloxypropylethyldiethoxysilane, 3-acryloxypropyltriethoxy Silane, 3-methacryloxypropyldimethylmethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyldiethylmethoxysilane, 3-methyl Acryloxypropylethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyldimethylethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyldiethylethoxysilane, 3-methacryloxypropylethyl Diethoxysilane, 3-methacryloxypropyltriethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, trimethoxysilane, ethyltrimethoxysilane, diethyldimethoxysilane, triethylmethoxysilane, propyltrimethoxysilane, dipropyltrimethoxysilane, Tripropylmethoxysilane, isopropyltrimethoxysilane, diisopropyldimethoxysilane, triisopropylmethoxysilane Methyltriethoxysilane, dimethyldiethoxysilane, triethoxysilane, ethyltriethoxysilane, diethyldiethoxysilane, triethylethoxysilane, propyltriethoxysilane, dipropyltriethoxysilane, tripropylethoxysilane, isopropyltriethoxysilane, diisopropyl Examples thereof include diethoxysilane and triisopropylethoxysilane. These silane compounds may be used alone or in combination of two or more.

  The silane compound may be a mixture of the silane compound and a hydroxyalkyl acrylate such as 4-hydroxybutyl acrylate. In addition, as a silane compound, it is more preferable that it is only the said silane compound.

  The amount of the silane compound is preferably 0.1 to 80 parts by weight with respect to 100 parts by weight of the inorganic oxide fine particles. When the amount of the silane compound is within the above range, both excellent wear resistance and scratch resistance can be ensured.

  As a method of surface-treating the inorganic oxide fine particles with a silane compound, for example, the inorganic oxide fine particles and the silane compound described above are treated at a temperature of 50 to 120 ° C., preferably 60 to 90 ° C. for 0.1 to 24 hours. Preferably, a method of surface-treating inorganic oxide fine particles by stirring for 0.5 to 8 hours can be mentioned.

Other Components The coating composition in the present invention may further contain a photopolymerization initiator, a curing catalyst, an ultraviolet absorber, a light stabilizer and the like as necessary in addition to the above components. The coating composition further comprises organic / inorganic fillers, plasticizers, flame retardants, heat stabilizers, antioxidants, lubricants, antistatic agents, mold release agents, foaming agents, nucleating agents, colorants, and crosslinks as necessary. An additive such as an agent, a dispersion aid, and a resin component may be included.

  When the coating composition is photocured, it preferably contains a photopolymerization initiator. Examples of the photopolymerization initiator include compounds such as acetophenone series, benzoin series, benzophenone series, thioxanthone series, and acylphosphine oxide series. You may further contain the photoinitiator adjuvant and / or sharpener etc. which show an effect in combination with a photoinitiator.

  Examples of photopolymerization initiators include trichloroacetophenone, diethoxyacetophenone, 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4-methylthio Phenyl) -2-morpholinopropan-1-one, benzoin methyl ether, benzyldimethyl ketal, benzophenone, thioxanthone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, methylphenylglyoxylate, camphorquinone, benzyl, anthraquinone, 4 , 4′-bis (dimethylamino) benzophenone and the like. These photopolymerization initiators may be used alone or in combination of two or more.

  As the ultraviolet absorber, for example, a hydroxyphenyltriazine-based organic ultraviolet absorber can be used. As the light stabilizer, for example, a hindered amine light stabilizer can be used.

  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 -Cyanoates such as ethylhexyl-2-cyano-3,3-diphenyl acrylate Relates, or salicylates such as phenyl salicylate, p-octylphenyl salicylate, or benzylidene malonates such as diethyl-p-methoxybenzylidene malonate, 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) Triazines such as 1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol, or 2- (2′-hydroxy-5-methacryloxyethylphenyl) -2H-benzotriazole Of 2- (2′-hydroxy-5-acryloxyethylphenyl) -2H-benzotriazole and a vinyl monomer copolymerizable with this monomer A copolymer or the like 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 (octylphenol) Nickel complexes such as rusulfide, nickel complex-3,5-di-t-butyl-4-hydroxybenzyl phosphate monoethylate, nickel dibutyldithiocarbamate, etc. can be used. Two or more types may be used in combination.

  The coating composition containing a curable resin and inorganic oxide fine particles used in the present invention is prepared by mixing the above-described curable resin, inorganic oxide fine particles, and other components as necessary according to ordinary techniques in the art. Can be prepared. In preparing the coating composition, a commonly used solvent (such as water or an organic solvent) may be used as necessary.

Manufacturing method of transparent laminate according to the first embodiment The manufacturing method of the transparent laminate 1 according to the first embodiment of the present invention is:
A preparatory step of preparing a plate-like transparent resin base material having a heat resistance of 70 ° C. or higher, a substantially uniform thickness of 1 mm or more, and an elastic modulus of 1 GPa or more at room temperature;
A coating composition is applied on at least one surface of the transparent resin substrate and then cured to provide a transparent protective film having a thickness of 5 μm or more and 150 μm or less on the transparent resin substrate. Protective film forming step,
Is included.

  A step of adhering a spacer on the transparent resin substrate 2 may be included before the coating composition is applied. By coating the coating composition after adhering the spacer, there is an advantage that a protective film having a predetermined thickness can be obtained more easily.

As the curing means for the coating composition, a means for photocuring the coating composition by irradiating light at an atmospheric temperature lower than the heat resistant temperature of the transparent resin substrate is preferable. As such photocuring means, for example, using a mercury lamp, the illuminance in the wavelength region of 200 nm to 400 nm is 1 × 10 ⁻² mW / cm ^{2 to} 1 × 10 ⁴ mW / cm ² , and the integrated light quantity in the wavelength region Is preferably 5 × 10 ² mJ / cm ² or more and 3 × 10 ⁴ mJ / cm ² or less.

  The photocuring can be carried out under the atmosphere. Preferably, it is carried out in an atmosphere in which the oxygen partial pressure is reduced to the atmosphere or less, preferably 1% or less by purging with nitrogen. Further, the photocuring step may be performed while wiping a gas having a lower oxygen partial pressure than the atmosphere, for example, a gas in which nitrogen is mixed in the atmosphere, onto the surface of the coating composition. Further, the photocuring step may be performed by placing a transparent member such as a transparent film, an organic composition that does not undergo a curing reaction with the coating composition, a laminate, or glass on the upper portion. Moreover, you may include the heating process as needed before the photocuring process. For example, after coating the coating composition and before curing, a process of heating at a temperature sufficiently lower than the heat-resistant temperature of the transparent resin substrate 2, for example, 80 ° C., and removing the excess coating composition with a film or the like from above. May be included.

  As described above, the transparent laminate 1 including the transparent protective film 3 having both excellent wear resistance and scratch resistance can be produced by the method for producing the transparent laminate 1 of the present embodiment. Moreover, since the transparent protective film 3 can be rapidly provided by photocuring, a yield can be improved rather than the manufacturing method including a baking process. Moreover, the photocuring process and the whole manufacturing method can be simplified by carrying out the photocuring process with the above illuminance and integrated light quantity.

  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 to the atmosphere or less, preferably 1% or less, such oxygen inhibition can be suppressed. Moreover, the smoothness of the transparent laminated body 1 can be improved by implementing a heating process before a photocuring process. Moreover, the smoothness 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 the transparent laminate 1 of this embodiment, the thickness and elastic modulus of the transparent resin substrate 2 are set within a predetermined range. Thereby, it is possible to ensure the load resistance for withstanding the impact and load assumed during use in the actual use environment while reducing the weight of the transparent laminate 1. Furthermore, the transparent laminated body 1 provided with the transparent protective film 3 which is hard to be cracked is obtained by setting heat resistance in the predetermined range. Moreover, it was excellent in providing the transparent protective film 3 containing the inorganic oxide microparticles 4 on the transparent resin substrate 2 with a thickness within a predetermined range using a curable resin containing an organic-inorganic composite. The transparent laminated body 1 provided with the transparent protective film 3 which is hard to be cracked, ensuring scratch resistance and abrasion resistance is obtained.

  Moreover, since the transparent resin base material 2 contains a highly versatile polycarbonate resin or acrylic resin, the transparent laminated body 1 can be manufactured easily.

  Moreover, when the transparent protective film 3 contains an ultraviolet absorber, the ultraviolet absorbing power and heat ray absorbing power of the transparent protective film 3 can be improved. Moreover, since the transparent protective film 3 contains a light stabilizer, it is possible to prevent deterioration of the transparent laminate 1 due to ultraviolet rays or the like. As a result, the weather resistance of the transparent laminate 1 can be improved as a result.

Next, the effect | action by which the transparent laminated body 1 contains the inorganic oxide fine particle 4 is demonstrated using FIG.
FIG. 6A shows a state where the wear wheel 11 containing the inorganic oxide fine particles is rotated and moved back and forth with respect to the transparent protective film 3 and a load is applied. At this time, when the wear wheel 11 is rotated, a shear stress is applied in the direction indicated by the symbol (a) in FIG. 6B. As a result, the inorganic oxide has a sufficiently large average particle diameter as compared with the material constituting the transparent protective film 3. It is considered that the shear stress is dispersed due to the presence of the material fine particles 4. Therefore, it is possible to prevent the transparent protective film 3 from peeling off in the form of flakes, and thus it is possible to ensure the excellent wear resistance of the transparent laminate 1. FIG. 6 assumes a Taber abrasion test based on JIS R3212 described later.

  The transparent laminate 1 according to the present embodiment has a protective film formed by curing of a curable resin containing an organic-inorganic composite in addition to the inorganic oxide fine particles 4 being included, and thus has excellent wear resistance. Both scratch resistance and scratch resistance can be ensured. Thereby, the transparent laminated body 1 which fully satisfy | fills the specification of the Taber abrasion property employ | adopted by JIS specification (JISR3212) etc. is obtained.

  In a more preferred embodiment, the inorganic oxide fine particles 4 have a mean particle diameter within a predetermined range and are surface-treated with a silane compound having a weight ratio within the predetermined range. Can be suitably dispersed in the protective protective film 3, and the inorganic oxide fine particles and the curable resin can be covalently bonded. Therefore, the abrasion resistance of the transparent laminate 1 is improved by the inorganic oxide fine particles 4 and The effect of improving scratch resistance can be enhanced. Depending on the composition of the silane compound, intermolecular forces such as hydrogen bonds and π bonds can be applied between the silane compound surface-treated on the inorganic oxide fine particles and the curable resin. The effect of improving the abrasion resistance and scratch resistance of the transparent laminate 1 by the oxide fine particles 4 can be enhanced.

Transparent Laminate According to Second Embodiment FIG. 7 shows a schematic diagram of a transparent laminate 51 according to the second embodiment of the present invention. FIG. 8 is an enlarged view of the transparent protective film 53 portion of FIG. The transparent laminate 51 according to the second embodiment of the present invention includes a plate-like transparent resin base material 52, a transparent primer layer 55 provided on at least one surface of the transparent resin base material 52, and a transparent primer layer 55. And a provided transparent protective film 53. 7 shows the transparent laminate 51 in which the transparent primer layer 55 and the transparent protective film 53 are provided only on one surface of the transparent resin base material 52, these are provided on both surfaces of the transparent resin base material 52. It may be done.

Primer Composition The transparent laminate 51 according to the present embodiment is different from the transparent laminate 1 of the first embodiment in that a transparent primer layer 55 is interposed between the transparent resin substrate 52 and the transparent protective film 53. . Other configurations are the same as those in the first embodiment, and the description thereof will be omitted below.

  The transparent primer layer 55 is prepared by painting and curing the primer composition. The obtained transparent primer layer preferably has a thickness of 5 μm or more in order to ensure excellent weather resistance. The upper limit of the thickness of the primer layer is preferably 100 μm or less, and more preferably 70 μm or less.

  The primer composition forming the transparent primer layer includes a polymerizable compound including a (meth) acrylate compound and / or a (meth) acrylate copolymer. (Meth) acrylate compounds include alicyclic unsaturated compounds and non-alicyclic compounds. One aspect of the preferred primer composition in the present invention includes a polymerizable compound containing an alicyclic unsaturated compound. Here, the quantity of the alicyclic unsaturated compound contained in a polymeric compound is contained in 5-100 weight part with respect to 100 weight part of polymeric compounds. The alicyclic unsaturated compound is, for example, a di (meth) acrylate compound represented by the following general formula (6). Such a polymerizable compound can be radically polymerized when the curable resin that is the main component of the transparent protective film 53 is a resin capable of radical polymerization.

  In the general formula (6), R is a hydrogen atom or a methyl group, and Z is represented by the following formula (7) or (8).

  Specific examples of the alicyclic unsaturated compound include dimethylol tricyclodecane diacrylate, 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] pentadecanediacrylate, pen Cyclo [6.5.1.13,6.02,7.09,13] pentadecanedimethacrylate, pentacyclo [6.5.1.13,6.02,7.09,13] pentadecanedimethacrylate, 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 may be used alone or in combination of two or more.

  The polymerizable compound contained in the primer composition may contain an acyclic unsaturated compound in addition to the alicyclic unsaturated compound. Unsaturated compounds are generally roughly 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 functional unsaturated compounds 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. In addition, as reactive monofunctional monomers, (meth) acrylic acid, styrene, vinyl acetate, N-vinylpyrrolidone, methyl methacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, n-hexyl acrylate Cyclohexyl acrylate, n-decyl acrylate, isobornyl acrylate, dicyclopentenyloxyethyl acrylate, phenoxyethyl acrylate, trifluoroethyl methacrylate, -hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxy Propyl 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, and tetraethylene glycol, which are unsaturated compounds other than the above general formula (6). Diacrylate, hydroxypivalate neopentyl glycol diacrylate, polyethylene 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.

  The transparent primer layer 55 may include, for example, a compound such as an acetophenone-based, benzoin-based, benzophenone-based, thioxanthone-based, or acylphosphine oxide-based photopolymerization initiator. The photopolymerization initiator acts as a polymerization initiator in the photocuring step included in the method for producing the transparent laminate 51 described later. Further, the transparent primer layer 55 may include a photoinitiator assistant or a sharpening agent that exhibits an effect in combination with a photopolymerization initiator.

  Specific examples of the photopolymerization initiator include trichloroacetophenone, diethoxyacetophenone, 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4-methylthio Phenyl) -2-morpholinopropan-1-one, benzoin methyl ether, benzyldimethyl ketal, benzophenone, thioxanthone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, methylphenylglyoxylate, camphorquinone, benzyl, anthraquinone, Michler's ketone and the like can be used.

  Another aspect of the primer composition preferred in the present invention comprises a polymerizable compound comprising a (meth) acrylate copolymer. Examples of the (meth) acrylate copolymer include a (meth) acrylate copolymer obtained by polymerizing the reactive monofunctional monomer and / or reactive polyfunctional monomer by a commonly used method. In embodiments where the primer composition includes such a (meth) acrylate copolymer, it is preferable to include an isocyanate curing agent. Examples of the isocyanate curing agent include hexamethylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, and dimers, trimers or multimers thereof. In the primer composition, the amount of the isocyanate curing agent is preferably 1 to 2 equivalents relative to 1 equivalent of the hydroxy group of the (meth) acrylate copolymer.

  Furthermore, at least one of the transparent protective film 53 and the transparent primer layer 55 may include the ultraviolet absorber and the light stabilizer described in the first embodiment.

  As mentioned above, according to the transparent laminated body 51 of this embodiment, in addition to the effect obtained by the transparent laminated body 1 of 1st Embodiment, the following effect is acquired. That is, a part of the ultraviolet and heat ray absorbing function of the transparent protective film 53 can be distributed to the transparent primer layer 55. Further, since the transparent primer layer 55 can contain an ultraviolet absorber and a heat ray absorber, a transparent protective film that can occur when only the transparent protective film 53 contains a large amount of an ultraviolet absorber and a heat ray absorber. Softening of 53 and inhibition of curing during photocuring can be suppressed. Accordingly, it is possible to further improve the weather resistance while ensuring the excellent wear resistance and scratch resistance of the transparent protective film 53 of the transparent laminate 51. As a result, a transparent laminate 51 suitable for use in a vehicle window that can withstand long-term use can be obtained.

  In addition, as described above, when a load is applied to the transparent protective film 53, the scratches generated in the transparent protective film 53 are increased according to the deformation. However, the deformation is suppressed by interposing the primer layer 55. be able to. Therefore, a part of the flaw prevention function of the transparent protective film 53 can be distributed to the transparent primer layer 55.

Manufacturing Method of Transparent Laminate According to Second Embodiment The manufacturing method of the transparent laminate 51 according to the second embodiment of the present invention is as follows.
A preparatory step of preparing a plate-like transparent resin base material having 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; ,
A primer layer forming step of coating a primer composition containing a (meth) acrylate compound on at least one surface of the transparent resin substrate to provide a primer layer having a thickness of 5 μm or more;
Using the coating composition, a film portion composed of the coating composition is formed on the primer layer, and then cured to form a transparent protective film having a thickness of 5 μm or more and 80 μm or less on the primer layer. Providing a transparent protective film forming step;
Is included.

  A step of adhering a spacer on the transparent resin substrate 2 may be included before the primer composition is applied. By applying the primer composition after bonding the spacers, there is an advantage that a primer layer having a predetermined thickness can be obtained more easily.

  The uncured primer layer thus formed can be cured using the above-described curing means for the coating composition.

  Next, a film part made of the coating composition is formed on the obtained primer layer, and then cured to provide a transparent protective film. Any of the coating means for the coating composition described above may be used. Subsequently, a transparent protective film is formed by curing. As the curing means for these coating compositions, the above-described curing means can be used.

  Moreover, in the manufacturing method of the transparent laminated body 51, you may implement what is called wet on wet coating which coats a coating composition in the state which the primer composition which comprises the transparent primer layer 55 does not dry. When wet-on-wet coating is performed, the primer composition may be heated or irradiated for a short period of time before the coating composition is applied.

  As mentioned above, according to the manufacturing method of the transparent laminated body 51 of this embodiment, in addition to abrasion resistance and damage resistance, the transparent laminated body 51 provided with the transparent protective film 3 excellent in weather resistance can be produced. Is possible.

  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 transparent laminated body by this invention and the manufacturing method of a transparent laminated body are given and demonstrated with an Example and a comparative example, this invention is not limited to a following example. In the examples, parts and% mean parts by weight and% by weight.

Preparation Example 1 Preparation of Organic-Inorganic Composite Diisopropoxybisacetylacetonate Titanium (Nippon Soda Co., Ltd., “T-50”, solid content: 16 in a reaction vessel equipped with a stirrer, thermometer and cooling tube. 50.2) 200.2 parts by weight and 137.0 parts by weight of ethanol (an absolute ethanol ≧ 99.5% manufactured by Aldrich Japan) were stirred and dissolved. Thereafter, 38.6 parts by weight of ion-exchanged water was added with stirring. This solution was stirred and heated for 2 hours while being heated to 40 ° C. to obtain a hydrolyzate solution [A-1] of a yellow transparent metal compound at a solid content of 5.0% by weight.
264.8 parts by weight of vinyltrimethoxysilane [B-1] (manufactured by Shin-Etsu Chemical Co., Ltd., “KBM-1003”) and 3-methacryloxypropyltrimethoxysilane [B-2] (Shin-Etsu Chemical Co., Ltd.) The liquid [C-1] ([B-1] / [B-2] = 70/30: mol) prepared by mixing 190.2 parts by weight of “KBM-503”, manufactured by the manufacturer. Next, 453.1 parts by weight of [A-1] and 455.0 parts by weight of [C-1] were mixed by stirring, 92.0 parts by weight of ion-exchanged water was added, and the mixture was stirred and condensed for 1 day [D-1 ] Was produced.
451.8 parts by weight of urethane acrylate oligomer (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., “UV7600B”) was dissolved in 364.1 parts by weight of methyl isobutyl ketone. In this solution, 18.1 parts by weight of 2-methyl-1- (methylthiophenyl) -2-morpholinopropan-1-one (“Irgacure (registered trademark) 907” manufactured by BASF) was dissolved as a photopolymerization initiator, [E-1] was obtained.
[D-1] 166.1 parts by weight and [E-1] 834.0 parts by weight so that the solid content ratio is [D-1] / [E-1] = 10% by weight / 90% by weight. Were mixed to prepare a target organic-inorganic composite solution [F-1] (solid content concentration 52.0% by weight) having a polyhedral structure or an incomplete polyhedral structure.

Preparation Example 2-1 Preparation of fine particles (P-1 (23)) surface-treated with a silane compound In a reaction vessel equipped with a stirrer, a thermometer and a cooling pipe, isopropanol-dispersed colloidal silica sol (average particle size of 10 ˜15 nm, solid content 30% by weight, manufactured by Nissan Chemical Industries, Ltd .; IPA-ST) 100 parts by weight (silica solid content 30 parts by weight), and 3-methacryloxypropyltrimethoxysilane (Toray Dow) as the silane compound 7 parts by weight of Corning Silicone Co., Ltd. (SZ-6030) were added. Then, it heated gradually, stirring, and after the temperature of the reaction solution reached 68 degreeC, it heated for 5 hours and surface-treated, and the silica fine particle surface-treated with the silane compound was created. The weight part of the silane compound used for the surface treatment was 23 parts by weight with respect to 100 parts by weight of the solid content of the silica fine particles.

Preparation Example 2-2 Preparation of fine particles (P-2 (0.1)) surface-treated with a silane compound As silica fine particles, isopropanol-dispersed colloidal silica sol (average particle size 70-100 nm, solid content 30% by weight, Nissan Chemical Industries ( IPA-ST-ZL) 100 parts by weight (silica solid content 30 parts by weight) and silane compound 3-methacryloxypropyltrimethoxysilane (Toray Dow Corning Silicone Co., Ltd.) Silica fine particles surface-treated with a silane compound were prepared in the same manner as in Preparation Example 2-1, except that the amount of SZ-6030) was changed from 7 parts by weight to 0.03 parts by weight. The weight part of the silane compound used for the surface treatment was 0.1 part by weight with respect to 100 parts by weight of the solid content of the silica fine particles.

Preparation Example 2-3 Preparation of fine particles (P-2 (23)) surface-treated with a silane compound 3-Methacryloxypropyltrimethoxysilane (Toray Dow Corning Silicone Co., Ltd.); SZ- Except that the amount of 6030) was changed from 0.03 parts by weight to 7 parts by weight, silica fine particles surface-treated with a silane compound were prepared in the same manner as in Preparation Example 2-2. The weight part of the silane compound used for the surface treatment was 23 parts by weight with respect to 100 parts by weight of the solid content of the silica fine particles.

Preparation Example 2-4 Preparation of fine particles (P-2 (80)) surface-treated with a silane compound 15 parts by weight of 3-methacryloxypropyltrimethoxysilane and 9 parts by weight of 4-hydroxybutyl acrylate were used. Except that, silica fine particles surface-treated with a silane compound were prepared in the same manner as in Preparation Example 2-2. The weight part of the silane compound used for the surface treatment was 80 parts by weight with respect to 100 parts by weight of the solid content of the silica fine particles.

Preparation Example 2-5 Preparation of fine particles (P-3 (23)) surface-treated with a silane compound Zirconia (average particle size 91 nm, Nissan Chemical Co., Ltd.) as metal fine particles in a reaction vessel equipped with a stirrer, thermometer and cooling pipe Manufactured by Kogyo Co., Ltd .; ZR-30AL, dispersed in 2-propanol, solid content 30% by weight, 100 parts by weight of 3-methacryloxypropyltrimethoxysilane (manufactured by Toray Dow Corning Silicone Co., Ltd.); SZ-6030) 7 parts by weight were added. Subsequently, the mixture was gradually heated to 82 ° C. with stirring, and further heated for 5 hours for surface treatment to produce zirconia fine particles. The weight part of the silane compound used for the surface treatment was 23 parts by weight with respect to 100 parts by weight of the solid content of the zirconia fine particles.

Preparation Example 2-6 Preparation of Fine Particles Treated with Silane Compound (P-4 (23)) Zinc oxide (average particle diameter 65 nm, (as a metal fine particle in a reaction vessel equipped with a stirrer, thermometer, and cooling pipe) 3-methacryloxypropyltrimethoxysilane (Toray Dow Corning Silicone Co., Ltd.) for 100 parts by weight of F-2, solid content 30% by weight and dispersed in 2-propanol; SZ −6030) 7 parts by weight were added, followed by gradually heating to 82 ° C. with stirring, followed by further surface treatment by heating for 5 hours to produce fine zinc oxide particles. The part by weight was 23 parts by weight with respect to 100 parts by weight of the solid content of the zinc oxide fine particles.

  “Fine particles (parts by weight)” in Tables 1 and 2 are solid parts by weight of fine particles with respect to 100 parts by weight of the curable resin in the transparent laminate. In the table below, “P1 to P4” means the kind of fine particles, and the numbers in parentheses mean the parts by weight of the silane compound used for the surface treatment (the amount relative to 100 parts by weight of the solid content of the fine particles).

Preparation Example of Coating Composition 100 parts by weight of the curable resin having the composition described in the following table and the inorganic oxide fine particles shown in the following table were mixed in parts by weight (in terms of solid part by weight), and the mixture was subjected to reduced pressure. The volatile solvent was removed while gradually heating. At this time, the final temperature was 80 ° C.
Subsequently, 2.5 parts by weight of 1-hydroxycyclohexyl phenyl ketone as a photopolymerization initiator was mixed to obtain a transparent inorganic oxide fine particle-containing coating composition.

Preparation Examples of Primer Compositions Used in Examples 14 to 26, Comparative Example 5 and Reference Examples 1 and 2, (meth) acrylate compounds, polymerization initiators, ultraviolet absorbers, light stabilizers and the like shown in the following table were mixed. A primer composition was prepared.

Examples of producing transparent laminates of Examples 1 to 14 and Comparative Examples 1 to 4 As a transparent resin substrate, polycarbonate (manufactured by Teijin Chemicals Ltd .: L-1250) or polymethyl methacrylate (manufactured by Kaneka Corporation) is used. It was. First, 1) A spacer was bonded on a transparent resin substrate having a substantially uniform thickness of 3 mm so that the transparent protective film had a predetermined thickness. Subsequently, 2) the coating composition was cast and heated at 80 ° C. for 3 minutes. Subsequently, 3) Pressing with a PET film, the excess coating composition was removed. After that, 4) Light with a wavelength range of 200 nm or more and 400 nm or less is irradiated with a mercury lamp under a condition of illuminance of 505 mW / cm ² in a state covered with a PET film, and cured with an accumulated exposure amount of 8400 mJ / cm ^2. To produce a transparent laminate.

Example 15 to 25, Comparative Example 5 and Reference Examples 1 and 2, Preparation Example of Transparent Laminate Containing Transparent Primer Layer As a transparent resin substrate, polycarbonate (manufactured by Teijin Chemicals Ltd .: L-1250) or polymethyl Methacrylate (manufactured by Kaneka Corporation) was used. First, 1) The coating composition was cast on a PET film, and excess coating composition was removed with a blade. Subsequently, 2) a spacer was bonded onto the transparent resin substrate so that the transparent primer layer had a predetermined thickness, the primer composition constituting the transparent primer layer was cast, and heated at 80 ° C. for 3 minutes. . Subsequently, 3) Using a PET film in a state where the coating composition constituting the transparent protective film is adhered, the transparent resin substrate in a state where the primer composition constituting the transparent primer layer is adhered is pressed to remove excess transparency. The primer composition which becomes the primer layer was removed. Next, 4) irradiation 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 in a state covered with a PET film, and cured with an accumulated exposure amount of 8400 mJ / cm ² ; A transparent primer layer and a transparent protective film were provided to prepare a transparent laminate.

  Table 1 below shows the material of the transparent resin base material used in each Example and Comparative Example, and the composition and thickness of the transparent protective film for the transparent laminate having no transparent primer layer.

  In addition, Table 2 below shows the transparent laminate having a transparent primer layer, the material of the transparent resin substrate used in each Example and Comparative Example, the composition and thickness of the transparent primer layer, and the transparency protective film. Composition and thickness are indicated.

In the said Table 1, 2, each symbol shows the following.

Resin substrate S1: Polycarbonate (PC) (manufactured by Teijin Chemicals Ltd .: L-1250), thickness 3 mm
S2: Polymethyl methacrylate (PMMA) (manufactured by Kaneka Corporation), thickness 3 mm

Curable resin A: Organic-inorganic composite obtained in Preparation Example B: Dipentaerythritol hexaacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: Light acrylate DPE-6A)
C: Tricyclodecane diacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: Light acrylate DCP-A)
D: 2-hydroxy-3-acryloyloxypropyl methacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: Light Ester G-201P)

Ultraviolet absorbers UV1 to UV3: hydroxyphenyltriazine ultraviolet absorbers (manufactured by BASF Japan Ltd .: TINUVIN400, TINUVIN477, TINUVIN479)

Light stabilizer hindered amine light stabilizer (manufactured by BASF Japan Ltd .: TINUVIN123)

Inorganic oxide fine particles P1: isopropanol-dispersed colloidal silica (manufactured by Nissan Chemical Industries, Ltd .: IPA-ST, average particle size of 10 to 15 nm)
P2: Isopropanol-dispersed colloidal silica (manufactured by Nissan Chemical Industries, Ltd .: IPA-ST-ZL, average particle size 70-100 nm)
P3: 2-propanol-dispersed zirconia (manufactured by Nissan Chemical Industries, Ltd .: ZR-30AL, average particle size 91 nm)
P4: 2-propanol-dispersed zinc oxide (Huxitec Co., Ltd .: F-2, average particle size 65 nm)

(Meth) acrylate compound (Table 2 only)
PA: dimethylol tricyclodecane diacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: Light acrylate DCP-A)
PB: PEG400 # diacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: Light acrylate 9EG-A)

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

Tables 1 and 2 show 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 laminates 1 and 51 before each test was visually observed. The case where the transparent laminates 1 and 51 were not cracked or peeled off was marked as ◯.

Scratch resistance test A test was conducted using a scratch resistance test apparatus shown in FIG. The wound element 14 covered with cotton and attached to the weighted arm 13 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 piece 14 and the test piece G. The test was carried out at a load applied by the weight arm 13 of 2N, the moving distance of the wound element 14 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 values of scratch resistance shown in Tables 1 and 2 indicate 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 from the light source 21 with the measuring device shown in FIG. When the gloss retention (= surface gloss value after test / surface gloss value before test) exceeded 70%, it was judged that excellent scratch resistance was secured.

Abrasion resistance test A taber abrasion test was performed in accordance with JIS R3212, and the haze (%) of the transparent laminate after the wear wheel had rotated 500 times was measured. The numerical values in Table 1 represent (the haze value after the test) − (the haze value before the test). When the change in haze before and after the test was less than 9 %, it was judged that excellent wear resistance was secured.

As shown in FIG. 11, using a weather resistance test apparatus equipped with a xenon light source 31 and a sprinkler 32, 1) with a black panel temperature of 73 ° C. and a humidity of 35%, an illuminance of 180 W / m ² . Light was irradiated for 60 minutes. 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 amount was 200 MJ / m ² and 600 MJ / m ² (Table 2). The external appearance change of the transparent laminated bodies 1 and 51 was observed visually. If there was no cracking or color change, it was rated as ○.

First, the test results of Table 1 (no transparent primer layer) will be described.
In Examples 1 to 3 and Comparative Examples 1 and 2, the test was performed under the same conditions except for the thickness of the transparent protective film. When the thickness of the transparent protective film was in the range of 5 μm to 150 μm (Examples 1 to 3), the gloss retention exceeded 70%. On the other hand, in Comparative Example 1 in which the thickness of the transparent protective film is less than 5 μm and in Comparative Example 2 in which the thickness of the transparent protective film is 200 μm, the gloss retention was less than 70%. This is considered that sufficient scratch resistance could not be ensured when the thickness of the transparent protective film was out of the range of 5 μm or more and 150 μm or less.

  In Examples 4-7, 11, and 12, the test was performed with the same conditions except for the type and content of the inorganic oxide fine particles. In these examples, 5 to 400 parts by weight of inorganic oxide fine particles are included with respect to 100 parts by weight of the curable resin. In these examples, the gloss retention was over 70%, and the haze change was less than 10%. Accordingly, it can be said that when the inorganic oxide fine particles are contained in an amount of 5 to 400 parts by weight with respect to 100 parts by weight of the curable resin, excellent wear resistance and scratch resistance can be secured. Further, when the proportion of the inorganic oxide fine particles is less than 5 parts by weight, it is considered that sufficient wear resistance cannot be ensured.

  Even in Examples 8 to 10 in which the test was performed by changing the ratio of the organic-inorganic composite in the curable resin, the gloss retention was more than 70% and the haze change was less than 10%. The organic-inorganic composite is up to about 75% (Example 8) in the Examples, but it is considered that excellent wear resistance and scratch resistance can be secured even in a proportion higher than this.

  Example 13 is an experimental example using a coating composition containing an ultraviolet absorber and a light stabilizer. Even when these components were included, good scratch resistance and wear resistance were ensured.

  Even in Example 14 in which the base resin was changed to polymethyl methacrylate, the gloss retention was more than 70%, and the haze change was less than 10%. Even if the base resin is polymethyl methacrylate and the test is performed under the conditions of each example, it is considered that excellent wear resistance and scratch resistance are secured.

  In Comparative Example 3 that does not contain inorganic oxide fine particles and Comparative Example 4 that uses a coating composition that does not contain an organic-inorganic composite, it was impossible to achieve both wear resistance and scratch resistance performance. . In Comparative Example 3, since the inorganic oxide fine particles were not included, the wear resistance was greatly deteriorated. In Comparative Example 4, since the organic-inorganic composite was not included, the scratch resistance was greatly deteriorated.

  In these examples, as shown in Tables 1 and 2, the surface treatment is performed so that the weight ratio of the silane compound is 0.1 wt% or more and 80 wt% or less with respect to the inorganic oxide fine particles. . Within this range, it can be said that excellent wear resistance and scratch resistance are ensured.

In these examples and comparative examples, no cracks occurred in the initial appearance. Further, although not shown in Table 1, a weather resistance test (integrated irradiation light amount: 200 MJ / m ² ) assuming use in a harsh environment was performed on the transparent laminates used in the examples and comparative examples. However, cracking and yellowing did not occur in all the transparent laminates. From this, it can be said that the transparent laminated body by a present Example has ensured the outstanding weather resistance.

Next, the test results of Table 2 (with a transparent primer layer) will be described.
In these examples in which the thickness of the transparent protective film is 5 μm or more and 150 μm or less and the inorganic oxide fine particles are included in an amount of 5 parts by weight or more and 400 parts by weight or less with respect to 100 parts by weight of the curable resin, the gloss retention is 70%. The haze change was less than 10%. Therefore, in these examples, like the examples in Table 1, it can be said that excellent wear resistance and scratch resistance are ensured. In the examples shown in Table 2, it is conceivable that the transparent primer layer secures a part of the scratch-proof function of the transparent protective film.

  In these examples, as shown in Table 2, the surface treatment was performed so that the silane compound had a weight ratio of 0.1 wt% or more and 80 wt% or less with respect to the inorganic oxide fine particles. It can be said that excellent wear resistance and scratch resistance are ensured.

In these examples and comparative examples, no cracks occurred in the initial appearance. Moreover, in the weather resistance test (integrated irradiation light quantity: 200 MJ / m ² ) assuming use in a harsh environment, cracks and yellowing did not occur in the transparent laminates of all Examples and Comparative Examples. Therefore, it can be said that the transparent laminate according to the present example ensures excellent weather resistance.

Further, in each example in which the thickness of the transparent primer layer was 5 μm or more, even in a weather resistance test in which the integrated irradiation light amount was increased to 600 MJ / m ² on the assumption that the transparent primer layer was used in a severe environment for a long time, Yellowing did not occur. Therefore, when the thickness of the transparent primer layer is 5 μm or more, it can be said that better weather resistance is ensured.

  In addition, the transparent primer layers provided in the transparent laminates of the examples and comparative examples contain different types of ultraviolet absorbers or light stabilizers. Even when these types are changed, the results of the weather resistance test are the same. Results are obtained, and even when these are not included, it is considered that similar results are obtained.

  In Table 2, each test was performed using polycarbonate as the base resin. From the results shown in Table 1, it is clear that similar results can be obtained even when the base resin is polymethyl methacrylate.

  The present invention can be widely applied as a window material of a moving body such as a vehicle window material, and further as another window material.

1,51: Transparent laminate,
2, 52: transparent resin base material,
3, 53: Transparent protective film,
4, 44: inorganic oxide fine particles,
55: Transparent primer layer

Claims (9)

A transparent laminate comprising a plate-like transparent resin substrate and a transparent protective film provided on at least one surface of the transparent resin substrate,
The transparent resin substrate has a heat resistance of 70 ° C. or higher,
The transparent protective film is a protective film having a thickness of 5 μm or more and 150 μm or less obtained by applying and curing a coating composition;
The coating composition contains a curable resin containing an organic-inorganic composite, and inorganic oxide fine particles having an average particle size of 10 nm to 100 nm,
Wherein the amount of the inorganic oxide fine particles contained in the coating composition state, and are 100 parts by weight to 400 parts by weight relative to the resin component 100 parts by weight contained in the coating composition,
The inorganic oxide fine particles are surface-treated with a silane compound,
The amount of the silane compound is 0.1 to 80 parts by weight with respect to 100 parts by weight of the inorganic oxide fine particles.
Transparent laminate. The transparent resin base material includes a polycarbonate resin or an acrylic resin, and has a substantially uniform thickness of 1 mm or more, an elastic modulus of 1 GPa or more at room temperature, and a Vickers hardness of 10 kgf / mm ² or more,
The thickness of the transparent protective film is 10 μm or more and 80 μm or less,
The organic-inorganic composite is a composite prepared using a photosensitive compound, an organosilicon compound, and an ultraviolet curable compound, and the photosensitive compound is selected from the group consisting of titanium, zirconium, and aluminum. Including at least one of
The inorganic oxide fine particles are at least one inorganic oxide fine particle selected from the group consisting of silicon oxide, titanium oxide, tin oxide, zircon oxide, cerium oxide, zinc oxide, antimony oxide, and double oxides thereof. The
The transparent laminate according to claim 1. Further comprising a transparent primer layer interposed between the transparent resin substrate and the transparent protective film,
The transparent primer layer is a layer obtained by coating and curing a primer composition containing a (meth) acrylate compound, and the transparent primer layer has a thickness of 5 μm or more,
The transparent protective film has a thickness of 5 μm or more and 80 μm or less,
The transparent laminate according to claim 1. The transparent resin base material includes a polycarbonate resin or an acrylic resin, and has a substantially uniform thickness of 1 mm or more, an elastic modulus of 1 GPa or more at room temperature, and a Vickers hardness of 10 kgf / mm ² or more,
The organic-inorganic composite is a composite prepared using a photosensitive compound, an organosilicon compound, and an ultraviolet curable compound, and the photosensitive compound is selected from the group consisting of titanium, zirconium, and aluminum. Including at least one of
The inorganic oxide fine particles are at least one inorganic oxide fine particle selected from the group consisting of silicon oxide, titanium oxide, tin oxide, zircon oxide, cerium oxide, zinc oxide, antimony oxide, and double oxides thereof. The
The transparent laminate according to claim 3.   It is a window material of a moving body, The transparent laminated body of any one of Claims 1-4 characterized by the above-mentioned. A preparatory step of preparing a plate-like transparent resin base material having a heat resistance of 70 ° C. or higher, a substantially uniform thickness of 1 mm or more, and an elastic modulus of 1 GPa or more at room temperature;
A coating composition is applied on at least one surface of the transparent resin substrate and then cured to provide a transparent protective film having a thickness of 5 μm or more and 150 μm or less on the transparent resin substrate. Protective film forming step,
A method for producing a transparent laminate, comprising:
The coating composition contains a curable resin containing an organic-inorganic composite, and inorganic oxide fine particles having an average particle size of 10 nm to 100 nm,
The amount of the inorganic oxide fine particles is 100 parts by weight or more and 400 parts by weight or less with respect to 100 parts by weight of the curable resin contained in the coating composition.
The inorganic oxide fine particles are surface-treated with a silane compound,
The amount of the silane compound is 0.1 to 80 parts by weight with respect to 100 parts by weight of the inorganic oxide fine particles.
A method for producing a transparent laminate. A preparatory step of preparing a plate-like transparent resin base material having 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; ,
A primer layer forming step of coating a primer composition containing a (meth) acrylate compound on at least one surface of the transparent resin substrate to provide a primer layer having a thickness of 5 μm or more;
With co computing composition, the membrane portion is formed consisting of coating composition onto the primer layer, followed by curing, on the primer layer, providing a transparent protective layer having a thickness of 80μm or more 5μm A transparent protective film forming step;
A method for producing a transparent laminate, comprising:
The coating composition contains a curable resin containing an organic-inorganic composite, and inorganic oxide fine particles having an average particle size of 10 nm to 100 nm,
The amount of the inorganic oxide fine particles is 100 parts by weight or more and 400 parts by weight or less with respect to 100 parts by weight of the curable resin contained in the coating composition.
The inorganic oxide fine particles are surface-treated with a silane compound,
The amount of the silane compound is 0.1 to 80 parts by weight with respect to 100 parts by weight of the inorganic oxide fine particles.
A method for producing a transparent laminate. The curing means in the transparent protective film forming step is a light having a wavelength range of 200 nm or more and 400 nm or less at an atmospheric temperature lower than the heat resistant temperature of the transparent resin substrate, and an illuminance of 1 × 10 ⁻² mW / cm ² or more 1 X10 ⁴ mW / cm ² or less, and a means for photocuring by irradiating under a condition where the integrated light quantity in the wavelength region is 5 × 10 ² mJ / cm ² or more and 3 × 10 ⁴ mJ / cm ² or less,
The manufacturing method of the transparent laminated body of Claim 6 or 7. The organic-inorganic composite is a composite prepared using a photosensitive compound, an organosilicon compound, and an ultraviolet curable compound, and the photosensitive compound is selected from the group consisting of titanium, zirconium, and aluminum. Including at least one of
The inorganic oxide fine particles are at least one inorganic oxide fine particle selected from the group consisting of silicon oxide, titanium oxide, tin oxide, zircon oxide, cerium oxide, zinc oxide, antimony oxide, and double oxides thereof. The
The manufacturing method of the transparent laminated body in any one of Claims 6-8.

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