TW201202363A - Production method of resin composition for hard coating and resin composition for hard coating - Google Patents

Abstract

<Subject> To provide a production method of resin composition for hard coating, which satisfies various performance conditions such as mechanically physical properties of wear resistance and surface hardness, weather resistance, storage stability, and to provide a resin composition for hard coating which is obtained by using the production method thereof. <Solution> The production method of resin composition for hard coating includes: a first step of covalently bonding a thiol group and an acryloyl group and/or a methacryloyl group by using an addition reaction of a modifier having a thiol group and a three-or-more-functional (meth)acrylate monomer, to thereby obtain a polyfunctional (meth)acrylate monomer modified agent; and a second step of modifying a metallic oxide microparticle by using the polyfunctional (meth)acrylate monomer modified agent obtained from the first step.

Description

[Technical Field] The present invention relates to a method for producing a resin composition for hard coating of (meth)acrylate-based fine particles in which inorganic fine particles are blended, and a resin composition for hard coating. [Prior Art] A resin composition in which inorganic fine particles are blended in a resin is known for the purpose of improving mechanical properties such as heat resistance of an acrylic resin such as acrylonitrile (hereinafter referred to as P M M A ). With respect to these resin compositions, it is known that a resin composition in which mechanical properties are improved by performing a sol-gel reaction with an alkoxyalkyl group-containing acrylic polymer and a metal alkoxide. (refer to the patent document υ. These resin compositions are applied as a hard coating liquid to a resin substrate such as a plastic sheet, a plastic lens, or a plastic film, and can be used to improve the mechanical properties of the substrate. In the coating liquid for hard coating, a coating liquid for hard coating containing an organic resin matrix component and a coated metal oxide fine particle formed by a polymer decane coupling agent film is known (refer to Patent Document 2). [Patent Document 1] [Patent Document 1] JP-A-2004-277512 (Patent Document 2) JP-A-2009-083223 (Summary of Invention) 3 201202363 [Problems to be Solved by the Invention] The resin composition has a function as a hard coat by being applied to a resin substrate. · τ expects that, in general, hard coating can improve wear resistance and surface mechanical properties, but it is difficult At the same time, it is possible to improve the mechanical properties and weather resistance of the machine-inorganic coating solution for hard coating, and there is a problem that the alum solution and the cloth cloth have problems in the nature of the coating, and it is expected to satisfy the composition. In view of the problems of the above-mentioned prior art, the technique of the present invention provides a method for producing a resin composition for hard coating which can satisfy various performance conditions such as mechanical properties such as abrasion resistance and surface hardness, and weather resistance and properties. 2, and a resin composition for hard coating by the method. [Means for Solving the Problem] As a result of intensive research, the present inventors have found that a modifier containing a thiol group (thiol group) is included. A metal oxide fine particle modified by a polyfunctional (meth)acrylic acid monomer modification modifier obtained by an addition reaction of a (meth)acrylic acid vine monomer having a functional group or more, and an organic-inorganic hard coating type The tree mash product can be synthesized only in a simple manner, and the mechanical properties of the surface hardness and the abrasion resistance, as well as the weather resistance and the storage stability are good, and can be suitably used as a resin composition for hard coating. In the description, the modifier used is particularly suitable for the use of a decane coupling agent having a sterol group which is not represented by the formula (1). HS-(CH2)n-Si(Ri)x(10)2)3 χ · ••(1) (R and Κ2 each independently represent a lower alkyl group selected from the carbon number 丨4 and a base of the 201202363 group, η represents an integer of 1 to 11 of the number of chains of the potassium group, and X is ruthenium or has a thiol group. Examples of the decane coupling agent include 3 _ 美美丙美 _ 曱 methoxy decane, 3-mercaptopropyl triethoxy decane, 3 _ propyl propyl carbaryl oxy sulphate, 3- syl propyl propyl Further, in the present invention, a trifunctional or higher functional group is used. Further, in the present invention, a trifunctional or higher functional group (indenyl group) is used. The acrylate monomer can be used as listed below. Further, the "·· · · · C methyl acrylate" acrylate on the mark means "···Acrylate" or "·..••methyl acrylate". First, a trifunctional or higher (fluorenyl) acrylate may, for example, be exemplified by trimethyl methacrylate trimethyl propyl citrate, succinimide τ * twig pitch propane diacrylate, ethylene oxide modified Trimethylolpropane triacrylate, | double alpha-succinyl alcohol triacrylate S, pentaerythritol tetraacrylic acid vinegar, dipentaerythritol hexaacetic acid vinegar, tetramethylol methane triacrylate vinegar, tetramethylol Methane tetraacrylate vinegar, hydrazine. _ Residual ethyl) isocyanurate triacrylate or the like, such as a branched or cyclic (fluorenyl) acrylate or urethane acrylate, but is not limited thereto. Furthermore, these may be used in combination of one type or plural types. In addition, examples of the metal oxide fine particles to be used include, for example, oxidized oxide (Si〇2), oxidized (Al2〇3), oxidized (Zr〇2), oxidized (1) (1), and tin-doped oxidation. Indium (-, tin oxide (called zinc oxide (Zn〇), oxidized bromine (Sb2〇3, Sb2〇5, etc.)' and such composite fine particles, etc. Further, the metal oxide fine particles of this type have a surface on the surface The particle size of the metal oxide fine particles used in the present embodiment is flat 201202363. The average-secondary particle diameter is iGGnm or less, preferably the following q average-under (four) is mnm or less, and the hard coating resin composition is The specific transparency of the (meth) acrylate resin is also maintained after the strand is hardened. Further, the 'content of the metal oxide fine particles' has a relationship with the polyfunctional (trifunctional or higher) (meth)acrylic acid acrylate monomer and the surface. The amount of the metal oxide fine particles to be mixed is preferably 20% by weight, and % by weight, and preferably 40% by weight or less. When the metal oxide fine particles are less than 2% by weight, the effect is hard to be manifested. , metal oxide particles more than 6 〇 weight At the time, the obtained resin composition is liable to become brittle. Further, a highly reactive metal &amp; alkoxide such as ruthenium, titanium, iridium or aluminum may be added together with the metal oxide fine particles, or may be added in place of the metal oxide fine particles. Further, a bifunctional or lower (meth)acrylic acid vinegar monomer is added to the resin composition containing the metal oxide fine particles modified by the polyfunctional (meth) acrylate monomer described above. The weathering fastness (durability) and the abrasion resistance can be improved. The (meth) acrylate monomer having a bifunctional or lower functional group which can be used in the resin composition for hard coating of the present invention is, for example, (methyl). Ethyl acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-butoxyethyl (meth)acrylate, decyloxy polyethylene glycol (meth) acrylate , (fluorenyl) benzyl acrylate, isobornyl (meth)acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, N - propylene decyloxyethyl hexahydroindole Imine, glycerol mono(indenyl) acrylate, 2-based 3-propyl propyl propyl (meth) acrylate, (mercapto) methacrylate, (meth) acrylate 2 _ Hydroxybutyrate

S 6 201202363 Ester, ethylene glycol bis(indenyl) acrylate, 1,3-propanediol bis(indenyl) acrylate, 1,4-heptanediol bis(indenyl) acrylate, 1,6-hexane Alcohol di(meth) acrylate, diethylene glycol di(meth) acrylate, tetraethylene glycol di(decyl) acrylate, 2-butane-1, 4-di(decyl) acrylate, Cyclohexane-1,4-dimethanol bis(indenyl) acrylate, i(5-pentyl) bis(indenyl)acrylate, tri-decyl ethane bis(indenyl) acrylate, trihydroxy fluorenyl Linear, branched, etc. of propane bis(indenyl) acrylate, dipropylene glycol bis(indenyl) acrylate, hydrazine, 3-butanediol di(meth) acrylate, dioxane diol diacrylate Chain, cyclic (meth) acrylate or bifunctional urethane acrylate or the like, but not limited thereto. Furthermore, these types or combinations can be used in combination. Further, the content of the bifunctional or lower (meth) acrylate monomer is 30% by weight or less, more preferably 1% by weight based on the polyfunctional (trifunctional or higher) (meth) acrylate monomer. ~μ% by weight. When the (meth) acrylate monomer having a bifunctionality is more than 3% by weight, the resulting resin composition coating film (hard coat layer) tends to be soft. The fluorine-containing polyoxane, the dilute acid, and the fluorine-containing are not limited to these. Further, the fluorine resin which can be used in the resin composition for hard coating of the present invention is a perfluoropolyether acrylate, a perfluoropolyether methacrylate, a fluorine-containing cyclic polyoxane, or a fluorine-containing ring. Polyoxyalkylene

Examples can be exemplified by hydrazine (chloromethyl) three 201202363 azine, 2, 4-trimethyl fluorenyl _ (4'-methoxystyryl)-6-triazine, 2-[2-(coopan- 3-yl)ethidyl]_4,6-bis(trichloroindenyl)-S-trimethyl, 2,4,6-fluorene (trichloromethyl)-S-triazine and other triazine compounds, Benzoin compounds such as benzoin methyl ether, benzoin ethyl ether, benzoin C &amp; |, benzoin butyl ether, diethoxy acetophenone, 4-phenoxy acetophenone, 2-benzyl- 2-Dimethylamino-1-(4-indole-morpholinophenyl)butane-propanol, benzophenone, 2-hydroxy-2-mercaptopropiophenone, 1-hydroxycyclohexylphenyl An acetophenone compound such as a ketone or a 1-hydroxycyclohexylethyl benzene benzene, a thioxanthone (1:1^〇 meaning 3111±〇116), a 2-methyl-sodium ketone, a 2,4_2 a thioxanthone compound such as methyl ketone or 2-ox thioxanthone, benzyl dimethyl acetal, 2, 4, 6-trimethyl benzoin diphenyl phosphine oxide, N, N-di The isoamyl acetyl benzoate or the fluorenyl phosphine oxide may be used in combination of one type or two types or more. The amount of addition is 1% by weight or less, preferably 0.5 to 5% by weight based on the (meth) acrylate single system. Next, a method of producing the resin composition of the present invention will be described. First, in order to obtain metal oxide fine particles modified with a polyfunctional (meth) acrylate monomer modification modifier, a modifier having a thiol group (fluorenyl group) and 3 g of a (meth) acrylate monomer alone or more The mixture is mixed in a prescribed amount to prepare a mixture. In order to react the resulting mixture under basic conditions, for example, by adding a certain amount of triethylamine, it is allowed to react for a predetermined period of time at a temperature of from room temperature to 9 Torr to carry out a hydrazine addition reaction. In the addition reaction under such basic conditions, the thiol group and the acryloyl group and/or the fluorenyl fluorenyl group having a trifunctional or higher (meth) acrylate acid monomer are used in the addition reaction. Covalent bonding (sulfur bonding,

S 8 201202363 -RS-R' -: The Michael (additional) reaction of Michael monomer modifier R and R' is an aliphatic and/or aromatic hydrocarbon chain to obtain a polyfunctional (meth)acrylic acid vinegar The reaction system has a thiol group and/or a methacryl fluorenyl group having a thiol group and a trifunctional or higher (meth) acrylate monomer in a manner shown by the following Chemical Formula 1, and is added in a 1:1 ratio. In the reaction, unreacted acrylonitrile group and/or methacryl oxime group remain in the obtained polyfunctional (meth) acrylate monomer modification modifier. Further, by the sulfur bonding obtained by the reaction, -: R &amp; R, an aliphatic and/or aromatic hydrocarbon chain) imparts flexibility to the obtained polyfunctional (meth) acrylate monomer modification modifier. 【化1】

Chemical reaction formula (wherein Ra represents a residue of a polyfunctional (meth) acrylate monomer, R b — a residue of a modifier having no thiol group, and R′ represents an aliphatic and/or a fragrant group Tobacco chain) known as a polyfunctional (fluorenyl) acrylate monomer modification modifier

JjXJ -iS Field S is a metal oxide fine particle having a hydroxyl group dispersed on an organic solvent. In order to carry out the condensation reaction of the polyfunctional (meth) acrylate monomer modification 201202363 varnish with the metal oxide fine particles, the test or acid diluted with water is added and mixed. By stirring and reacting, a solution containing metal oxide fine particles modified with a polyfunctional (meth) acetoacetate monomer modification modifier is obtained. By adding a predetermined amount of the above polymerization initiator to the obtained solution, the target hard-coated (tetra) lipid composition can be obtained. The base number of the surface of the oxidized stone particles of the present invention is 1.68 mm / l / g (refer to 17 'V〇lume 47' Issue 11, 2006, 3754-3759), the number of the base of the surface of the oxidized stone particles, The replacement of the polyfunctional (meth)acrylic acid vinegar monomer modification modifier was calculated as the surface shaving rate. When the surface repair rate is too low, the surface hardness and abrasion resistance are poor, and when it is too high, the storage stability of the resin composition is deteriorated. The surface modification ratio 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 the case where the wear resistance, the weather resistance and the impact resistance are improved, the addition of a difunctional or lower (mercapto) acrylate precursor or a fluororesin together with the initiator is added. The bifunctional or less (fluorenyl) acrylate monomer used in the resin composition for hard coating of the present invention is 3 重量% by weight based on the polyfunctional (trifunctional or higher) (fluorenyl) acrylate monomer. Hereinafter, it is more preferably 1 〇 reset % 25 wt%. In addition, the fluororesin used in the resin composition for a hard coating of the present invention is 0% by weight based on the total amount of the resin composition. Further, the resin composition for hard coating of the present invention, if necessary, It can be suitably combined with a photosensitizer, a leveling agent, an antifoaming agent, a fluidity adjusting agent, a light stabilizer, an antioxidant 'coloring agent, a pigment, and the like. 201202363 Further, the resin composition for hard coating of the present invention is simple in production process and can be produced at low cost. The hard coating resin composition is applied to the surface of the substrate by spin coating, spray coating, dipping, bar coating, roll coating, mold molding, blade coating, die coating, roll coating, gravure coating, screen printing. After applying a predetermined thickness, such as brush coating, it is photopolymerized by irradiation with ultraviolet rays, and is hardened to form a hard coat layer having an effect of improving surface hardness and abrasion resistance on the substrate. Before the coating of the resin composition, the substrate is subjected to arc discharge, plasma treatment, etc., and the adhesion between the coating and the substrate can be improved. The resin composition for hard coating of the present month is not limited to the ρ·Α resin sheet, and a polycarbonate resin, an acrylonitrile butadiene styrene resin, a gas-ethylene resin, a polycyclic hydrocarbon resin, and a poly Terephthalic acid 乙乙@|Resin, poly-p-dicarboxylic acid propylene vinegar resin, cellulose triacetate resin, polyethylene resin, PMMA resin and polycarbonate resin, 2 layers and 3 layers of resin, etc. , film, molding materials. In general, the sheet thickness is 〇〇_ and the film is 30 to 300//m. The film thickness of the hard coating layer is 50/zm, preferably 1~20#m〇 UV irradiation system is composed of low pressure mercury lamp, high pressure mercury lamp, ultra high pressure mercury lamp, electrodeless lamp, xenon lamp, metal halide lamp, carbon The sub-outline from the light source such as an arc lamp, an LED lamp, or a tungsten lamp is used for film formation. Further, after the substrate is coated with the resin composition for hard coating of the present invention to form a hard coat layer, an existing anti-reflection film can be directly formed on the hard coat layer. The direct anti-reflection film formed on the hard coat layer also has good adhesion without peeling off. Further, the resin composition for hard coating forming the antireflection film 11 201202363 has a film property (abrasion resistance, surface hardness, etc.) which is not easily lowered. Further, the existing antifouling agent is applied to the hard coat layer formed by coating the resin composition for hard coating of the present invention, and the slidability can be improved. [Effects of the Invention] According to the resin composition for hard coating of the present invention, high abrasion resistance and surface hardness (pencil hardness) can be obtained, and the weather resistance of the coating layer after film formation can be satisfied and the coating can be performed. Preservation stability of the liquid. [Embodiment] Next, although the examples and comparative examples of the present invention are described, the present invention is not limited thereto. <Example 1> Addition of 3-mercaptopropyltrimethoxyoxane to 90 g of a polyfunctional amino phthalate acrylate monomer (manufactured by Kyoeisha Chemical Co., Ltd., UA-510H) (Shin-Etsu Chemical Industry Co., Ltd. Manufactured, KBM803) 6.42 g, added triethylamine (manufactured by Kishida Chemical Co., Ltd.) 〇. 4〇8g, at 70. (: heating for 2 hours to prepare a polyfunctional (meth) acrylate monomer modification modifier. The addition reaction was confirmed by NMR. Addition of cerium oxide particles was added to the polyfunctional (fluorenyl) acrylate monomer modification modifier. MIBK (methyl isobutyl ketone) solution (manufactured by Nissan Chemical Industry Co., Ltd., MIBK-ST, Si〇2 30wt%, average particle size 1〇~20nm) 300g, square, to value after mixing, add methyl ethyl The mixture of 21 g of ketone and pure water of 2.64 g was mixed at room temperature for one night, and the reaction of oxidized hard particles modified with a polyfunctional amino carboxylic acid vinegar The solution was concentrated by an evaporator, and the solid content was 55% by weight, followed by filtration.

S 12 201202363 Addition of photoradical polymerization initiator to the above concentrate (Ciba

Manufactured by Speciality Chemical Company, Irgacure 184) 2·27g, all-in-one polyacrylic acid vinegar (made by Solvaysolexis, AD-1 700) 1. 26g, difunctional amino phthalate acrylate (manufactured by Toagosei Co., Ltd., ARONIX) M-1700) 11.65g was stirred and the resin composition for coating (hard coating liquid) was produced. The hard coating liquid was applied to a transparent PMMA substrate (Delaglas, manufactured by Asahi Kasei Techno-plus Co., Ltd.) having a thickness of 2 mm using a hard coater, and irradiated with a high-pressure mercury lamp at about 9 〇〇mJ/cm 2 in an air atmosphere. The UV rays form a hard coat layer with a film thickness of about 11 #m. The hard coating layer on the PMMA sheet obtained in the above manner was subjected to the following measurement and test, and evaluated. Further, these measurements and tests were carried out 24 hours or more after the hard coat layer was produced. Further, in the following Examples 2 to 14 and Comparative Example 1, the same flaws and tests were carried out, and the results were shown in the table [Writing pen hardness test]. The surface of the 垔 垔 layer was directly retained according to the vertical/body. The cylindrical core of the pencil 'only cuts the wood: the second two retains the core 5~6mm. Then, using the abrasive paper, the front end of the core was examined in a flat manner, and the front end of the core was flattened with abrasive paper. Will be wrong to make two: two testers. When the tester is in a horizontal position, the end is gamma to the coated surface. The way the load of the shaft g is. : The front end of the pen is placed on the surface of the coating film, while maintaining the above-mentioned load, a test: W: M multi-moving speed to move the tester. The scratch test hardness of at least 3 or more is not changed by the knife test. The hardest pen hardness of the ship that does not cause scratches is used as the pencil hardness of the test. The hardness of the ship's pen is increased (hardened) in the following order. (soft) 6Β· 5Β· 4Β· 3Β· 2Β· Β· HB· F. Η. 2Η· 3Η· 4H. 5Η · 6Η (hard) [steel sling (st ee 1 woo 1) test] Hard coating The surface of the layer was evaluated using the #0000 steel wool (Bonstar, manufactured by B〇nstar Sales Co., Ltd., Bonstar) at 1.5 kg load/cm2, and the number of scratches at the time of repeated wiping was evaluated on the following basis. The test was carried out at a speed of 1 〇cm and 1 round trip/second, and the number of scratches in the 5 mm angle where the scratches were the most was visually calculated. When the scratch is 0: a

No scratches and fog: AB

Scratches are 1~5 bars: B scratches are 6~10 bars: c

Scratches are 11~1 5 :D

Scratches are 16~20: E

Scratches are 21 or more :F

[Light resistance test] For the PMMA substrate coated with the hard coating liquid, a super xenon weather meter (SX75) (manufactured by SUGA Testing Machine Co., Ltd.) was used, and the black panel temperature was 63 Torr. The exposure test after hours 'evaluates the appearance after the test. [heat resistance test]

S 14 201202363 The P匪A substrate coated with the hard coating liquid was kept at 80 ° C for 1 〇〇〇, and the appearance after the test was evaluated. [Solidity of liquid] 50 ml of the hard coating liquid was stored in a dark place at 50 ° C for 3 months, and the state of the coating liquid was observed and evaluated. The above results are shown in Table 1. Further, a large amount of propylene glycol monodecyl ether (hereinafter referred to as PGM) was added to the resin composition for hard coating (hard coating liquid) of Example 1, and then concentrated by an evaporator. The same procedure was repeated to obtain a resin composition for hard coating of a PGM solvent. <Example 2> When the same concentration step as in Example 1 was carried out until the solid content was 55%, 2.27 g of lRGACURE 184 was added, followed by stirring to prepare a hard coating liquid. The coating, measurement and test of the PMMA plate were carried out in the same manner as in Example i using this hard coating liquid, and evaluated. The above results are shown in Table i. <Example 3> The same concentration step as in Example 1 was carried out until the solid content was 55 wt%.

The results are shown in Table 1. &lt;Example 4&gt;

From the town to the solid content of 55wt% 1 · 26g AD-1700 after mixing 201202363 mix to make a hard coating liquid. The coating, measurement, and test of the PMMA sheet were evaluated in the same manner as in Example i using this hard coating liquid. 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, and after adding 8 g of triethylamine oxime, it was heated at 70 ° C for 2 hours. After heating, the reaction solution was dehydrated at 70 C to remove triethylamine. To the reaction mixture, 300 g of MIBK-ST was added, and after stirring at room temperature, a mixture of 2 g of methyl ethyl ketone and 2.64 g of 0 - 5 wt% aqueous acetic acid solution was added, and the mixture was stirred at room temperature overnight. Thereafter, the same concentration step as in Example 1 was carried out until the solid content was 55 wt%. After adding 2.27 g of IRGACURE 184, the mixture was stirred to prepare a hard coating liquid. The coating, measurement, and test of the PMMA sheet were evaluated in the same manner as in Example 1 using this hard coating liquid. The above results are shown in Table 1. <Example 6> A hard coating liquid was prepared in the same manner as in Example 2 except that 9 g of a tetrafunctional amino phthalate acrylate (EBECRYL 8210 manufactured by Dice Co., Ltd.) was used instead of UA-510H. The application, measurement, and test of the PMMA plate were carried out in the same manner as in Example 1 using this hard coating liquid, and the evaluation was carried out. The above results are shown in Table 1. <Example 7> A hard coating liquid 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. The coating, measurement, and test of the PMMA plate were carried out in the same manner as in Example 1 using this hard coating liquid, and evaluated.

16 S 201202363 The above results are shown in Table 1. <Example 8> A hard coating liquid was prepared in the same manner as in Example 1 except that 5.89 g of 3-bromopropylmethyldimethoxy decane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM802) was used instead of KBM803. The coating, measurement, and test of the PMMA plate were carried out in the same manner as in Example 1 using this hard coating liquid, and evaluated. The above results are shown in Table 1. <Example 9> A hard coating liquid was prepared in the same manner as in Example 2 except that UA-510H 72 g, KBM8 03 7.70 g, triethylamine 〇_490g, and MIBK-ST 36 0g were used. The coating, measurement, and test of the PMMA sheet were evaluated in the same manner as in Example 1 using this hard coating liquid. The above results are shown in Table 1. <Example 10> A hard coating liquid was prepared in the same manner as in Example 2 except that UA-510H 108 g, KBM803 5.14 g, triethylamine oxime. 326 g, and MIBK-ST 24Og. The coating, measurement, and test of the p-A plate were carried out in the same manner as in Example 1 using this hard coating liquid, and evaluated. The above results are shown in Table 1. <Example 11> A hard coating liquid was prepared in the same manner as in Example 2 except that KBM803 was 3.21 g and triethylamine oxime was used. The coating, measurement, and test of the PMMA plate were carried out in the same manner as in Example 1 using this hard coating liquid, and evaluated. The above results are shown in Table 1. <Example 12> A hard coating liquid was produced in the same manner as in Example 2 of 201202363 except that KBM803 12·48 g and triethylamine oxime. 912 g. The coating, measurement, and test of the PMMA plate were carried out in the same manner as in Example 1 using this hard coating liquid, and evaluated. The above results are shown in Table 1. <Example 13 &gt; The same as Example 3 except that 11.65 g of a monofunctional acrylate ar〇N IX --140 (manufactured by Toagosei Co., Ltd.) was used instead of 八1?(^1 and elbow_17〇〇). The hard coating liquid was prepared and the coating, measurement, and test of the PMMA board were carried out in the same manner as in Example 1 and evaluated. The above results are shown in Table 1. <Example 14> In addition to use A hard coating liquid was prepared in the same manner as in Example 3 except that AESCRYL 4858 (manufactured by Dice 1-Cytec Co., Ltd.) of a difunctional urethane acrylate of 19.67 g was used in the same manner as in Example 3. The hard coating was used. The coating liquid was applied to a transparent PMMA substrate (manufactured by Asahi Kasei Techno-Plus Co., Ltd. 'Delaglas) having a thickness of 1 min, and irradiated with ultraviolet rays of about 600 mL/cm 2 in a high-pressure mercury lamp under an air atmosphere to form a hard coating having a film thickness of about 11 μm. The measurement and the test were carried out in the same manner as in Example 1. The above results are shown in Table 1. <Comparative Example 1 &gt; In addition to 90 g of decyl methacrylate (manufactured by Kyoeisha Chemical Co., Ltd., LIGHT-ESTER) M) In addition to UA-510H, Example 2 was produced in the same manner a hard coating liquid. The hard coating solution used in Example 1 to the same manner as the coated PMMA plate, test and measurement, be evaluated. The results are shown above in Table 1.

S 201202363 <Comparative Example 2 &gt; Furan was added to UA-510H 90g, KBM803 6·42g, 300ml, tetrahydrobutyronitrile as a solvent for thermal polymerization initiator (AIBN manufactured by Kishida Chemical Co., Ltd.) 0.245g 'Replace with gas fluoride at 7〇. 〇 Start heating. After the start of heating, the whole gelation was carried out for 20 minutes, and 1.5 g of the gelled product was added to 20 g of acetone, and the mixture was stirred for 24 hours without being dissolved. The above results are shown in Table 19 201202363. Further, the hard coat layers (Examples 1, 2, 3, 4, 8, 13, 14) on the PMMA sheet obtained in the above manner were subjected to the following tests and evaluated, and the results are shown. In Table 2. These measurements and tests were carried out after 24 hours or more after the hard coat layer was produced. [Moisture resistance test] The appearance of the test was evaluated by applying a hard-coated PMMA substrate at 85 ° C and a humidity of 85% at a constant temperature for 500 hours or 1 〇 〇 hr. [Thermal Cycling Test] The PMMA substrate coated with hard coating was evaluated at _4 (after ar storage for 1 hour, at 85T: at 1 hour for 1 hour, and after 1 cycle, the appearance after the test was evaluated. [Balling test] The hard-coated PMMA substrate was fixed on a cylindrical oxidized jig, and the steel ball (resonance, diameter i3/i6 吋) was freely dropped from the height of 2 〇 Cm toward the center, and the appearance after the test was evaluated.

S 20 201202363 No ball change test without appearance change ^ 5 No appearance change No appearance change No appearance change Thermal cycle test No appearance change μ No appearance change W· LO dish No appearance change No appearance change No appearance change Wetness test ^ -1J ^ § § X) J i CN1 瑞 碟 J iz female CNI carbon ^ Λ 3 J m = i ^ = female οα #. 4 λ3 ί 7 δ OJ #, Η steel wool test - &lt; Μ pencil hardness S == CO 3= CD SC CO S: CO ι-Γ* 3 αζ ς〇Fluororesin AD-1700 1.26g #- AD-1700 1.26g AD-1700 1.26gm AD-1700 1.26g Additive monofunctional or difunctional ARONIX M-1700 11.65g ARONIX M-1700 11.65g #. ARONIX M-1700 11.65g ARONIX Μ-140 11.65g EBECRYL 4858 19. 67g 矽 矽 MIBK-ST 300g MIBK-ST 300g MIBK-ST 300g MIBK-ST 300g MIBK-ST 300g MIBK-ST 300g MIBK-ST 300g Triethylamine 0.408g Triethylamine oxime 0. 408g Triethylamine 0. 408g Triethylamine 0. 408g Triethylamine 0. 408g Triethyl Amine 0. 408g Triethylamine 0. 408g (meth) acrylate monomer UA-510II UA-510H cn> UA-510H m σΐ UA-510H CTi UA-510II Μ-510H CD UA-510II b〇03⁄4 decane coupling agent KBM803 6.42g KBM803 6. 42g KBM803 6. 42g KBM803 6. 42g KBM803 5. 89g KM803 6. 42g ΚΒΜ803 6. 42g Example 〇〇CO 〇 〇CO inch 201202363 (Results) As shown in Tables 1 and 2, the resin compositions of Examples 1 to 14 can obtain high abrasion resistance and surface hardness, and the weather resistance of the coating layer after film formation, The storage stability of the hard coating liquid is good. [Simple diagram description] None [Main component symbol description] None

S 22

Claims (1)

201202363 VII. Patent application scope: The method of hard coating _ heart-making method, Qian Zheng is based on the modification agent with alcohol base and the (methyl) acrylate acid on the 3 official Covalently combining a thiol group with an acrylonitrile group or a methacryl oxime group, and the first step of the (meth) acrylic acid acetal monomer modification modifier; The second step of modifying the metal oxide fine particles by the above-mentioned multi-layered Sflb (fluorenyl) acrylate monomer modification modifier obtained in the first step is the resin composition for hard coating according to claim 1. The method 'wherein the aforementioned covalent bond in the first step is a thiol group-containing modifier 盥3 which has a disulfide bond of the above (meth) acrylate monomer (A /, 3 s s) ' _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ The above-mentioned broth coupling agent of two thiol groups of the sulphate W. 4. Hard coating as described in the third paragraph of the patent application scope A method for producing a resin composition, wherein, after the second step of the needle, +, seedling m, and the second step, a bifunctional-(meth)acrylate monomer and/or a fluororesin is added. The above-mentioned second step of the hard coating described in the section is based on the production method of the resin composition in the range of 丨 to 4, wherein the organic-inorganic composite is characterized in that the composite 6. A hard coating resin composition for a hard coating resin composition 23 201202363 The material is a thiol group having a thiol group-containing decane coupling agent, and a trifunctional or higher group (A) The propylene sulfhydryl group and/or the mercapto propylene aryl group of the propyl acrylate monomer are formed by a disulfide bond (-RS-R' -: R and R, which are aliphatic and/or aromatic smoke chains). The metal oxide fine particle modified by the polyfunctional (meth) acrylate monomer modification modifier. The resin composition for hard coating according to claim 6 of the patent application' Acrylate monomer and/or fluororesin. 8. Hard as described in claim 7 The resin composition for coating' contains a photopolymerization initiator.