JP5752947B2 - Method for producing resin composition for hard coat, and resin composition for hard coat - Google Patents

Description

  The present invention relates to a method for producing a resin composition for (meth) acrylate-based hard coat containing inorganic fine particles, and a resin composition for hard coat.

  For the purpose of improving the mechanical properties, heat resistance, etc. of an acrylic resin such as polymethyl methacrylate (hereinafter referred to as PMMA), a resin composition in which inorganic fine particles are blended in the resin is known. As such a resin composition, there is known a resin composition that improves mechanical properties by causing a sol-gel reaction between an acrylic polymer having an alkoxysilyl group and a metal alkoxide (see Patent Document 1). Such a resin composition can be applied as a hard coat liquid to a resin substrate such as a plastic sheet, a plastic lens, or a plastic film, and used to enhance the mechanical properties of the substrate. Further, as such an organic-inorganic hard coat coating solution, a hard coat coating solution comprising an organic resin matrix component and coated metal oxide fine particles coated with a polymer silane coupling agent is known. (See Patent Document 2).

JP 2004-277512 A JP 2009-083223 A

The above-described resin composition can be expected to have a function as a hard coat when applied to a resin substrate.
In general, hard coats can improve mechanical properties such as scratch resistance and surface hardness, but it is difficult to improve both mechanical properties and weather resistance at the same time. In many cases, the coating solution has a problem in the storage stability of the coating solution, and a resin composition capable of satisfying such various performance conditions is desired.

  In view of the above-mentioned problems of the prior art, a method for producing a resin composition for hard coat, which can satisfy various performance conditions such as mechanical properties such as scratch resistance and surface hardness, weather resistance, storage stability, Another object of the present invention is to provide a hard coat resin composition obtained by using the method.

  As a result of intensive studies, the present inventors have conducted a polyfunctional (meth) acrylate monomer modification modification obtained by addition reaction of a modifier having a thiol group (mercapto group) and a tri- or higher functional (meth) acrylate monomer. Organic-inorganic hybrid resin compositions containing metal oxide fine particles modified with an agent can be synthesized by a simple method, and have surface hardness and scratch resistance mechanical properties, weather resistance, and storage stability. It was found that it was good and could be used particularly suitably as a resin composition for hard coat.

  In the present invention, as the modifying agent to be used, a silane coupling agent having a thiol group as represented by the general formula (1) can be particularly preferably used.

_{HS- (CH 2) n-Si} (R 1) x (OR 2) 3-x ··· Equation (1)
(R ¹ and R ² each independently represents a group selected from a lower alkyl group having 1 to 4 carbon atoms and a phenyl group. N is an integer of 1 to 11 representing the chain number of a methylene group, and x is , 0, 1 or 2.)
Examples of the silane coupling agent having a thiol group include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylethyldiethoxysilane, and 1-mercaptomethyl. Examples thereof include methyldimethoxysilane and 11-mercaptoundecyltrimethoxysilane.

  In the present invention, the following trifunctional or higher functional (meth) acrylate monomers may be those listed below. In the description, “... (Meth) acrylate” represents “... Acrylate” or “.

  First, as the trifunctional or higher functional (meth) acrylate monomer, for example, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, ethylene oxide-modified trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol Examples include branched chain, cyclic (meth) acrylates, and urethane acrylates such as hexaacrylate, tetramethylolmethane triacrylate, tetramethylolmethane tetraacrylate, and tris (2-hydroxyethyl) isocyanurate triacrylate. , Not limited to those listed here. These can be used alone or in combination.

Examples of the metal oxide fine particles used include silica (SiO ₂ ), alumina (Al ₂ O ₃ ), zirconia (ZrO ₂ ), titania (TiO ₂ ), ITO (tin-doped indium oxide), and tin oxide (SnO). ₂ ), zinc oxide (ZnO), antimony oxide (Sb ₂ O ₃ , Sb ₂ O ₅ etc.), and composite fine particles thereof. Such metal oxide fine particles have hydroxyl groups on the surface.

  The average primary particle diameter of the metal oxide fine particles used in the present embodiment is 100 nm or less, preferably 30 nm or less. When the average primary particle size is 100 nm or less, the transparency specific to the (meth) acrylate resin is maintained even after the hard coat resin composition is cured with ultraviolet rays.

  The content of the metal oxide fine particles is preferably 20% by weight to 70% by weight with respect to the mixed amount of the polyfunctional (trifunctional or higher) (meth) acrylate monomer and the metal oxide fine particles having a hydroxyl group on the surface. More preferably, it is 40% by weight to 60% by weight. If the metal oxide fine particles are less than 20% by weight, the effect is hardly exhibited. Moreover, when it exceeds 60 weight%, the obtained resin composition tends to become weak. A highly reactive metal alkoxide such as silicon, titanium, zirconium, or aluminum can be added together with the metal oxide fine particles, or can be added instead of the metal oxide fine particles.

  In addition, weather fastness (durability) can be obtained by adding a bifunctional or lower (meth) acrylate monomer or fluororesin to a resin composition containing metal oxide fine particles modified with the above-mentioned polyfunctional (meth) acrylate monomer modification modifier. ) And scratch resistance can be improved.

  Examples of the bifunctional or lower (meth) acrylate monomer that can be used in the hard coat resin composition of the present invention include, for example, methyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-butoxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, glycidyl (meta ) Acrylate, N-acryloyloxyethyl hexahydrophthalimide, glycerin di (meth) acrylate, 2-hydroxy-3-acrylopropyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate 2-hydroxybutyl (meth) acrylate, ethylene glycol di (meth) acrylate, 1,3-propylene glycol di (meth) acrylate, 1,4-heptanediol di (meth) acrylate, 1,6-hexanediol di (meta) ) Acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 2-butene-1,4-di (meth) acrylate, cyclohexane-1,4-dimethanol di (meth) acrylate, 1,5-pentanedi (Meth) acrylate, trimethylolethane di (meth) acrylate, trimethylolpropane di (meth) acrylate, dipropylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, dioxane Recall diacrylate linear, branched, cyclic (meth) acrylates, or difunctional following may be mentioned urethane acrylate, and the like, not limited to those listed here. These can be used alone or in combination. The content of the bifunctional or lower (meth) acrylate monomer is 30% by weight or less, more preferably 10% by weight to 25% by weight, based on the polyfunctional (trifunctional or higher) (meth) acrylate monomer. When the bifunctional or lower (meth) acrylate monomer exceeds 30% by weight, the obtained resin composition coating film (hard coat layer) tends to be soft.

The fluororesin that can be used in the hard coat resin composition of the present invention includes perfluoropolyether acrylate, perfluoropolyether methacrylate, fluorinated polysiloxane, fluorinated cyclic polysiloxane, and fluorinated cyclic polysiloxane acrylate. Fluorine-based resins such as fluorine-containing cyclic polysiloxane methacrylate can be used, and the present invention is not limited to those mentioned here. These can be used alone or in combination.
In particular, a fluororesin that is excellent in compatibility with a non-fluorine organic compound and is photocurable is preferable, and the scratch resistance can be improved even with a very small addition amount.

  Examples of photopolymerization initiators for curing the obtained hard coat resin composition with ultraviolet rays include tris (chloromethyl) triazine, 2,4-trichloromethyl- (4′-methoxystyryl)- 6-triazine, 2- [2- (furan-2-yl) ethenyl] -4,6-bis (trichloromethyl) -S-triazine, 2,4,6-tris (trichloromethyl) -S-triazine, etc. Triazine compounds, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin butyl ether and other benzoin compounds, diethoxyacetophenone, 4-phenoxydichlorolacetophenone, 2-benzyl-2-dimethylamino-1- (4- Morpholinophenyl) -butan-1-one, benzophenone, Acetophenone compounds such as 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, 1-hydroxycyclohexyl acetophenone, thioxanthones such as thioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, 2-chlorothioxanthone Compound, benzyl dimethyl ketal, 2,4,6-trimethylbenzoindiphenylphosphine oxide, isoamyl N, N-dimethylaminobenzoate, acylphosphine oxide, etc., and these may be used alone or in combination of two or more. May be used. The addition amount is 10 wt% or less, preferably 0.5 to 5 wt%, based on the meth) acrylate monomer.

Next, the manufacturing method of the resin composition of this invention is demonstrated.
First, in order to obtain metal oxide fine particles modified with a polyfunctional (meth) acrylate monomer modification modifier, a predetermined amount of a modifier having a thiol group (mercapto group) and a trifunctional or higher (meth) acrylate monomer are mixed. To make a mixture.

（式中Ｒａは多官能（メタ）アクリレートモノマーの残基、Ｒｂはチオール基を有する修飾剤の残基をそれそれ示し、Ｒ’は脂肪族及び／又は芳香族炭化水素鎖を示す） In order to react the resulting mixture under alkaline conditions, for example, a slight amount of triethylamine is added, and the mixture is reacted for a predetermined time in the range of room temperature to 90 ° C. to cause an addition reaction. In such an addition reaction under alkaline conditions, the thiol group of the modifier and the acryloyl group and / or methacryloyl group of the tri- or higher functional (meth) acrylate monomer are covalently bonded (sulfide bond, —R—S—R). '-: R and R' are Michael addition reactions that are aliphatic and / or aromatic hydrocarbon chains), and a polyfunctional (meth) acrylate monomer modified modifier is obtained.
This reaction is obtained because the thiol group possessed by the modifier and the acryloyl group and / or methacryloyl group possessed by the tri- or higher-functional (meth) acrylate monomer are subjected to a 1: 1 addition reaction, as shown in Chemical Formula 1 below. An unreacted acryloyl group and / or methacryloyl group remains in the polyfunctional (meth) acrylate monomer-modified modifier.
In addition, a sulfide bond obtained by this reaction (—R—S—R′—: R and R ′ are aliphatic and / or aromatic hydrocarbon chains), the resulting polyfunctional (meth) acrylate monomer modification modifier. Gives flexibility.

(In the formula, Ra represents a residue of a polyfunctional (meth) acrylate monomer, Rb represents a residue of a modifier having a thiol group, and R ′ represents an aliphatic and / or aromatic hydrocarbon chain)

  A predetermined amount of metal oxide fine particles having a hydroxyl group on the surface dispersed in an organic solvent is added to the obtained polyfunctional (meth) acrylate monomer modification modifier. In order to advance the condensation reaction between the polyfunctional (meth) acrylate monomer-modified modifier and the metal oxide fine particles, an alkali or acid diluted in water is added and stirred. By stirring and reacting, a solution containing metal oxide fine particles modified with a polyfunctional (meth) acrylate monomer modification modifier is obtained. A predetermined amount of the above-mentioned polymerization initiator is added to the obtained solution to obtain the desired hard coat resin composition.

In the present invention, the number of hydroxyl groups on the surface of the silica particles is 1.68 mmol / g (reference: Polymer, Volume 47, Issue 11, 2006, 3754-3759). The surface modification rate was calculated by calculating whether the acrylate monomer modified modifier was replaced.
If the surface modification rate is too low, the surface hardness and scratch resistance are poor, and if it is too high, the storage stability of the resin composition is poor. The surface modification rate of the metal oxide fine particles is preferably in the range of 10 to 85%, more preferably in the range of 40 to 65%.

Furthermore, in order to further improve the scratch resistance, weather resistance and impact resistance, a bifunctional or lower (meth) acrylate monomer or a fluororesin is added in accordance with the addition of the polymerization initiator. The bifunctional or lower (meth) acrylate monomer used in the resin composition for hard coat of the present invention is 30% by weight or less, more preferably 10% by weight, based on the polyfunctional (trifunctional or higher) (meth) acrylate monomer. ~ 25% by weight. Moreover, the fluororesin used for the resin composition for hard coats of this invention is 0.01 to 1 weight% with respect to the resin composition whole quantity.
Furthermore, the resin composition for hard coats of the present invention contains a photosensitizer, a leveling agent, an antifoaming agent, a fluidity modifier, a light stabilizer, an antioxidant, a colorant, a pigment, and the like as necessary. May be.

In addition, the resin composition for hard coats of the present invention has a simple manufacturing process and can be manufactured at low cost. Spin coating, spray coating, dip coating, bar coating, flow coating, cap coating, knife coating, die coating, roll coating, gravure coating, screen printing, brush coating, etc. After being used and applied to a predetermined thickness, a hard coat layer having an effect of improving surface hardness and scratch resistance is formed on the substrate by irradiating with ultraviolet rays and photopolymerizing and curing.
Moreover, the adhesiveness of a hard-coat layer and a base material can be improved by performing a corona discharge, a plasma process, etc. with respect to a base material before the coating of the resin composition for hard-coats.

  The resin composition for hard coat of the present invention is not limited to PMMA resin sheet, but polycarbonate resin, acrylonitrile butadiene styrene resin, vinyl chloride resin, polycycloolefin resin, polyethylene terephthalate resin, polybutylene terephthalate resin, triacetyl cellulose resin, polyethylene It can be used for various sheets, films and molding materials such as resin, two-layer and three-layer resins obtained by bonding PMMA resin and polycarbonate resin. The sheet generally has a thickness of 0.3 to 100 mm, and the film has a thickness of 30 to 300 μm.

The thickness of the hard coat layer is 1 to 50 μm, preferably 1 to 20 μm. UV irradiation is performed by using ultraviolet rays emitted from a light source such as a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, an electrodeless lamp, a xenon lamp, a metal halide lamp, a carbon arc lamp, an LED lamp, or a tungsten lamp.
In addition, after apply | coating to a board | substrate using the resin composition for hard coats of this invention and forming a hard-coat layer, the existing antireflection film can also be directly formed on this hard-coat layer. Even if an antireflection film is formed directly on the hard coat layer, the adhesiveness is not peeled off. Moreover, even if an antireflection film is formed, the film properties (scratch resistance, surface hardness, etc.) of the resin composition for hard coat are not easily lowered. Furthermore, the existing antifouling agent can be applied on the hard coat layer to which the resin composition for hard coat of the present invention is applied to improve the slipperiness.

  According to the resin composition for hard coat of the present invention, high scratch resistance and surface hardness (pencil hardness) are obtained, and the weather resistance of the coating layer after film formation and the storage stability as a hard coat liquid are satisfied. Can be made.

  Next, although the Example and comparative example regarding this invention are given and demonstrated, this invention is not limited to these.

<Example 1>
To 90 g of polyfunctional urethane acrylate monomer (Kyoeisha Chemical Co., Ltd., UA-510H), add 6.42 g of 3-mercaptopropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., KBM803) and triethylamine (Kishida Chemical Co., Ltd.) 0.408 g was added and heated at 70 ° C. for 2 hours to prepare a polyfunctional (meth) acrylate monomer-modified modifier. The addition reaction was confirmed by NMR. 300g of silica particle dispersed MIBK (methyl isobutyl ketone) solution (manufactured by Nissan Chemical Industries, MIBK-ST, SiO2 30wt%, average particle size 10-20nm) is added to the polyfunctional (meth) acrylate monomer modified modifier. After stirring, a mixed solution of 21 g of methyl ethyl ketone and 2.64 g of pure water was added and stirred overnight at room temperature to prepare a reaction solution containing silica particles modified with a polyfunctional urethane acrylate monomer modified modifier. This solution was concentrated by an evaporator to adjust the solid content to 55 wt%, and then filtered.
2.27g of photo radical polymerization initiator (Ciba Specialty Chemicals, Irgacure 184), 1.26g of perfluoropolyether acrylate (Solvay Solexis, AD-1700), bifunctional urethane acrylate (Toagosei) 11.65 g of ARONIX M-1700 (manufactured by Co., Ltd.) was added and stirred to prepare the desired hard coat resin composition (hard coat solution).
Apply the above hard coat solution to a transparent PMMA base material (Delagrass, manufactured by Asahi Kasei Technoplus Co., Ltd.) with a thickness of 2mm using a bar coater, and apply it to an air atmosphere in a high-pressure mercury lamp to about 900mJ / cm ² Was applied to form a hard coat layer having a thickness of about 11 μm.
The hard coat layer on the PMMA plate obtained as described above was evaluated by performing the following measurements and tests. These measurements and tests were performed after 24 hours or more had passed since the hard coat layer was produced. The following Examples 2 to 14 and Comparative Example 1 were evaluated by performing the same measurements and tests, and the results are shown in Table 1.
[Pencil hardness test]
The pencil hardness of the hard coat layer surface was measured according to JIS-K-5600.
Specifically, leave the pencil cylindrical shin as it is, scrape only the wood part and leave 5-6mm of shin. Thereafter, the tip of the shin is flattened with abrasive paper. The tip of the shin is made flat on the abrasive paper every time during the test. Set a pencil on the tester specified by JIS. This tester is designed so that the tip of the pencil has a load of 45 ± 1 ° and 750 ± 10 g with respect to the coating surface when in the horizontal position.
After placing the tip of the pencil on the coating surface, the tester is moved 7 mm or more at a moving speed of 0.5 to 1 mm / s while maintaining the above load. While changing the test part, increase the hardness of the pencil until a scar of at least 3 mm or more occurs. The hardness of the hardest pencil that did not cause scars was taken as the pencil hardness in this test.
The pencil hardness increases (hardens) in the following order.
(Soft) 6B ・ 5B ・ 4B ・ 3B ・ 2B ・ B ・ HB ・ F ・ H ・ 2H ・ 3H ・ 4H ・ 5H ・ 6H (Hard)
[Steel Wool Resistance Test]
The number of scratches when the hard coat layer surface was rubbed at 1.5 kg load / cm ² for 10 reciprocations using # 0000 steel wool (Bonster Sales Co., Ltd., Bonstar) was evaluated according to the following criteria.
The test was performed at a stroke length of 10 cm and a speed of 1 reciprocation / second, and the number of scratches in a 5 mm square with the most scratches was visually counted.
No scratches: A
No scratches but cloudy: AB
1-5 scratches: B
6-10 scratches: C
11-15 scratches: D
16-20 scratches: E
More than 21 scratches: F
[Light resistance test]
The PMMA base material coated with the hard coating solution was subjected to an exposure test up to 1000 hours at a black panel temperature of 63 ° C. using a Super Xenon Weather Meter SX75 (manufactured by Suga Test Instruments Co., Ltd.), and the appearance after the test was evaluated.
[Heat resistance test]
The PMMA substrate coated with the hard coat solution was stored at a constant temperature of 80 ° C. for up to 1000 hours, and the appearance was evaluated after the test.
[Liquid stability]
50 ml of the hard coating solution was stored at 50 ° C. in the dark, and the state of the coating solution after 3 months was observed and evaluated.
The above results are shown in Table 1.
In addition, after adding a lot of propylene glycol monomethyl ethers (henceforth PGM) to the resin composition for hard-coats (hard-coat liquid) of Example 1, it concentrated by the evaporator. By repeating the same operation, a PGM solvent hard coat resin composition can be obtained.

<Example 2>
The concentration process was performed in the same manner as in Example 1 to adjust the solid content to 55 wt%, and then 2.27 g of Irgacure 184 was added and stirred to prepare a hard coat solution. Using this hard coat solution, coating, measurement and testing on PMMA plates were carried out in the same manner as in Example 1 for evaluation. The above results are shown in Table 1.

<Example 3>
In the same manner as in Example 1, the concentration step was performed to adjust the solid content to 55 wt%, and then Irgacure 184 2.27 g and ARONIX M-1700 11.65 g were added and stirred to prepare a hard coat solution. Using this hard coat solution, the coating, measurement and testing on the PMMA plate were carried out in the same manner as in Example 1 for evaluation. The above results are shown in Table 1.

<Example 4>
In the same manner as in Example 1, the concentration step was performed to adjust the solid content to 55 wt%, and then Irgacure 184 2.27 g and AD-1700 1.26 g were added and stirred to prepare a hard coat solution. Using this hard coat solution, the coating, measurement and testing on the PMMA plate were carried out in the same manner as in Example 1 for evaluation. The above results are shown in Table 1.

<Example 5>
In the same manner as in Example 1, 6.42 g of KBM803 was added to 90 g of UA-510H, 0.408 g of triethylamine was added, and the mixture was heated at 70 ° C. for 2 hours. After heating, the reaction solution was depressurized at 70 ° C. to remove triethylamine. After adding 300 g of MIBK-ST to this reaction solution and stirring at room temperature, a mixed solution of 21 g of methyl ethyl ketone and 2.64 g of 0.5 wt% acetic acid aqueous solution was added and stirred overnight at room temperature. Thereafter, the solid content was adjusted to 55 wt% in the same manner as in Example 1, and 2.27 g of Irgacure 184 was added and stirred to prepare a hard coat solution. Using this hard coat solution, the coating, measurement and testing on the PMMA plate were carried out in the same manner as in Example 1 for evaluation. The above results are shown in Table 1.

<Example 6>
A hard coat solution was prepared in the same manner as in Example 2 except that 90 g of tetrafunctional urethane acrylate (Daicel Cytec Co., Ltd., EBECRYL 8210) was used instead of UA-510H. Using this hard coat solution, the coating, measurement and testing on the PMMA plate were carried out in the same manner as in Example 1 for evaluation. The above results are shown in Table 1.

<Example 7>
A hard coat solution was produced in the same manner as in Example 2 except that 90 g of pentaerythritol triacrylate (manufactured by Kyoeisha Chemical Co., Ltd., light acrylate PE-3A) was used instead of UA-510H. Using this hard coat solution, the coating, measurement and testing on the PMMA plate were carried out in the same manner as in Example 1 for evaluation. The above results are shown in Table 1.

<Example 8>
A hard coat solution was prepared in the same manner as in Example 1 except that 5.89 g of 3-mercaptopropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM802) was used instead of KBM803. Using this hard coat solution, the coating, measurement and testing on the PMMA plate were carried out in the same manner as in Example 1 for evaluation. The above results are shown in Table 1.

<Example 9>
A hard coat solution was prepared in the same manner as in Example 2 except that 72 g of UA-510H, 7.70 g of KBM803, 0.490 g of triethylamine, and 360 g of MIBK-ST were used. Using this hard coat solution, the coating, measurement and testing on the PMMA plate were carried out in the same manner as in Example 1 for evaluation. The above results are shown in Table 1.

<Example 10>
A hard coat solution was prepared in the same manner as in Example 2 except that 108 g of UA-510H, 5.14 g of KBM803, 0.326 g of triethylamine, and 240 g of MIBK-ST were used. Using this hard coat solution, the coating, measurement and testing on the PMMA plate were carried out in the same manner as in Example 1 for evaluation. The above results are shown in Table 1.

<Example 11>
A hard coat solution was prepared in the same manner as in Example 2 except that 3.21 g of KBM803 and 0.204 g of triethylamine were used. Using this hard coat solution, the coating, measurement and testing on the PMMA plate were carried out in the same manner as in Example 1 for evaluation. The above results are shown in Table 1.

<Example 12>
A hard coat solution was prepared in the same manner as in Example 2 except that 12.48 g of KBM803 and 0.912 g of triethylamine were used. Using this hard coat solution, the coating, measurement and testing on the PMMA plate were carried out in the same manner as in Example 1 for evaluation. The above results are shown in Table 1.

<Example 13>
A hard coat solution was prepared in the same manner as in Example 3 except that 11.65 g of ARONIX M-140 (manufactured by Toagosei Co., Ltd.), which is a monofunctional acrylate, was used instead of ARONIX M-1700. Using this hard coat solution, the coating, measurement and testing on the PMMA plate were carried out in the same manner as in Example 1 for evaluation. The above results are shown in Table 1.

<Example 14>
A hard coat solution was prepared in the same manner as in Example 1 except that 19.67 g of EBECRYL 4858 (manufactured by Daicel Cytec Co., Ltd.), which is a bifunctional urethane acrylate, was used instead of ARONIX M-1700. This hard coat solution is applied to a transparent PMMA substrate (made by Asahi Kasei Technoplus Co., Ltd., Delaglass) with a thickness of 1 mm using a dip coat, and this is about 600 mJ / cm ² using a high-pressure mercury lamp in an air atmosphere. Ultraviolet rays were irradiated to form a hard coat layer having a thickness of about 11 μm. Measurements and tests were performed and evaluated in the same manner as in Example 1. The above results are shown in Table 1.

<Comparative Example 1>
A hard coat solution was prepared in the same manner as in Example 2 except that 90 g of methyl methacrylate (Kyoeisha Chemical Co., Ltd., Light Ester M) was used instead of UA-510H. Using this hard coat solution, the coating, measurement and testing on the PMMA plate were carried out in the same manner as in Example 1 for evaluation. The above results are shown in Table 1.

<Comparative Example 2>
Add UA-510H 90g, KBM803 6.42g, solvent 300ml tetrahydrofuran, thermal polymerization initiator azoisobutyronitrile (Kishida Chemical Co., Ltd., AIBN) 0.245g, replace with nitrogen gas and start heating at 70 ° C did. The whole gelled 20 minutes after the start of heating. 1.5 g of the gelled product was added to 20 g of acetone and stirred for 24 hours, but it did not dissolve. The above results are shown in Table 1.

In addition, the hard coat layers (Examples 1, 2, 3, 4, 8, 13, 14) on the PMMA plate obtained as described above were subjected to the following tests and evaluated, and the results are shown in Table 2. Indicated. These measurements and tests were carried out after 24 hours or more had passed since the hard coat layer was produced.
[Moisture resistance test]
The PMMA substrate coated with a hard coat was stored at 85 ° C. and a constant humidity of 85% for 500 hours or 1000 hours, and the appearance was evaluated after the test.
[Thermal cycle test]
The PMMA base material coated with the hard coat was stored at -40 ° C. for 1 hour and then at 85 ° C. for 1 hour as 1 cycle, and the appearance was evaluated.
[Falling ball test]
A PMMA base material coated with a hard coat is fixed on a cylindrical aluminum jig, and a steel ball (weight 36g, diameter 13/16 inch) is dropped freely from a height of 20cm to evaluate the appearance after the test. did.

(result)
As shown in Tables 1 and 2, the resin compositions of Examples 1 to 14 can obtain high scratch resistance and surface hardness, weather resistance of the coating layer after film formation, and storage as a hard coat coating solution. The stability was shown to be good.

Claims (5)

Multifunctional (meth) acrylate monomer modification modifier by covalently bonding a thiol group and an acryloyl group and / or methacryloyl group using an addition reaction between a modifier having a thiol group and a tri- or higher functional (meth) acrylate monomer A first step of obtaining
A second step of modifying the polyfunctional (meth) acrylate monomer-modified modifier obtained in the first step to metal oxide fine particles;
A third step of adding a fluororesin after the second step;
The manufacturing method of the resin composition for hard-coats characterized by having. 2. The method for producing a resin composition for hard coat according to claim 1, wherein the covalent bond in the first step is a sulfide bond between the modifier having the thiol group and the trifunctional or higher functional (meth) acrylate monomer. The manufacturing method of the resin composition for hard-coats characterized by these. 3. The method for producing a resin composition for hard coat according to claim 2, wherein the modifier is a silane coupling agent having a thiol group. 4. The method for producing a hard coat resin composition according to claim 3, wherein the third step further comprises adding a bifunctional or lower (meth) acrylate monomer . In the organic-inorganic hybrid hard coat resin composition, the hybrid material is a sulfide in which the thiol group of the silane coupling agent having a thiol group and the acryloyl group and / or methacryloyl group of a tri- or higher functional (meth) acrylate monomer Metal oxide fine particles modified with a combined polyfunctional (meth) acrylate monomer modification modifier , and the hard coat resin composition further comprises a bifunctional or lower (meth) acrylate monomer and a fluororesin A resin composition for hard coat , characterized by the above.