WO2013146477A1

WO2013146477A1 - Silica-containing coating resin composition and laminate body

Info

Publication number: WO2013146477A1
Application number: PCT/JP2013/057842
Authority: WO
Inventors: 美幸神谷; 齋藤　憲
Original assignee: 新日鉄住金化学株式会社
Priority date: 2012-03-30
Filing date: 2013-03-19
Publication date: 2013-10-03
Also published as: TW201400563A; JPWO2013146477A1

Abstract

Provided are: a coating resin composition that can impart wear resistance close to glass using light curing, which can cure in a shorter time period than thermal curing, and can be applied to a wet process without using a dry process such as in a vacuum chamber; and a laminate body. The silica-containing coating resin composition contains: a radical polymerizable compound (A) having a hydroxyl group and a (meth)acrylic group and is represented by general formula (1) (where R is an organic functional group having a (meth)acryloyl group, X is hydrogen or an organic functional group having a (meth)acryloyl group, and n is an integer that is 0 or 1); a photoinitiator; and silica microparticles (B) having an average particle size of 1-100 nm. For every total of 100 parts by weight of the radical polymerizable compound (A) and the silica microparticles (B), the silica microparticles (B) are contained in the range of 60-85 parts by weight. The laminate body is provided with a hard coating layer formed using the silica-containing coating resin composition.

Description

Silica-containing coating resin composition and laminate

The present invention relates to a silica-containing coating resin composition and a laminate, and is a resin composition suitable for forming a hard coat layer on the surface of a transparent thermoplastic resin molded article, and a laminate thereof, The present invention relates to a coating resin composition and a laminate thereof that can satisfy the abrasion resistance equivalent to that of inorganic glass while ensuring transparency after curing.

Recently, in order to improve the fuel efficiency of automobiles and reduce carbon dioxide emissions, weight reduction of vehicle bodies has been demanded, and one of the methods that is being applied is the use of resin for automobile window glass. Conventionally, a molded article of a thermoplastic resin such as polycarbonate is lighter than glass, and thus is widely used as an alternative material. However, since polycarbonate (PC) has a lower surface hardness than glass and is easily scratched, the surface is protected by a method of applying a hard coat to the surface or a method of attaching a curable film to prevent it. .

The standard of abrasion resistance in plastic glass requires a high wear resistance equivalent to that of inorganic glass, with a haze change of 2% or less (ANSI Z 26.1) before and after the Taber abrasion test. As typical methods satisfying this, a method of forming a SiO thin film on a PC surface by plasma CVD, and a method of applying and curing a thermosetting silicone resin have been proposed. However, the former method is excellent in abrasion resistance with a Taber abrasion resistance of about 2%, but has a drawback that the process cost is high because a dry process such as a vacuum chamber is required. On the other hand, the latter method is low in process cost because it can be formed by a wet process, but it requires a high temperature and a long time for curing, so that the productivity is poor and the Taber abrasion resistance is not sufficiently satisfactory.

In order to solve the above-described problems, various types of photo-curable coating compositions that can be cured in a short time and are excellent in abrasion resistance because of being an inorganic component have been proposed and implemented.

For example, Patent Document 1 discloses a coating resin composition comprising a photocurable silica-containing acrylic resin to which an ultraviolet absorber is added, and a laminate in which this composition is coated on a polycarbonate molded product. This laminate has excellent wear resistance with 4.2% haze change before and after the Taber abrasion test, but the average particle size of silica that guarantees wear resistance has not been optimized, and the resin The silica content in the composition is 50 parts by weight, which is not high.

Patent Document 2 discloses a coating resin composition comprising a ladder-type polysilsesquioxane having a (meth) acryl group and an acrylic resin, and a laminate in which this composition is coated on a polycarbonate molded article. . Although this laminated body has little curing shrinkage at the time of photocuring and can be directly applied to a PC without using an adhesion layer, its wear resistance is not satisfactory.

JP 57-13214 A Japanese Patent Laid-Open No. 4-33936

An object of the present invention is to apply a wet process that does not use a dry process such as a vacuum chamber, and to use a photocuring that can be cured in a short period of time compared to a thermal curing, and a glass for a polycarbonate molded article or the like. An object of the present invention is to provide a resin composition capable of forming a hard coat layer having transparency and abrasion resistance close to those of the above.

As a result of repeated studies to achieve the above-mentioned problems, the inventors have highly blended silica fine particles having a specific average particle diameter with a radical polymerizable compound having a (meth) acryl group and a hydroxyl group. The present inventors have found that a resin composition capable of imparting transparency and abrasion resistance close to glass to a transparent thermoplastic resin such as polycarbonate can be obtained. Furthermore, by forming a top coat layer obtained by photocuring the composition on the surface of a transparent thermoplastic resin molded article such as polycarbonate via an adhesion layer obtained by photocuring radically polymerizable (meth) acrylate. The present inventors have found that a laminate having transparency close to glass and wear resistance can be obtained.

That is, the present invention provides the following general formula (1)

Where R is an organic functional group having a (meth) acryloyl group, X is an organic functional group having hydrogen or a (meth) acryloyl group, and n is an integer of 0 or 1. ) A radically polymerizable compound (A) having an acrylic group and a hydroxyl group, a photopolymerization initiator, and silica fine particles (B) having an average particle diameter of 1 to 100 nm, the radical polymerizable compound (A) and the silica fine particles (B The silica-containing coating resin composition is characterized in that the silica fine particles (B) are contained in the range of 60 to 85 parts by weight in a total of 100 parts by weight.

The present invention also provides a photocurable resin composition comprising a topcoat layer (I) obtained by photocuring the above silica-containing coating resin composition, a radically polymerizable (meth) acrylate, and a photopolymerization initiator. A laminate in which a hard coat layer comprising two layers of an adhesive layer (II) to be cured is provided on at least one surface of a thermoplastic resin molded product, comprising a silica-containing coating resin composition and a photocurable resin Each of the compositions is coated and photocured to form a hard coat layer.

The radically polymerizable compound (A) having a (meth) acryl group and a hydroxyl group in the present invention is represented by the general formula (1). In the general formula (1), R is an organic functional group having a (meth) acryloyl group, and X is an organic functional group having hydrogen or a (meth) acryloyl group. n is an integer of 0 or 1. In order to obtain a laminate with good transparency, it is important that the unsaturated compound contains a hydroxyl group. This is presumably because the hydroxyl group acts on the silanol groups present on the surface of the silica fine particles to suppress the aggregation of the silica fine particles and enhance the dispersibility of the silica fine particles in the resin. On the other hand, in a radically polymerizable compound having no hydroxyl group, when a large amount of silica fine particles are blended, the dispersion may not be uniformly dispersed in the resin due to agglomeration, and transparency may be deteriorated.

具体 Specific examples of the general formula (1) include pentaerythritol triacrylate, glycerin dimethacrylate, glycerol acrylate methacrylate, and the like. Since these compounds have a hydroxyl group in the molecule, for example, they can interact with the hydroxyl groups present on the surface of silica fine particles typified by colloidal silica, and it is possible to control the colloidal silica in the resin composition. Enables a large amount of uniform mixing in. These radically polymerizable compounds may be used alone or in combination of two or more.

The silica fine particle (B) in the present invention is not particularly limited as long as it is a silicon oxide, but it may be colloidal silica (colloidal silica) dispersed in an organic solvent from the viewpoint of dispersibility in the resin. preferable. Furthermore, the silica fine particles (B) are more preferably surface-treated with a silane coupling agent having a (meth) acryl group. The surface treatment method of the silica fine particles is not particularly limited, and a commercially available product that has been surface-treated with a silane coupling agent having a (meth) acryl group in advance may be used. When used, the surface treatment with a silane coupling agent may be performed by a known method.

The silica fine particles (B) are blended in the range of 60 to 85 parts by weight, preferably in the range of 75 to 85 parts by weight, in a total of 100 parts by weight of the radical polymerizable compound (A) and the silica fine particles (B). It is good to have. If the blending amount of the silica fine particles (B) is less than 60 parts by weight, the abrasion resistance cannot be sufficiently exhibited. On the other hand, if it exceeds 85 parts by weight, the transparency may be lowered.

The average particle diameter of the silica fine particles (B) is preferably 1 to 100 nm in order to ensure the transparency of the silica-containing coating resin composition (C). Furthermore, if the average particle size is in the range of 1 to 100 nm, a plurality of silica fine particles having different particle sizes can be used in combination. The average particle diameter of the silica fine particles represents the number average particle diameter measured by a dynamic light scattering method.

Moreover, in obtaining the laminated body in this invention, the silica-containing coating resin composition (C) and the photocurable resin composition (D) are applied in two coats and two baked so that coating and photocuring are performed for each composition. In addition to coating, two-coat one-bake coating (photocuring together after applying two compositions), which is more advantageous in terms of process cost, can also be applied. In the 2-coat 1-bake coating, in addition to the process cost, resin mixing occurs at the interface between the topcoat layer (I) and the adhesion layer (II), so that improvement in interlayer adhesion can be expected. However, when the silica-containing coating resin composition (C) containing only finer silica particles having an average particle size of 15 nm or less is used in 2-coat 1-bake coating, the topcoat layer (I) and the adhesion layer ( As the resin of II) is mixed, the silica fine particles flow out to the adhesion layer (II) side, and wear resistance is reduced. The outflow of the silica fine particles occurs because the radical polymerizable (meth) acrylate used in the photocurable resin composition (D) and the silica fine particles having an average particle size of 15 nm or less are easily compatible. In order to prevent this outflow, in the case of using 2-coat 1-bake coating, silica fine particles having an average particle diameter of 16 to 100 nm, which is difficult to be compatible with the radical polymerizable (meth) acrylate used in the photocurable resin composition (D), are used. More preferably, silica fine particles having an average particle diameter of 30 to 100 nm are preferably used. However, when a plurality of silica fine particles having an average particle diameter in the range of 1 to 100 nm are used in combination, the silica fine particles having an average particle diameter of 16 to 100 nm are contained in the silica-containing coating resin composition (C) ( B) If 50 parts by weight or more is contained with respect to 100 parts by weight, a part of silica fine particles of 15 nm or less may be mixed.

As the photopolymerization initiator contained in the silica-containing coating resin composition (C), compounds such as acetophenone-based, benzoin-based, benzophenone-based, thioxanthone-based, and acylphosphine oxide-based compounds can be suitably used. Specifically, trichloroacetophenone, diethoxyacetophenone, 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2 -Morpholinopropan-1-one, benzoin methyl ether, benzyldimethyl ketal, benzophenone, thioxanthone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, methylphenylglyoxylate, camphorquinone, benzyl, anthraquinone, Michler's ketone, etc. can do. These photopolymerization initiators may be used alone or in combination of two or more. Further, for the purpose of accelerating the photocuring reaction, a photoinitiator assistant or a sharpening agent that exhibits an effect in combination with a photopolymerization initiator can be used in combination.

The addition amount of the photopolymerization initiator of the silica-containing coating resin composition (C) is based on a total of 100 weights of the radical polymerizable compound (A) having a (meth) acrylic group and a hydroxyl group and the silica fine particles (B). The range is 0.1 to 10 parts by weight, and preferably 0.5 to 10 parts by weight. If this addition amount is less than 0.1 parts by weight, curing will be insufficient, and the strength and rigidity of the resulting laminate will be low, while if it exceeds 10 parts by weight, problems such as coloring of the laminate may occur. is there.

The silica-containing coating resin composition (C) of the present invention may further contain a cage silsesquioxane resin represented by the following general formula (3).
[RSiO _3/2 ] _n (3)
(In the formula, R represents a (meth) acryloyl group or the following formula (4), and n represents 8, 10, 12 or 14).

(Wherein R ¹ represents a hydrogen atom or a methyl group, and m represents an integer of 1 to 3)

The cage silsesquioxane resin has the following general formula (5)
RSix ₃ (5)
(In the formula, R represents a (meth) acryloyl group or the following general formula (4), and X represents a hydrolysis group selected from an alkoxy group or an acetoxy group)

(Wherein R ¹ represents a hydrogen atom or a methyl group, and m represents an integer of 1 to 3) is hydrolyzed and partially condensed in the presence of an organic polar solvent and a basic catalyst. The obtained hydrolysis product can be obtained by recondensing in the presence of a nonpolar solvent and a basic catalyst.

Such a cage silsesquioxane resin has a reactive functional group composed of an organic functional group having a (meth) acryloyl group on all silicon atoms in the resin, and has a controlled molecular weight distribution and molecular structure. A cage silsesquioxane resin is preferred. Further, the molecular structure of such a cage silsesquioxane resin may not be a completely closed polyhedron, and may be a structure in which a part is cleaved, for example. Moreover, the average molecular weight of such cage-type silsesquioxane resin is not particularly limited, and such cage-type silsesquioxane resin may be an oligomer. By adding this cage silsesquioxane to the silica-containing coating resin composition (C) of the present invention, in addition to the Taber abrasion resistance, the pencil hardness, which is one of the methods for evaluating the surface hardness, is improved. An effect is obtained. Such a cage silsesquioxane resin can be contained in an amount of 1 to 100 parts by weight with respect to 100 parts by weight of the radical polymerizable compound (C) having a (meth) acryl group and a hydroxyl group. If the content is less than 1 part by weight, the effect of improving the pencil hardness cannot be obtained, and if the content exceeds 100 parts by weight, no further improvement of the effect can be seen, and it has a (meth) acryl group and a hydroxyl group. Since the effect of the hydroxyl group which a radically polymerizable compound (C) has is reduced, it is not preferable.

Various additives can be added to the silica-containing coating resin composition (C) without departing from the object of the present invention. Examples of various additives include solvents, organic / inorganic fillers, antioxidants, light stabilizers, ultraviolet absorbers, leveling agents, antistatic agents, colorants, crosslinking agents, dispersion aids, resin components, and the like. .

Among these, the solvent can be used for the purpose of adjusting the viscosity when the silica-containing coating resin composition (C) is applied. Specific examples include alcohols such as ethyl alcohol, n-propyl alcohol, isopropyl alcohol and n-butyl alcohol, and ketones such as methyl ethyl ketone and methyl isobutyl ketone.

ラジカル The radically polymerizable (meth) acrylate used in the photocurable resin composition (D) is preferably a polyfunctional acrylate, and more preferably a bifunctional acrylate or an acrylate oligomer. Since the bifunctional or higher polyfunctional acrylate has a large volume shrinkage at the time of photocuring, the adhesion may be lowered. Specific examples of the bifunctional acrylate include 1,9-nonanediol diacrylate, tetraethylene glycol dimethacrylate, dicyclopentanyl dimethylol di (meth) acrylate and the like. These radically polymerizable (meth) acrylates may be used singly or as a mixture of two or more kinds, or these oligomers may be used. Among them, dicyclopentanyl dimethylol di (meth) acrylate moderately erodes the surface of the polycarbonate resin, so that adhesion is improved. In addition, since the linear expansion coefficient of the photocured product is 70 ppm / K, which is close to the linear expansion coefficient (60 to 80 ppm / K) of a general polycarbonate resin, it is preferable because the heat resistance is improved. . On the other hand, when an acrylate such as tetraethylene glycol dimethacrylate having high erodibility to polycarbonate is used, it is preferably mixed with other acrylates or acrylate oligomers for the purpose of preventing a decrease in transparency.

As the photopolymerization initiator contained in the fluorescent curable resin composition (D), compounds such as acetophenone-based, benzoin-based, benzophenone-based, thioxanthone-based, and acylphosphine oxide-based compounds can be preferably used. Specifically, trichloroacetophenone, diethoxyacetophenone, 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2 -Morpholinopropan-1-one, benzoin methyl ether, benzyldimethyl ketal, benzophenone, thioxanthone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, methylphenylglyoxylate, camphorquinone, benzyl, anthraquinone, Michler's ketone, etc. can do. These photopolymerization initiators may be used alone or in combination of two or more. In addition, for the purpose of accelerating the photocuring reaction, a photoinitiator assistant or a sensitizer that exhibits an effect in combination with a photopolymerization initiator can be used in combination.

Various additives can be added to the fluorescent curable resin composition (D) without departing from the object of the present invention. Examples of various additives include solvents, organic / inorganic fillers, antioxidants, light stabilizers, ultraviolet absorbers, heat ray absorbers, leveling agents, colorants, and the like.

Among these, the solvent can be used for the purpose of adjusting the viscosity when the photocurable resin composition (D) is applied. Specific examples include using alcohols such as ethyl alcohol, n-propyl alcohol, isopropyl alcohol and n-butyl alcohol, aromatic hydrocarbons such as toluene and xylene, ketones such as methyl ethyl ketone and methyl isobutyl ketone, and the like. it can.

The method for applying the silica-containing coating resin composition (C) and the photocurable resin composition (D) onto the transparent thermoplastic resin molded product is not particularly limited, but includes a cast method and a spin coat method. , Spray coating method, dip coating method, flow coating method and the like. In addition, the heating conditions for drying when the solvent is contained in the silica-containing coating resin composition (C) and the photocurable resin composition (D) are not particularly limited. It is preferable that the time is from minute to one hour. In addition, the silica-containing coating resin composition (C) is applied after the photocurable resin composition (D) is applied onto a thermoplastic resin molded article such as polycarbonate and then photocured (2 coats 2 bake). Coating) or coating without photocuring (2 coats and 1 bake coating), but the latter method is used to improve the interlayer adhesion between the topcoat layer (I) and the adhesion layer (II). Is preferred.

As a method of photocuring the silica-containing coating resin composition (C) and the photocurable resin composition (D), the topcoat layer is irradiated by irradiating ultraviolet rays having a wavelength of 10 to 400 nm or visible rays having a wavelength of 400 to 700 nm. A hard coat layer comprising (I) and the adhesion layer (II) can be formed. The wavelength of light to be used is not particularly limited, but near ultraviolet light having a wavelength of 200 to 400 nm is particularly preferably used. As a lamp used as an ultraviolet ray generation source, a low-pressure mercury lamp (output: 0.4 to 4 W / cm), a high-pressure mercury lamp (40 to 160 W / cm), an ultra-high pressure mercury lamp (173 to 435 W / cm), a metal halide lamp (80 to 160 W / cm), pulse xenon lamp (80 to 120 W / cm), electrodeless discharge lamp (80 to 120 W / cm), and the like. Each of these ultraviolet lamps is characterized by its spectral distribution, and is therefore selected according to the type of photopolymerization initiator used.

透明 The transparent thermoplastic resin molded product used in the present invention is preferably made of polycarbonate. The shape of the molded product is not particularly limited, and may be a flat plate or a curved surface. Moreover, you may contain various additives in the range which does not deviate from the objective of this invention. Specific examples include colorants, organic / inorganic fillers, antioxidants, light stabilizers, ultraviolet absorbers, heat ray absorbers, and the like. In addition to polycarbonate, for example, a product made of polymethyl methacrylate (PMMA), polyethylene terephthalate (PET), cycloolefin polymer (COP), or cycloolefin copolymer (COC) may be used as the transparent thermoplastic resin molded product. May be.

厚み The thickness of the transparent thermoplastic resin molded article of the present invention is preferably 1000 to 5000 μm. This is because it is disadvantageous in terms of strength if it is thinner than 1000 μm, and transparency may be lowered if it exceeds 5000 μm. If strength or transparency is not questioned, it may be outside this range.

The laminate of the present invention is formed between the topcoat layer (I) obtained by photocuring the silica-containing coating resin composition (C) and a transparent thermoplastic resin molded product such as polycarbonate which is a transparent thermoplastic resin. The adhesive layer (II) obtained by photocuring a photocurable resin composition (D) comprising a radically polymerizable (meth) acrylate and a photopolymerization initiator, and having a thickness of the topcoat layer (I). ) Is preferably 5 to 100 μm, and the thickness of the adhesion layer (II) is preferably 1 to 100 μm. If the thickness of the topcoat layer (I) is smaller than this range, the intended wear resistance will not be exhibited, and if it is larger than this range, the molded product may be deformed by curing shrinkage. Further, if the thickness of the adhesion layer (II) is smaller than this range, the adhesion force as the adhesion layer cannot be ensured, and if it is larger than this range, wear resistance may be lowered.

The silica-containing coating resin composition of the present invention comprises a transparent thermoplastic resin such as polycarbonate by highly blending silica fine particles having an average particle diameter of 1 to 100 nm with a radical polymerizable compound having a (meth) acryl group and a hydroxyl group. It is possible to impart abrasion resistance without impairing the transparency of the film. Also, a top coat layer obtained by photocuring the silica-containing coating resin composition is applied to the surface of a transparent thermoplastic resin molded product such as polycarbonate via an adhesion layer obtained by photocuring radically polymerizable (meth) acrylate. And by making it photocure, the laminated body which has transparency and abrasion resistance close | similar to glass can be provided.

1 is a cross-sectional view of the laminate obtained in Example 1. FIG.

Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to the following examples. In addition, evaluation of the Taber abrasion resistance, initial total light transmittance, and pencil hardness in each example was implemented by the method shown below. A cage silsesquioxane resin having a methacryl group was produced according to Synthesis Example 1 below.

(Taber abrasion test)
Using a wear wheel (Taber CS-10F), the test was carried out under the conditions of 60 ± 2 rpm, 500 g load, and 1000 rpm. And it evaluated by the haze change ((DELTA) H) before and behind a test. The haze measurement was performed with a haze meter according to JIS K 7105.

(Initial total light transmittance)
The total light transmittance according to JIS K 7361 was measured with a haze meter.

(Pencil hardness test)
This was performed in accordance with JIS K5600-5-4 scratch hardness (pencil method).

(Synthesis Example 1)
A reaction vessel equipped with a stirrer, a dropping funnel and a thermometer was charged with 40 ml of 2-propanol (IPA) as a solvent and 5% tetramethylammonium hydroxide aqueous solution (TMAH aqueous solution) as a basic catalyst. Into the dropping funnel, 15 ml of IPA and 12.69 g of 3-methacryloxypropyltrimethoxysilane (SZ-6030 manufactured by Toray Dow Corning Silicone Co., Ltd.) were added, and 3-methacryloxypropyltrimethoxy was stirred at room temperature while stirring the reaction vessel. The IPA solution of silane was added dropwise over 30 minutes. After completion of dropwise addition of 3-methacryloxypropyltrimethoxysilane, the mixture was stirred for 2 hours without heating. After stirring for 2 hours, the solvent was removed under reduced pressure and dissolved in 50 ml of toluene. The reaction solution was washed with saturated brine until neutral, and then dehydrated with anhydrous magnesium sulfate. 8.6 g of hydrolysis product (silsesquioxane) was obtained by filtering off anhydrous magnesium sulfate and concentrating. This silsesquioxane was a colorless viscous liquid soluble in various organic solvents.

Next, 20.65 g of the silsesquioxane obtained above, 82 ml of toluene, and 3.0 g of 10% TMAH aqueous solution were placed in a reaction vessel equipped with a stirrer, a Dinsterk, and a cooling tube, and the water was gradually heated to maintain the water. Left. Further, the mixture was heated to 130 ° C., and toluene was recondensed at the reflux temperature. The temperature of the reaction solution at this time was 108 ° C. After stirring for 2 hours after refluxing toluene, the reaction was terminated. The reaction solution was washed with saturated brine until neutral, and then dehydrated with anhydrous magnesium sulfate. Anhydrous magnesium sulfate was filtered off and concentrated to obtain 18.77 g of a target siliceous silsesquioxane (mixture). The obtained cage-type silsesquioxane was a colorless viscous liquid soluble in various organic solvents.

Mass spectrometry after separation by liquid chromatography of the reaction product after the recondensation reaction confirmed that molecular ions with ammonium ions were confirmed in the molecular structures of the following structural formulas (i), (ii) and (iii). The ratios of T8: T10: T12 and others are about 2: 4: 1: 3, and it can be confirmed that this is a silicone resin mainly composed of a saddle type structure. T8, T10, and T12 correspond to the order of formulas (i), (ii), and (iii) (R is represented by formula (4) (where R ¹ = methyl group, m = 3). Yes).

[Example 1]
In a reaction vessel, 20 parts by weight of pentaerythritol triacrylate, 5 parts by weight of a cage-type silsesquioxane resin having a methacryl group obtained in Synthesis Example 1 above, a colloidal surface modified with a silane coupling agent having a methacryl group 75 parts by weight of silica fine particles (average particle diameter 40 nm) (MEK-AC-4101 manufactured by Nissan Chemical Co., Ltd.) and 0.7 parts by weight of 1-hydroxycyclohexyl phenyl ketone (manufactured by BASF Japan Ltd .: Irgacure 184) as a photopolymerization initiator After stirring and stirring, the volatile solvent was removed under reduced pressure to obtain a silica-containing coating resin composition.

Next, 25 parts by weight of tetraethylene glycol dimethacrylate and 75 parts by weight of dicyclopentanyl dimethylol diacrylate were used as a photopolymerization initiator, 1-hydroxycyclohexyl phenyl ketone (manufactured by BASF Japan Ltd .: Irgacure 184) 2.5. A part by weight was added and mixed to obtain a photocurable resin composition.

The photocurable resin composition was applied to the surface of a polycarbonate flat plate (Carbo Glass Polish Clear: manufactured by Asahi Glass Co., Ltd.) having a thickness of 3 mm and a square of 100 × 100 mm using a spin coater. Next, the silica-containing coating resin composition was applied using a spin coater so as to have a film thickness of 15 μm, and then irradiated with ultraviolet light at 8400 mJ / cm ² using a high-pressure mercury lamp to form a top coat as shown in FIG. A laminate comprising the layer (I), the adhesion layer (II) and the polycarbonate substrate was obtained.

[Example 2]
In a reaction vessel, 15 parts by weight of pentaerythritol triacrylate, 10 parts by weight of glycerin dimethacrylate, 10 parts by weight of a cage silsesquioxane obtained in Synthesis Example 1 above, and a silane coupling agent having a methacrylic group 65 parts by weight of surface-modified colloidal silica fine particles (average particle diameter 40 nm) (MEK-AC-4101 manufactured by Nissan Chemical Co., Ltd.) and 1-hydroxycyclohexyl phenyl ketone (manufactured by BASF Japan Ltd .: Irgacure 184) as a photopolymerization initiator After 0.9 part by weight was added and stirred, the volatile solvent was removed under reduced pressure to obtain a silica-containing coating resin composition.

Next, 25 parts by weight of 1,9-nonanediol diacrylate and 75 parts by weight of tetraethylene glycol dimethacrylate, 2.5 parts by weight of 1-hydroxycyclohexyl phenyl ketone (manufactured by BASF Japan Ltd .: Irgacure 184) as a photopolymerization initiator Parts were added and mixed to obtain a photocurable resin composition.

Next, after applying each of the silica-containing coating resin composition and the photocurable resin composition in the same manner as in Example 1, photocuring was performed to obtain a laminate.

Example 3
In a reaction vessel, 10 parts by weight of pentaerythritol triacrylate, 12 parts by weight of glycerin dimethacrylate, 3 parts by weight of a cage silsesquioxane resin having a methacryl group obtained in Synthesis Example 1 above, and a methacryl group having an average particle diameter of 15 nm Colloidal silica fine particles (MEK-AC-2101 manufactured by Nissan Chemical Co., Ltd.) whose surface is modified with a silane coupling agent having a silane coupling agent and whose surface is modified with a silane coupling agent having a methacryl group having an average particle diameter of 40 nm 45 parts by weight of fine silica particles (MEK-AC-4101 manufactured by Nissan Chemical Co., Ltd.) and 0.7 parts by weight of 1-hydroxycyclohexyl phenyl ketone (BASF Japan Co., Ltd .: Irgacure 184) as a photopolymerization initiator were added and stirred. Remove the volatile solvent under reduced pressure To obtain a coating resin composition.

Next, 25 parts by weight of tetraethylene glycol dimethacrylate and 75 parts by weight of dicyclopentanyl dimethylol diacrylate are mixed with 2.5 parts by weight of 1-hydroxycyclohexyl phenyl ketone as a photopolymerization initiator, and mixed. A curable resin composition was obtained.

Example 4
55.5 parts by weight of pentaerythritol triacrylate, 10 parts by weight of glycerin dimethacrylate, 25.5 parts by weight of colloidal silica fine particles surface-modified with a silane coupling agent having a methacryl group having an average particle diameter of 15 nm (Nissan Chemical) MEK-AC-2101), colloidal silica fine particles surface-modified with a silane coupling agent having a methacryl group having an average particle size of 40 nm (MEK-AC-4101, Nissan Chemical Co., Ltd.), 8.5 parts by weight, average 51 parts by weight of colloidal silica fine particles (MEK-AC-5101 manufactured by Nissan Chemical Co., Ltd.) surface-modified with a silane coupling agent having a methacryl group having a particle diameter of 100 nm, and 1-hydroxycyclohexyl phenyl ketone (photopolymerization initiator) BASF Japan KK made: Irgacure1 4) Place the 0.5 parts by weight, after stirring, the volatiles removed solvent component under reduced pressure to obtain a silica-containing resin composition for coating.

Next, 50 parts by weight of 1,9-nonanediol diacrylate and 50 parts by weight of tetraethylene glycol dimethacrylate, 2.5 parts by weight of 1-hydroxycyclohexyl phenyl ketone (manufactured by BASF Japan Ltd .: Irgacure 184) as a photopolymerization initiator Parts were added and mixed to obtain a photocurable resin composition.

Example 5
In a reaction vessel, 5 parts by weight of pentaerythritol triacrylate, 20 parts by weight of glycerin dimethacrylate, colloidal silica fine particles (average particle size 40 nm) surface-modified with a silane coupling agent having a methacryl group (MEK-AC manufactured by Nissan Chemical Co., Ltd.) -4101) and 75 parts by weight of 1-hydroxycyclohexyl phenyl ketone (manufactured by BASF Japan Ltd .: Irgacure 184) as a photopolymerization initiator, and after stirring, the volatile solvent was removed under reduced pressure. A silica-containing coating resin composition was obtained.

Next, 25 parts by weight of tetraethylene glycol dimethacrylate, 75 parts by weight of dicyclopentanyldimethylol diacrylate, 2.5 parts by weight of 1-hydroxycyclohexyl phenyl ketone (BASF Japan Ltd .: Irgacure 184) as a photopolymerization initiator And 0.3 part by weight of bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (manufactured by BASF Japan Ltd .: Irgacure 819), 2- (2,4-dihydroxyphenyl) -4, 1 part by weight of a reaction product of 6-bis- (2,4-dimethylphenyl) -1,3,5-triazine and (2-ethylhexyl) -glycidic acid ester (manufactured by BASF Japan Ltd .: Tinuvin 405), light stable Bis (1,2,2,6 as an agent 1 part by weight of a mixture of 6-pentamethyl-4-piperidyl) sebacate and

methyl

1,2,2,6,6-pentamethyl-4-piperidyl sebacate (BASF Japan Ltd .: Tinuvin 292) was mixed and mixed. A curable resin composition was obtained.

Example 6
In a reaction vessel, 25 parts by weight of pentaerythritol triacrylate, 75 parts by weight of colloidal silica fine particles (average particle size 40 nm) surface-modified with a silane coupling agent having a methacryl group, 1-hydroxycyclohexyl phenyl ketone (photopolymerization initiator) BASF Japan Co., Ltd. product: Irgacure 184) 0.7 part by weight was added and stirred, and then the volatile solvent was removed under reduced pressure to obtain a silica-containing coating resin composition.

Next, 25 parts by weight of tetraethylene glycol dimethacrylate, 75 parts by weight of dicyclopentanyldimethylol diacrylate, 2.5 parts by weight of 1-hydroxycyclohexyl phenyl ketone (BASF Japan Ltd .: Irgacure 184) as a photopolymerization initiator And mixed to obtain a photocurable resin composition.

Next, in the same manner as in Example 1, the silica-containing coating resin composition and the photocurable resin composition were applied, respectively, and then photocured to obtain a laminate.

Example 7
In a reaction vessel, 25 parts by weight of glycerin dimethacrylate, 75 parts by weight of colloidal silica fine particles (average particle size 40 nm) surface-modified with a silane coupling agent having a methacryl group, 1-hydroxycyclohexyl phenyl ketone (photopolymerization initiator) BASF Japan Co., Ltd. product: Irgacure 184) 0.7 part by weight was added and stirred, and then the volatile solvent was removed under reduced pressure to obtain a silica-containing coating resin composition.

Next, 35 parts by weight of tetraethylene glycol dimethacrylate and 65 parts by weight of 1,9-nonanediol diacrylate, 2.5 parts by weight of 1-hydroxycyclohexyl phenyl ketone (BASF Japan, Inc .: Irgacure 184) as a photopolymerization initiator , And 3 parts by weight of bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (BASF Japan KK: Irgacure 819), 2- (2,4-dihydroxyphenyl) -4,6- As a light stabilizer, 5 parts by weight of a reaction product of bis- (2,4-dimethylphenyl) -1,3,5-triazine and (2-ethylhexyl) -glycidic acid ester (manufactured by BASF Japan Ltd .: Tinuvin 405) Screw (1, 2, 2, 6, 6-pen 1 part by weight of a mixture of methyl-4-piperidyl) sebacate and

methyl

1,2,2,6,6-pentamethyl-4-piperidyl sebacate (manufactured by BASF Japan Ltd .: Tinuvin 292) is mixed and photocured. A resin composition was obtained.

Example 8
Colloidal silica surface-modified with 20 parts by weight of glycerin dimethacrylate, 5 parts by weight of a caged silsesquioxane resin having a methacrylic group obtained in Synthesis Example 1, and a silane coupling agent having a methacrylic group. 75 parts by weight of fine particles (average particle size 40 nm), 0.7 part by weight of 1-hydroxycyclohexyl phenyl ketone (manufactured by BASF Japan Ltd .: Irgacure 184) as a photopolymerization initiator, 2- (2,4-dihydroxyphenyl) as an ultraviolet absorber ) -4,6-bis- (2,4-dimethylphenyl) -1,3,5-triazine and (2-ethylhexyl) -glycidic acid ester reaction product (BASF Japan KK: Tinuvin 405) 5 weight Bis (2,2,6,6-tetramethyl decanedioate as a light stabilizer 1- (Octyloxy) -4-piperidinyl) ester, 1,1-dimethylethyl hydroperoxide and octane reaction product (BASF Japan KK: Tinuvin 123) 1 part by weight was added and stirred, then under reduced pressure The volatile solvent content was removed with a silica-containing coating resin composition.

Next, 70 parts by weight of dicyclopentanyldimethylol diacrylate, 30 parts by weight of 1,9-nonanediol diacrylate, 1-hydroxycyclohexyl phenyl ketone as a photopolymerization initiator (manufactured by BASF Japan Ltd .: Irgacure 184) 5 parts by weight and 3 parts by weight of bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (manufactured by BASF Japan Ltd .: Irgacure 819), benzenepropanoic acid as a UV absorber, 3- (2H-benzotriazole- 2-yl) -5- (1,1-dimethylethyl) -4-hydroxy, C7-9 side chain and linear alkyl ester (manufactured by BASF Japan Ltd .: Tinuvin 384-2), 5 parts by weight, as light stabilizer Bis (1,2,2,6,6-pentameth (Lu-4-piperidyl) sebacate and

methyl

1,2,2,6,6-pentamethyl-4-piperidyl sebacate (BASF Japan Co., Ltd .: Tinuvin® 292) 1 part by weight, mixed and photocured A resin composition was obtained.

[Comparative Example 1]
Surface modification with 20 parts by weight of dicyclopentanyldimethylol diacrylate, 5 parts by weight of a silsesquioxane resin having a methacrylic group obtained in Synthesis Example 1 above, and a silane coupling agent having a methacrylic group. 75 parts by weight of colloidal silica fine particles (average particle diameter: 40 nm) (MEK-AC-4101 manufactured by Nissan Chemical Co., Ltd.) and 1-hydroxycyclohexyl phenyl ketone (manufactured by BASF Japan Ltd .: Irgacure 184) as a photopolymerization initiator After adding 7 parts by weight and stirring, the volatile solvent was removed under reduced pressure to obtain a silica-containing coating resin composition.

Next, 25 parts by weight of 1,9-nonanediol diacrylate, 75 parts by weight of tetraethylene glycol dimethacrylate, and 2.5 parts by weight of 1-hydroxycyclohexyl phenyl ketone (BASF Japan, Inc .: Irgacure 184) as a photopolymerization initiator. And mixed to obtain a photocurable resin composition.

[Comparative Example 2]
Surface modification with 30 parts by weight of dicyclopentanyldimethylol diacrylate, 5 parts by weight of a silsesquioxane resin having a methacrylic group obtained in Synthesis Example 1 above, and a silane coupling agent having a methacrylic group. 65 parts by weight of colloidal silica fine particles (average particle 15 nm) (MEK-AC-2101 manufactured by Nissan Chemical Co., Ltd.) and 1-hydroxycyclohexyl phenyl ketone (BASF Japan KK: Irgacure 184) 0.9 as a photopolymerization initiator After adding a part by weight and stirring, the volatile solvent was removed under reduced pressure to obtain a silica-containing coating resin composition.

Then, after applying the silica-containing coating resin composition and the photocurable resin composition in the same manner as in Example 1, photocuring was performed to obtain a laminate.

[Comparative Example 3]
In a reaction vessel, 35 parts by weight of pentaerythritol triacrylate, 20 parts by weight of glycerin dimethacrylate, 12.5 parts by weight of lysyl sesquioxane having a methacryl group obtained in Synthesis Example 1 above, and a silane coupling having a methacryl group 32.5 parts by weight of colloidal silica fine particles (average particle diameter 40 nm) (Nissan Chemical Co., Ltd. MEK-AC-4101) and 1-hydroxycyclohexyl phenyl ketone (BASF Japan K.K.) as a photopolymerization initiator Manufactured: Irgacure 184) 1.6 parts by weight was added and stirred, and then the volatile solvent was removed under reduced pressure to obtain a silica-containing coating resin composition.

Next, 25 parts by weight of tetraethylene glycol dimethacrylate and 75 parts by weight of dicyclopentanyldimethylol diacrylate, 2.5 parts by weight of 1-hydroxycyclohexyl phenyl ketone (BASF Japan Ltd .: Irgacure 184) as a photopolymerization initiator Parts were added and mixed to obtain a photocurable resin composition.

[Comparative Example 4]
To 100 parts by weight of pentaerythritol triacrylate, 2.5 parts by weight of 1-hydroxycyclohexyl phenyl ketone (manufactured by BASF Japan Ltd .: Irgacure 184) as a photopolymerization initiator was added and stirred to obtain a coating resin composition.

Next, the photocurable resin composition is applied to the surface of a 3 mm thick polycarbonate flat plate (Carbo Glass Polish: manufactured by Asahi Glass Co., Ltd.) using a spin coater so as to have a film thickness of 50 μm, and using a high pressure mercury lamp. Ultraviolet rays were irradiated at 2800 mJ / cm ² to form an adhesion layer. Next, the coating resin composition was applied onto the adhesion layer using a spin coater so as to have a film thickness of 15 μm, and then irradiated with ultraviolet rays at 8400 mJ / cm ² using a high-pressure mercury lamp to obtain a laminate. It was.

[Comparative Example 5]
Add 75 parts by weight of glycerin dimethacrylate, 25 parts by weight of lysyl sesquioxane having a methacrylic group, and 2.5 parts by weight of 1-hydroxycyclohexyl phenyl ketone (manufactured by BASF Japan Ltd .: Irgacure 184) as a photopolymerization initiator. Thus, a coating resin composition was obtained.

Next, 65 parts by weight of 1,9-nonanediol diacrylate, 25 parts by weight of dicyclopentanyldimethylol diacrylate, 75 parts by weight of 1-hydroxycyclohexyl phenyl ketone (manufactured by BASF Japan Ltd .: Irgacure 184) as a photopolymerization initiator. ) 2.5 parts by weight were added and mixed to obtain a photocurable resin composition.

For the laminates obtained in Examples 1 to 8 and Comparative Examples 1 to 5, the initial total light transmittance, the initial haze before the Taber abrasion test, and the Taber abrasion resistance after the Taber abrasion test were changed. Evaluation was performed by (ΔH). The obtained results are shown in Table 1.

1: Top coat layer 2: Adhesion layer 3: Polycarbonate substrate

Claims

The following general formula (1)

Where R is an organic functional group having a (meth) acryloyl group, X is an organic functional group having hydrogen or a (meth) acryloyl group, and n is an integer of 0 or 1. ) A radically polymerizable compound (A) having an acrylic group and a hydroxyl group, a photopolymerization initiator, and silica fine particles (B) having an average particle diameter of 1 to 100 nm, the radical polymerizable compound (A) and the silica fine particles (B ) In a total amount of 100 parts by weight of silica fine particles (B) in the range of 60 to 85 parts by weight.
The silica-containing coating resin according to claim 1, wherein the silica fine particles (B) are silicon oxide and colloidal silica, and are further surface-treated with a silane coupling agent having a (meth) acryl group. Composition.
The silica-containing coating resin composition according to claim 1 or 2, wherein the silica fine particles (B) contain 50 parts by weight or more of silica fine particles having an average particle diameter of 16 to 100 nm with respect to 100 parts by weight of all silica fine particles. object.
A photocurable resin composition comprising a topcoat layer (I) obtained by photocuring the silica-containing coating resin composition according to claim 1, a radical polymerizable (meth) acrylate, and a photopolymerization initiator is photocured. A laminate in which a hard coat layer consisting of two layers with a caulking adhesive layer (II) is provided on at least one surface of a thermoplastic resin molded product, comprising a silica-containing coating resin composition and a photocurable resin composition A laminate having a hard coat layer formed by coating and photocuring each product.
The laminate according to claim 4, wherein the transparent thermoplastic resin molded article is made of polycarbonate.
The laminate according to claim 4 or 5, wherein the radically polymerizable (meth) acrylate contained in the photocurable resin composition is a polyfunctional (meth) acrylate.
7. The thickness of the top coat layer (I) is 5 to 100 μm, the thickness of the adhesion layer (II) is 1 to 100 μm, and the total thickness of the laminate is 1000 to 5000 μm. The laminated body of crab.