KR20110103885A - Method of preparing resin composition for hard coat and resin composition for hard coat - Google Patents

Abstract

[PROBLEMS] To provide a method for producing a hard coat resin composition capable of satisfying various performance conditions such as mechanical properties such as friction resistance and surface hardness, weather resistance and storage stability, and a hard coat resin composition obtained by using the method.
[Method] In the method for producing a resin composition for hard coat, a thiol group, an acryloyl group and / or a methacryloyl group using a thiol group-modifying agent and a trifunctional or higher functional (meth) acrylate monomer using an addition reaction It has a 1st step which covalently bonds and obtains a polyfunctional (meth) acrylate monomer modification modifier, and the 2nd step which modifies the polyfunctional (meth) acrylate monomer modification modifier obtained by the 1st step to metal oxide fine particles.

Description

Manufacturing method of resin composition for hard coat and resin composition for hard coat {METHOD OF PREPARING RESIN COMPOSITION FOR HARD COAT AND RESIN COMPOSITION FOR HARD COAT}

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

In order to improve the mechanical properties, heat resistance, etc. of acrylic resins, such as polymethylmethacrylate (henceforth "PMMA"), the resin composition which mix | blended inorganic fine particles in resin is known. In such a resin composition, the resin composition which improves a mechanical property by carrying out the sol-gel reaction of the acryl-type polymer which has an alkoxy silyl group, and a metal alkoxide is known (refer patent document 1). Such a resin composition may be used as a hard coat liquid to be applied to a resin substrate such as a plastic sheet, a plastic lens, a plastic film, and the like to improve mechanical properties of the substrate. Moreover, as a coating liquid for hard-coats which consists of such organic-inorganic, the coating liquid for hard-coats which consists of coating metal oxide microparticles | fine-particles formed by coating with an organic resin matrix component and a polymer silane coupling agent is known (refer patent document 2).

Patent Document 1: Japanese Patent Application Laid-Open No. 2004-277512 Patent Document 2: Japanese Unexamined Patent Publication No. 2009-083223

The resin composition described above can be applied to a resin substrate to be expected to have a function as a hard coat.

In general, the hard coat can improve mechanical properties such as friction resistance and surface hardness, but it is difficult to improve both mechanical properties and weather resistance at the same time, and the storage solution of the coating liquid in an organic-inorganic hard coat coating liquid In many cases, there is a problem of stability, and a resin composition capable of satisfying such various performance conditions is required.

In view of the problems of the prior art, a method for producing a resin composition for hard coat that can satisfy various performance conditions such as mechanical properties such as friction resistance and surface hardness, weather resistance, and storage stability, and obtained by using the method It is a technical problem to provide a hard coat resin composition.

MEANS TO SOLVE THE PROBLEM As a result of earnestly researching, the inventors modified | reformed the polyfunctional (meth) acrylate monomer modified | modified by the addition reaction of the modifier which has a thiol group (mercapto group), and a trifunctional or more (meth) acrylate monomer. Hard coat which can synthesize organic-inorganic hybrid resin composition containing zero-modified metal oxide fine particles by a simple method and has excellent surface hardness and friction resistance mechanical properties, weather resistance and storage stability. It was found that the resin composition can be used particularly suitably.

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

HS- (CH ₂ ) n-Si (R ¹ ) x (OR ² ) 3-x Formula (1)

(R ¹ and R ² each independently represent a group selected from a lower acrylic group having 1 to 4 carbon atoms and a phenyl group. N is an integer of 1 to 11 representing the chain number of the methylene group, and x is 0, 1 or 2)

Examples of the silane coupling agent having a thiol group include 3-mercapto propyl trimethoxy silane, 3-mercapto propyl triethoxy silane, 3-mercapto propyl methyl dimethoxy silane, and 3-mercapto propyl ethyl diethoxy silane. , 1-mercapto methyl methyl dimethoxy silane, 11-mercapto undecyl trimethoxy silane, and the like.

In addition, in this invention, the trifunctional or more than (meth) acrylate monomer used can use what was heard below. In addition, in the notation "…" (Meth) acrylates Some things… Acrylate ”or“. Methacrylate ”.

First, as a trifunctional or more than (meth) acrylate monomer, For example, a trimethol propane trimethacrylate, a trimetholpropane triacrylate, ethylene oxide modified trimetholpropane triacrylate, pentaerythritol triacryl acrylate. Branched chain shape, such as the rate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, tetrametholmethane triacrylate, tetrametholmethane tetraacrylate, and tris (2-hydroxyethyl) isocyanate acrylate, Although cyclic (meth) acrylates or urethane acrylate etc. are mentioned, It is not limited to what was illustrated here. Moreover, these can be used combining one type or two or more.

As the metal oxide fine particles to be used, for example, silica (SiO ₂ ), alumina (Al ₂ O ₃ ), zirconia (ZrO ₂ ), titania (TiO ₂ ), ITO (indium tin dope), tin oxide ( SnO ₂ ), zinc oxide (ZnO), antimony oxide (Sb ₂ O ₃ , Sb ₂ O ₅ , and the like), and a plurality of these fine particles. Moreover, such metal oxide fine particles have a hydroxyl group on the surface.

As a particle diameter of the metal oxide fine particle used by this embodiment, an average primary particle diameter is 100 nm or less, Preferably it is 30 nm or less. The transparency peculiar to the (meth) acrylate resin is maintained even after the hard coat resin composition is cured with ultraviolet rays having an average primary particle diameter of 100 nm or less.

In addition, 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 more) (meth) acrylate monomer and the metal oxide fine particles having a hydroxyl group on the surface thereof, more preferably Is 40% by weight to 60% by weight. If the metal oxide fine particles are less than 20% by weight, the effect is less likely to be expressed. Moreover, when it exceeds 60 weight%, the obtained resin composition will be soft. In addition, it is also possible to add highly reactive metal alkoxides such as silicon, titanium, zirconium and aluminum together with the metal oxide fine particles or to replace the metal oxide fine particles.

In addition, by adding a bifunctional or less (meth) acrylate monomer or fluororesin to a resin composition containing metal oxide fine particles modified with the polyfunctional (meth) acrylate monomer modification modifier, the weather resistance (durability) and friction resistance Can be improved.

As a bifunctional or less (meth) acrylate monomer which can be used for the hard-coat resin composition of this invention, methyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth), for example. Acrylate, n-butoxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, N-acryloyloxyethylhexahydrophthalimide, glycerindi (meth) acrylate, 2-hydroxy3-acryloyl Oxypropyl (meth) acrylate, tetrahydroperpril (meth) acrylate, 2-hydroxybutyl (meth) acrylate, ethylene glycol di (meth) acrylate, 1,3-propylene glycol di (meth) acrylate , 1,4-heptane diol di (meth) acrylic Nitrate, 1,6-hexanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 2-butyne-1,4-di (meth) acrylate, Cyclohexane-1,4-dimethanol di (meth) acrylate, 1,5-heptanedi (meth) acrylate, trimetholethanedi (meth) acrylate, trimethyllopropanedi (meth) acrylate, di Linear, branched, cyclic (meth) acrylates, or bifunctional compounds such as propylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, dioxane glycol diacrylate Although the following urethane acrylates etc. are mentioned, It is not limited to what was mentioned here as an example. Moreover, these can be used combining one or more types. The content of the bifunctional (meth) acrylate monomer is 30% by weight or less, more preferably 10% by weight to 25% by weight relative to the polyfunctional (trifunctional or higher) (meth) acrylate monomer. When the bifunctional or less (meth) acrylate monomer exceeds 30% by weight, the obtained resin composition coating film (hard coat layer) is likely to be soft.

Moreover, as a fluororesin which can be used for the resin composition for hard coats of this invention, a perfluoro polyethyl acrylate, a perfluoro polyethyl methacrylate, a fluorine-containing polysiloxane, a fluorine-containing cyclic polysiloxane, a fluorine-containing cyclic polysiloxane acrylate Although fluorine-type resins, such as a fluorine-containing cyclic polysiloxane methacrylate, are mentioned, It is not limited to what was illustrated here. Moreover, these can be used combining one type or several types.

In particular, a fluorine resin which is excellent in compatibility with non-fluorine-based organic compounds and capable of photocuring is preferable, and even in a very small amount of addition, the friction resistance can be improved.

In particular, tris (chloromethyl) triazine, 2,4-trichloromethyl- (4'-methoxysteel) -6-triazine as an example of a photopolymerization initiator for curing the obtained resin composition for hard coat with ultraviolet rays. , 2- [2- (fran-2-yl) ethynyl] -4,6-bis (trichloromethyl) -S-triazine, 2,4,6-tris (trichloromethyl) -S-triazine Tribenzoic compounds, such as benzoyl methyl ether, benzoyl ethyl ether, benzoyl isopropyl ether, and benzoyl butyl ether, such as benzoyl compounds, diethoxy acetophenone, 4-phenoxydichloroacetophenone, 2-benzyl-2- dimethylamino- 1- (4-morpholinophenyl) -butan-1-ol (2-benzyl-2- (dimethylamino) -1- (4-morpholinophenyl) 1-butanone), benzophenone, 2-hydroxy-2-methyl Acetophenone compounds, such as propiophenone, 1-hydroxycyclohexylphenyl ketone, and 1-hydroxycyclohexyl acetophenone, thioxanthone, 2-methyl thioxanthone, 2,4-dimethyl thioxanthone, 2 Thioxanthone compounds, such as -chloro thioxanthone, benzyl dimethyl ketal, 2,4,6- trimethyl benzoyl diphenyl phosphine oxide, N, N- dimethylamino benzoate isoamyl, acyl phosphine oxide, etc. are mentioned. However, you may use these 1 type or in combination of 2 or more types. The addition amount is 10 weight% or less with respect to a (meth) acrylate monomer, Preferably it is used at 0.5 to 5 weight%.

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-modifying modifier, a mixture of a modifier having a thiol group (mercapto group) and a trifunctional or higher (meth) acrylate monomer is mixed in a predetermined amount. To produce.

In order to make the obtained mixture react under alkaline conditions, a small amount of triethylamine is added, for example, it is made to react for predetermined time in the range of room temperature-90 degreeC, and addition reaction is performed. In such an addition reaction under alkaline conditions, the acryloyl group and / or the methacryloyl group of the thiol group and trifunctional or higher (meth) acrylate monomer of the modifier are covalently bonded (sulphide bond, -RS-R'- R and R 'are aliphatic and / or aromatic hydrocarbon chains) to form a Michael addition reaction to obtain a polyfunctional (meth) acrylate monomer modified formula.

This reaction is obtained because the acryloyl group and / or methacryloyl group of the thiol group and trifunctional or higher (meth) acrylate monomers of the modifier have a 1: 1 reaction as shown in the following formula (1). The polyfunctional (meth) acrylate monomer modified modifiers leave unreacted acryloyl groups and / or methacryloyl groups.

In addition, the polyfunctional (meth) acrylate monomer-modified modifier obtained by the sulfide bond (-RS-R'-; R and R 'are aliphatic and / or aromatic hydrocarbon chains) obtained by this reaction is flexible. Sex is conferred.

[Formula 1]

(Wherein 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.)

To the obtained polyfunctional (meth) acrylate monomer modified modifier, a predetermined amount of metal oxide fine particles having a hydroxyl group is added to a surface dispersed in an organic solvent. In order to advance the condensation reaction of the polyfunctional (meth) acrylate monomer-modified modifier with the metal oxide fine particles, an alkali or acid diluted with water is added and stirred. By making it react, stirring, the solution containing the metal oxide microparticles | fine-particles modified by the polyfunctional (meth) acrylate monomer modification modifier is obtained. The predetermined amount of the above-mentioned polymerization initiator is added to the obtained solution, and the target resin composition for hard coats is obtained.

In the present invention, the number of hydroxyl groups on the surface of the silica particles is 1.68 mmol / g (see Polymer, Volume 47, Issue 11, 2006, 3754-3759), and several percent of the hydroxyl groups on the surface of the silica particles are polyfunctional (meth) acrylates. The thing substituted by the monomer modification modifier was computed, and it was set as surface modification rate.

If the surface modification rate is too low, surface hardness and friction resistance are poor, and if 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%.

In addition, when improving friction resistance, weather resistance, or impact resistance, the bifunctional or less (meth) acrylate monomer or fluororesin is added at the time of addition of a polymerization initiator. The bifunctional or less (meth) acrylate monomer used in the resin composition for hard coat of the present invention is 30% by weight or less with respect to the (meth) acrylate monomer of polyfunctional (trifunctional or more), and preferably 10 It is 25% by weight. In addition, 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.

The hard coat resin composition of the present invention may be suitably blended with a photosensitizer, a leveling agent, an antifoaming agent, a fluidity regulator, an optical stabilizer, an antioxidant, a coloring agent, a pigment, and the like, as necessary.

In addition, the resin composition for hard coat of the present invention can be produced easily and inexpensively. The resin composition for hard coat is applied to the surface of the substrate by spin coating, spray coating, dip coating, bar coating, flow coating, cap coating, knife coating, die coating, roll coating, gravure coating, screen printing, brushing, or the like. After coating by a predetermined thickness, ultraviolet rays are irradiated, photopolymerized and cured to form a hard coat layer having an effect of improving surface hardness and friction resistance.

Moreover, before coating the resin composition for hard coat, corona discharge, plasma treatment, etc. can be performed with respect to a base material, and the adhesiveness of a hard coat layer and a base material can be improved.

The resin composition for hard coat of this invention is not limited to PMMA resin sheet, Polycarbonate resin, acrylonitrile butadiene styrene resin, vinyl chloride resin, polycycloolefin type resin, polyethylene terephthalate resin, polybutylene terephthalate resin, It can be used as various sheets, films, and film-forming materials such as two-layer and three-layer resins in which triacetyl cellulose resin, polyethylene resin, PMMA resin and polycarbonate resin are bonded. The sheets generally have a thickness of 0.3 to 100 mm and a film of 30 to 300 µm.

The film formation of the hard coat layer is set to 1 to 50 µm, preferably 1 to 20 µm. UV irradiation is formed by ultraviolet rays generated from light sources such as low pressure mercury lamp, high pressure mercury lamp, ultra high pressure mercury lamp, electrodeless lamp, xenon lamp, metal halide lamp, carbon arc lamp, LED lamp and tungsten lamp.

In addition, after applying a board | substrate using the resin composition for hard-coats of this invention, and forming a hard-coat layer, the existing anti-reflective film can also be directly formed on this hard-coat layer. Even if the anti-reflection film is formed directly on the hard coat layer, the adhesion is good and does not come off. Moreover, even if an anti-reflection film is formed, the film-forming properties (friction resistance, surface hardness, etc.) of the resin composition for hard coat hardly decrease. In addition, an existing antifouling agent may be applied onto the hard coat layer to which the resin composition for hard coat of the present invention is applied, thereby improving lubricity.

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

Next, although the Example and comparative example which concern on this invention are given, it demonstrates, but this invention is not limited to this.

≪ Example 1 >

To 90 g of a polyfunctional urethane acrylate monomer (manufactured by Kogyo Co., Ltd., UA-510H), 6.42 g of 3-mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM803) is added, and triethylamine ( 0.408 g of Kishida Chemical Co., Ltd. was added thereto, and heated at 70 ° C. for 2 hours to prepare a polyfunctional (meth) acrylate monomer-modified modifier. The addition reaction was confirmed by NMR. 300 g of silica particle-dispersed MIBK (methyl isobutyl ketone) solution (manufactured by Nissan Chemical Co., Ltd., MIBK-ST, SiO ₂ 30 wt%, average particle diameter 10-20 nm) in a polyfunctional (meth) acrylate monomer-modified modifier After the addition and stirring at room temperature, a mixed solution of 21 g of methyl ethyl ketone and 2.64 g of pure water was added, and stirred at room temperature overnight to prepare a reaction solution containing silica particles modified with a polyfunctional urethane acrylate monomer modified modifier. The solution was concentrated by an evaporator, the solid was 55% by weight, and then filtered.

2.27 g of radical photopolymerization initiators (product of Chiba Specialty Chemicals, Irgacure-184), perfluoropolyethyl acrylate (Solvay Solstices Co., AD-1700) to the above concentrate, difunctional urethane acryl 11.65 g of a rate (DONG-A Synthetic Co., Ltd. product, ARONIX M-1700) was added and stirred, and the target resin composition for hard coats (hard coat liquid) was prepared.

Coating the hard coat liquid on a transparent PMMA substrate (Deaglas, manufactured by Asahi Chemical Technoplus Co., Ltd.) having a thickness of 2 mm using a bar coater, and using the high pressure mercury lamp under an air atmosphere, about 900 mJ / cm 2. Was irradiated with ultraviolet light to form a hard coat layer having a thickness of about 11 μm.

Thus, the following measurement and test were performed and evaluated about the hard coat layer on the PMMA board | substrate obtained. In addition, these measurements and tests were performed after 24 hours or more after the hard coat layer was manufactured. In addition, the same measurement and test were performed and evaluated also about the following Examples 2-14 and Comparative Example 1, and the result was shown in Table 1.

[Pencil hardness test]

The pencil hardness was measured according to JIS-K-5600 with respect to the hard coat layer surface.

Specifically, the cylindrical core of the pencil is left as it is, only the wood portion is removed, and the core is left 5 to 6 mm. After that, the polishing paper is flattened. The pencil is set to the tester specified in JIS. The tester is designed so that the tip of the pencil is 45 ± 1 ° and 750 ± 10 g on the coating surface in the horizontal position.

After the tip of the pencil is provided on the coating film surface, the tester is moved 7 mm or more at a moving speed of 0.5 to 1 mm / s while maintaining the above-described load. While changing the test part, the hardness of the pencil was raised until the scar of at least 3 mm or more occurred. The hardness of the hardest pencil with no scar is the pencil hardness of this test.

Pencil hardness becomes high (hardens) in the following order.

(Soft) 6B, 5B, 4B, 3B, 2B, B, HB, F, H, 2H, 3H, 4H, 5H, 6H (hard)

[ Steel wool resistance  exam]

On the surface of the hard coat layer, the number of wounds at the time of 1.5 kg load / cm 2 and 10 round trip rubs using # 0000 steel cotton (Bon Star Sales Co., Bonstar) was evaluated based on the following criteria.

The test was made at a stroke length of 10 cm and a speed of 1 round trip / second, and the number of wounds within the largest 5 mm angle of the wound was visually counted.

0 wounds: A

There is no wound but there is blur: AB

1 to 5 wounds: B

6-10 wounds: C

11-15 wounds: D

16-20 wounds: E

More than 21 wounds: F

[ Light resistance  exam]

The PMMA base material coated with the hard coat solution was exposed to a black panel temperature of 63 ° C. for 1000 hours using a super-kisenon weather meter SX75 (manufactured by Suga Test Co., Ltd.), and the appearance after the test was evaluated.

[Heat resistance test]

The PMMA base material coated with the hard coat solution was kept constant at 80 ° C. for up to 1000 hours, and the appearance after the test was evaluated.

[Stability of liquid]

50 ml of the hard coat solution was stored at 50 ° C in a dark place, and evaluated by observing the state of the coating solution after 3 months.

The above results are shown in Table 1.

Further, a large amount of propylene glycol monomethyl ether (hereinafter referred to as PGM) was added to the resin composition for hard coat (heart coat solution) of Example 1, and then concentrated by an evaporator. The same operation was repeated to obtain a resin composition for hard coat of PGM solvent.

<Example 2>

In the same manner as in Example 1, the solid content was adjusted to 55% by weight, and then 2.27 g of irkacore-184 was added thereto, followed by stirring to prepare a hard coat liquid. Using this hard coat liquid, coating, measuring, and testing were carried out on the PMMA plate in the same manner as in Example 1, and evaluated. The above result was shown in Table 1.

<Example 3>

In the same manner as in Example 1, the solid content was adjusted to 55% by weight, and then 2.27 g of Irkacore-184 and 11.65 g of ARONIX M-1700 were added and stirred to prepare a hard coat liquid. Using this hard coat liquid, coating, measuring, and testing were carried out on the PMMA plate in the same manner as in Example 1, and evaluated. The above result was shown in Table 1.

<Example 4>

In the same manner as in Example 1, the solid content was adjusted to 55% by weight, and then 2.27 g of irkacore-184 and 1.26 g of AD-1700 were added and stirred to prepare a hard coat liquid. Using this hard coat liquid, coating, measuring, and testing were carried out on the PMMA plate in the same manner as in Example 1, and evaluated. The above result was 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, and 0.408 g of triethylamine was added thereto and heated at 70 ° C. for 2 hours. After heating, the reaction solution was decompressed at 70 ° C. and triethylamine was removed. 300 g of MIBK-ST was added to this reaction solution, and after stirring at room temperature, a mixed solution of 21 g of methyl ethyl ketone and 2.64 g of 0.5 wt% acetic acid solution was added, and the mixture was stirred at room temperature overnight. Thereafter, the solid content was 55% by weight in the same manner as in Example 1, and then 2.27 g of irkacore-184 was added and stirred to prepare a hardcore liquid. Using this hardcore liquid, coating, measuring, and testing were carried out on the same PMMA plate as in Example 1, and the evaluations were made. 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 a tetrafunctional urethane acrylate (manufactured by Daiser Cytec Co., EBECRYL 8210) was used instead of UA-510H. Using this hard coat liquid, coating, measuring, and testing were carried out on the PMMA plate in the same manner as in Example 1, and evaluated. The above results are shown in Table 1.

<Example 7>

A hard coat liquid was prepared in the same manner as in Example 2, except that 90 g of pentaerythritol triacrylate (manufactured by Gonghap Chemical Co., Ltd., light acrylate PE-3A) was used instead of UA-510H. Using this hard coat liquid, coating, measuring, and testing were carried out on the PMMA plate in the same manner as in Example 1, and evaluated. 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 liquid, coating, measuring, and testing were carried out on the PMMA plate in the same manner as in Example 1, and evaluated. The above results are shown in Table 1.

Example 9

A hard coat liquid 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 prepared. Using this hard coat liquid, coating, measuring, and testing were carried out on the PMMA plate in the same manner as in Example 1, and evaluated. The above results are shown in Table 1.

<Example 10>

A hard coat liquid 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 prepared. Using this hard coat liquid, coating, measuring, and testing were carried out on the PMMA plate in the same manner as in Example 1, and evaluated. The above results are shown in Table 1.

<Example 11>

A hard coat liquid 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 liquid, coating, measuring, and testing were carried out on the PMMA plate in the same manner as in Example 1, and evaluated. The above results are shown in Table 1.

<Example 12>

A hard coat liquid 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 liquid, coating, measuring, and testing were carried out on the PMMA plate in the same manner as in Example 1, and evaluated. 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 monofunctional acrylate ARONIX M-140 (manufactured by Dong-A Synthetic Co., Ltd.) was used instead of ARONIX M-1700. Using this hard coat liquid, coating, measuring, and testing were carried out on the PMMA plate in the same manner as in Example 1, and evaluated. 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 a bifunctional urethane acrylate EBECRYL 4858 (manufactured by Daicel Cytec Co., Ltd.) was used instead of ARONIX M-1700. The hard coat solution was coated on a transparent PMMA substrate (Asahi Kasei Techno Plus Co., Ltd., Deraglas) having a thickness of 1 mm using a dip coating machine, and then about 600 mJ / cm 2 using a high pressure mercury lamp under an air atmosphere. Was irradiated with ultraviolet light to form a hard coat layer having a thickness of about 11 μm. Measurement, testing and evaluation were made 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 (manufactured by Kong Chemical Co., Ltd., Lightester M) was used instead of UA-510H. Using this hard coat liquid, coating, measuring, and testing were carried out on the PMMA plate in the same manner as in Example 1, and evaluated. The above results are shown in Table 1.

Comparative Example 2

90 g of UA-510H, 6.42 g of KBM803, 300 ml of tetrahydrofuran as a solvent, 0.245 g of azoisobutyronitrile (AIBN, manufactured by Kishida Chemical Co., Ltd.) as a thermal polymerization initiator were added, and the resultant was replaced with nitrogen gas at 70 캜. Heated. The whole gelled until 20 minutes after the start of heating. 1.5 g of gelate was added to 20 g of acetone and stirred for 24 hours, but no dissolved. The above results are shown in Table 1.

In addition, the following test was performed about the hard-coat layer (Examples 1, 2, 3, 4, 8, 13, 14) on the PMMA board obtained as mentioned above, and the result was shown in Table 2. .

[Moisture resistance test]

The PMMA base material coated with the hard coat solution was kept constant at 500 ° C and 1000 hours at 85 ° C. and 85% humidity, and the appearance after the test was evaluated.

[Heat cycle test]

After the PMMA base material coated with the hard coat solution was stored at -40 ° C for 1 hour and then at 85 ° C for 1 cycle, 10 cycles were repeated, and the appearance was evaluated.

[Fall test]

The PMMA substrate coated with the hard coat solution was fixed on a cylindrical aluminum jig, and the steel balls (36 g in weight and 13/16 inches in diameter) were freely dropped to a height of 20 cm, and the appearance after the test was evaluated. .

(result)

As shown in Tables 1 and 2, it is understood that the resin compositions of Examples 1 to 14 had high frictional resistance and surface hardness, and had good weather resistance of the coating layer and storage stability as a hard coat coating liquid after film formation. there was.

Claims (8)

Modification of polyfunctional (meth) acrylate monomers by covalently bonding a thiol group to acryloyl group and / or methacryloyl group using an addition reaction between a modifier having a thiol group and a trifunctional or higher (meth) acrylate monomer A first step of obtaining an agent; And
And a second step of modifying the multifunctional (meth) acrylate monomer-modified modifier obtained in the first step into metal oxide fine particles. The method of claim 1,
The covalent bond in the first step is a sulfide bond (-RS-R'-; R and R 'is an aliphatic and / or aromatic hydrocarbon with a modifier having the thiol group and the trifunctional or higher (meth) acrylate monomer. Chain)). A method for producing a resin composition for hard coat. The method of claim 2,
The modifier is a method for producing a resin composition for a hard coat, characterized in that the silane coupling agent having a thiol group. The method of claim 3,
And a third step of adding a bifunctional or less (meth) acrylate monomer and / or a fluororesin after the second step. The method according to any one of claims 1 to 4,
The second step is a method for producing a resin composition for a hard coat, characterized in that under alkaline conditions. As a resin composition for hard coat of organic-inorganic hybrid,
The acryloyl group and / or methacryloyl group and sulfide bond (RS-R'-; R and R 'are aliphatic of the thiol group and the trifunctional or higher functional (meth) acrylate monomer of the silane coupling agent having a thiol group. And / or an aromatic hydrocarbon chain), and a metal oxide fine particle modified with a polyfunctional (meth) acrylate-modified modifier. The method of claim 6,
A resin composition for hard coats, further comprising a bifunctional or less acrylate monomer and / or a fluororesin. The method of claim 7, wherein
A resin composition for hard coat, further comprising a photopolymerization initiator.