JP5236326B2 - Hard coating composition, molded article, and lens - Google Patents

Description

  The present invention contains at least a specific silane compound and / or a compound in which it is partially condensed, a metal oxide fine particle, and a metal chelate compound, and has high scratch resistance while maintaining a practical level of adhesion. The present invention relates to a hard coat agent composition having excellent impact properties.

As lenses for spectacles, resin lenses are rapidly spreading instead of glass lenses for reasons such as lightness, impact resistance, and colorability. Conventionally, radically polymerized diethylene glycol bis (allyl carbonate) (hereinafter abbreviated as D.A.C.), polycarbonate (PC), polymethacrylic acid methacrylate (PMMA), and the like have been used for these purposes. However, since these lens resins have a refractive index of n _d = 1.49 to 1.58, in order to obtain optical characteristics equivalent to those of a glass lens, the center thickness, edge thickness, and curvature of the lens are increased. Resin having higher refractive index has been demanded because of the necessity and overall thickness.

As a countermeasure against such a problem, Patent Document 1 describes a resin obtained by thermally polymerizing a thiol compound and an isocyanate compound to form a thiourethane bond, and has a refraction of n _d = 1.60 to 1.67. The rate is obtained.

In addition, a resin obtained by forming an epithiosulfide bond by ring-opening thermal polymerization of a thioepoxy compound described in Patent Document 2 has a refractive index of n _d = 1.70 or more.

  On the other hand, since the resin lens is much inferior to the glass lens in terms of surface hardness and scratch resistance against the advantages such as lightness, impact resistance, and colorability, it prevents the surface from being scratched as a countermeasure. So-called hard coat treatment is indispensable.

  For this hard coat treatment, a thermosetting silicone hard coat agent is mainly used. Although the cured film has scratch resistance, it has a tendency to lack impact resistance due to poor flexibility.

  In order to compensate for this lack of impact resistance, a lens layer is further coated with a resin layer having impact resistance. (Patent Document 3)

  As described above, in order to apply a coating process having excellent scratch resistance and impact resistance to the surface of the resin lens, in the conventional technique, two separate layers for imparting scratch resistance and impact resistance are used. It is necessary to form. Therefore, the number of times of application is two times, and there is a problem that the manufacturing cost increases from the viewpoint of work efficiency.

  Although Patent Document 4 and Patent Document 5 exist as methods for imparting scratch resistance and impact resistance by only one application, the adjustment of the liquid is complicated and the storage stability is poor. Had a problem with.

Japanese Patent Laid-Open No. 9-110956 JP 2002-140883 A JP 05-214136 A JP 2005-139236 A JP 2007-119635 A

  An object of the present invention is to provide a hard coat agent composition that imparts both high scratch resistance and excellent impact resistance while maintaining a practical level of adhesion by only one application.

  In order to solve these problems, the present inventors have conducted intensive studies and found that they contain at least a specific silane compound and / or a compound in which it is partially condensed, metal oxide fine particles, and a metal chelate compound. The hard coat agent composition blended at a specific composition ratio was found to have high scratch resistance and excellent impact resistance while maintaining a practical level of adhesion.

That is, the present invention
[1] At least the following components (A) to (D) are contained, and in a total of 100 parts by weight of components (A) to (C), component (A) is 5 to 60 parts by weight, and component (B) is 35. -90 parts by weight, component (C) is 5-70 parts by weight, and component (D) is 0.01-10 parts by weight with respect to 100 parts by weight of the total of components (A)-(C). Hard coat agent composition.
Component (A): Silane compound represented by formula (1)

  Component (B): Silane compound represented by general formula (2), a compound in which it is partially condensed, or a mixture thereof

（上記式中、Ｒ ^６ は水素またはメチル基、Ｒ ^７ はメチル基またはエチル基を表す。
ｎ _７ 、ｎ _８ はそれぞれ独立に１〜１０の整数を表す。）
成分（Ｃ）：Ｓｉ、Ａｌ、Ｓｎ、Ｓｂ、Ｔａ、Ｃｅ、Ｌａ、Ｆｅ、Ｚｎ、Ｗ、Ｚｒ、Ｉｎ、Ｔｉから選ばれる金属の１種又は２種以上の酸化物微粒子又は複合微粒子である金属酸化物微粒子
成分（Ｄ）：Ｃｕ（ＩＩ）、Ｚｎ（ＩＩ）、Ｃｏ（ＩＩ）、Ｎｉ（ＩＩ）、Ｂｅ（ＩＩ）、Ｃｅ（ＩＩＩ）、Ｔａ（ＩＩＩ）、Ｔｉ（ＩＩＩ）、Ｍｎ（ＩＩＩ）、Ｌａ（ＩＩＩ）、Ｃｒ（ＩＩＩ）、Ｖ（ＩＩＩ）、Ｃｏ（ＩＩＩ）、Ｆｅ（ＩＩＩ）、Ａｌ（ＩＩＩ）、Ｃｅ（ＩＶ）、Ｚｒ（ＩＶ）又はＶ（ＩＶ）を中心金属原子とする、アセチルアセトネート、アミノ酸、ルイス酸、又は有機酸金属塩の中から選ばれる少なくとも一つである金属キレート化合物 (In the above formula, R ¹ is an organic group having a cationic polymerizable group represented by the general formulas (5) and (6) , R ² and R ³ are each independently hydrogen or an alkyl group, and n ₁ represents an integer of ₁ to 3.)

(In the above formula, R ⁶ represents hydrogen or a methyl group, and R ⁷ represents a methyl group or an ethyl group.
n ₇ and n ₈ each independently represents an integer of 1 to 10. )
Component (C): Si, Al, Sn, Sb, Ta, Ce, La, Fe, Zn, W, Zr, In, Ti, one or more kinds of oxide fine particles or composite fine particles Metal oxide fine particle component (D): Cu (II), Zn (II), Co (II), Ni (II), Be (II), Ce (III), Ta (III), Ti (III), Mn Centered on (III), La (III), Cr (III), V (III), Co (III), Fe (III), Al (III), Ce (IV), Zr (IV) or V (IV) Metal chelate compound which is at least one selected from metal acetate, acetylacetonate, amino acid, Lewis acid, or organic acid metal salt

[2] The component (E) further contains a compound having a dimethylsiloxane skeleton represented by the general formula (3) as a component (E), and the component (E) with respect to a total of 100 parts by weight of the components (A) to (C). The hard coat agent composition according to [1], wherein the content of is no greater than 10.0 parts by weight.

(In the above formula, n ₂ is an integer of ₁ to 10,000.)

[3] The hard coat agent composition according to [2], wherein the compound having a dimethylsiloxane skeleton is a polyether-modified polydimethylsiloxane represented by the general formula (4).

(In the above formula, R ⁴ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ⁵ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a cationic polymerizable group, or an ethylenically unsaturated group, n ₃ and n ₄ are integers of 1 to ₅ , n ₅ is an integer of 1 to 30, n ₆ is an integer of 1 to 70, and n ₅ / n ₆ is 1 or less.

[4] A molded article having a cured film obtained by applying the hard coat agent composition according to any one of [1] to [3] to the surface of a substrate and then curing the hard coat agent composition.

[5] The molded article according to [4], wherein the substrate is made of at least one selected from a thiourethane resin or a thioepoxy resin.

[6] A lens having a cured coating film obtained by applying the hard coating agent composition according to any one of [1] to [3] to the surface of a substrate and then curing the hard coating agent composition.

[7] The lens according to [6], further comprising an antireflection film provided on the cured coating film.

  The hard coat agent composition of the present invention is excellent in both scratch resistance and impact resistance while maintaining a practical level of adhesion.

  The present invention will be described in detail below.

At least the following components (A) to (D) are contained, and in a total of 100 parts by weight of components (A), (B), and (C), component (A) is 5 to 60 parts by weight, and component (B) is 35 to 90 parts by weight, 5 to 60 parts by weight of component (C), and 0.01 to 10 parts by weight of component (D) with respect to a total of 100 parts by weight of components (A), (B), and (C) A hard coat agent composition characterized by the above.
Component (A): Silane compound represented by formula (1) Component (B): Silane compound represented by general formula (2) or a compound in which it is partially condensed, or a mixture component (C) thereof : Metal oxide fine particle component (D): Metal chelate compound

  The component (A) of the present invention is 1,3,5-N-tris (3-trimethoxysilylpropyl) isocyanurate represented by the formula (1).

  Specific examples of the component (A) may be commercially available, for example, trade name “Silane Coupling Agent X-12-965” (manufactured by Shin-Etsu Chemical), trade name “NUC Silicone Y-11597” (Nihon Unicar) Made).

  The silane compound as the component (B) in the present invention or a compound in which it is partially condensed will be described. The silane compound used in the present invention is a silane compound represented by the general formula (2) or a compound in which it is partially condensed.

(In the above formula, R ¹ is an organic group having a cationic polymerizable group, R ² and R ³ are each independently hydrogen or an alkyl group, and n ₁ represents an integer of ₁ to 3)

In the above R ² and R ³ , an alkyl group having 1 to 4 carbon atoms is preferable, and specific examples include methyl group, ethyl group, n- and i-propyl group, n-, i- and t-. A butyl group etc. are mentioned.

The cationic polymerizable group R ¹ is not particularly limited, but preferably includes a group having a (methyl) glycidyl ether group, an oxetanyl group, an epoxycyclohexyl group, and the like. A silane compound having a cationically polymerizable group represented by the general formulas (5) and (6) is preferable from the viewpoint of curability, hard coat property, adhesion, and availability of the compound.

(In the above formula, R ⁶ represents hydrogen or a methyl group, and R ⁷ represents a methyl group or an ethyl group.
n ₇ and n ₈ each independently represents an integer of 1 to 10. )
These compounds are used alone or in combination of two or more.

  Specific examples of these silane compounds include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyldimethylmethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylethyldiethoxysilane, 3-glycidoxypropyldiethylethoxysilane, 3-ethyl-3-{[3- (trimethoxysilyl) propoxy] methyl} oxetane, 3-ethyl-3-{[ 3- (triethoxysilyl) propoxy] methyl} oxetane and the like.

These compounds can form a three-dimensional network structure and can improve hard coat properties. Further, these compounds are also called silane coupling agents and have a function of promoting adhesion with thiourethane resins or thioepoxy resins. These silane compounds may be used as they are, but in order to further increase the reactivity, the alkoxysilyl group (Si—O—R ² ) represented by the general formula (2) is previously added with hydrochloric acid water. Hydrolysis using an acidic catalyst such as ammonia, or a basic catalyst such as aqueous ammonia to form a silanol (Si—OH) or partially condense to form a siloxane bond (Si—O—Si). It is more preferable to use it in the state.

  The metal oxide fine particles of component (C) will be described. By applying a hard coating agent containing at least components (A), (B), and (D) to a plastic lens substrate having a refractive index of 1.6 or more by increasing the refractive index of the plastic lens substrate, a hard coat layer is formed. Causes interference fringes. Therefore, the refractive index is adjusted by blending metal oxide fine particles into the hard coat layer.

As such metal oxide fine particles, one or more oxide fine particles of a metal selected from Si, Al, Sn, Sb, Ta, Ce, La, Fe, Zn, W, Zr, In, and Ti are used. Or a composite fine particle can be illustrated. Specifically, inorganic oxide fine particles such as SiO ₂ , SnO ₂ , Sb ₂ O ₅ , CeO ₂ , ZrO ₂ , TiO _2, etc. are colloidally dispersed in a dispersion medium such as water, alcohols or other organic solvents. Or composite fine particles composed of two or more inorganic oxides of Si, A1, Sn, Sb, Ta, Ce, La, Fe, Zn, W, Zr, In, and Ti are mixed with water, alcohol or The thing disperse | distributed colloidally to the other organic solvent can be illustrated. In any case, the particle size is preferably about 1 to 300 nm.

  Further, in order to improve dispersion stability in the coating liquid, it is also possible to use those obtained by treating the surface of these fine particles with an organosilicon compound.

  Examples of the organosilicon compound used in this case include monofunctional silane, bifunctional silane, trifunctional silane, and tetrafunctional silane. In the treatment, the hydrolyzable group may be untreated or hydrolyzed. In addition, after the treatment, it is preferable that the hydrolyzable group reacts with the —OH group of the fine particles, but there is no problem in stability even if a part of the hydrolyzable group remains.

  The metal chelate compound of component (D) will be described. The metal chelate compound used in the present invention acts as a curing catalyst for the hard coat agent. Preferred metal chelate compounds are Cu (II), Zn (II), Co (II), Ni (II), Be (II), Ce (III), Ta (III), Ti (III), Mn (III). , La (III), Cr (III), V (III), Co (III), Fe (III), Al (III), Ce (IV), Zr (IV), V (IV), etc. as the central metal atom And amino acids such as acetylacetonate, amine and glycine, Lewis acid, organic acid metal salts and the like. Of these, acetylacetonate of Al (III) and Fe (III) is more preferable in terms of curing conditions, pot life of the coating liquid, and the like. The addition amount is desirably in the range of 0.01 to 10.0 parts by weight with respect to 100 parts by weight of the total of components (A) to (C). Further, perchloric acids can be used in combination. Preferred perchloric acids include perchloric acid, ammonium perchlorate, magnesium perchlorate and the like.

  In the present invention, in a total of 100 parts by weight of the components (A) to (C), the component (A) is 5 to 60 parts by weight, the component (B) is 35 to 90 parts by weight, and the component (C) is 5 to 60 parts by weight. Component (D) is 0.01 to 10 parts by weight with respect to 100 parts by weight as a total of components (A), (B) and (C). When the component (A) is 60 parts by weight or less, sufficient scratch resistance can be obtained. If the component (A) is 5 parts by weight or more, the possibility that the film becomes brittle and sufficient impact resistance cannot be obtained can be reduced. When the component (B) is 35 parts by weight or more, sufficient scratch resistance and adhesion can be obtained. If the amount is too small, sufficient scratch resistance and adhesion may not be obtained. When the component (B) is 90 parts by weight or less, the possibility that the film becomes brittle and sufficient impact resistance cannot be obtained can be reduced. When the component (C) is 5 parts by weight or more, interference fringes become strong, and the possibility that sufficient scratch resistance cannot be obtained can be reduced. It can suppress that a hard-coat layer becomes cloudy and an external appearance deteriorates that a component (C) is 60 weight part or less. When the component (D) is 0.01 parts by weight or more with respect to 100 parts by weight of the total of the components (A) to (C), sufficient curing speed and scratch resistance can be obtained.

As a particularly preferred combination of components (A) to (D), specifically, as component (A), 1,3,5-N-tris (3-trimethoxysilylpropyl) isocyanate represented by formula (1) Nurate, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane as component (B), and inorganic oxide fine particles such as TiO ₂ and ZrO ₂ as dispersion medium such as water , Colloidally dispersed in alcoholic or other organic solvents, or composite fine particles composed of two or more inorganic oxides of Si, Sn, Zr, Ti in water, alcoholic or other organic solvents Further, the component (D) is an acetylacetonate of Al (III).

  A silicate compound can also be added to improve the scratch resistance of the hard coat layer. The silicate compound used in the present invention is a compound obtained by partially hydrolyzing a tetrafunctional alkoxysilane or a tetrafunctional alkoxysilane. Commercially available products can be used as the silicate compound. For example, as a silicate containing (3-ethyloxetane-3-yl) methoxy group, oxetanyl silicate (OX-SC), (trade name, manufactured by Toagosei Co., Ltd.) As silicates having a methoxy group or an ethoxy group, ethyl silicate 28, ethyl silicate 28P (all trade names of Colcoat Co.), methyl silicate, ethyl silicate, M silicate 51, M silicate 60, silicate 40 (any Can also be used preferably.

  The compound having a dimethylsiloxane skeleton represented by the general formula (3) as the component (E) in the present invention will be described. Generally, a part of the side chain of dimethylsiloxane represented by the general formula (4) is modified with a polyether such as ethylene oxide or propylene oxide, or silsesquioxane is added to the dimethylsiloxane main chain or side chain. What was combined etc. is used suitably.

(In the above formula, n ₂ is an integer of ₁ to 10,000.)

(In the above formula, R ⁴ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ⁵ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a cationic polymerizable group, or an ethylenically unsaturated group, n ₃ and n ₄ are integers of 1 to ₅ , n ₅ is an integer of 1 to 30, n ₆ is an integer of 1 to 70, and n ₅ / n ₆ is 1 or less.

  Since the surface tension can be adjusted by adding the component (E), there is an effect of preventing repelling when coating the resin surface or improving the smoothness of the coating film. Further, since the dimethylsiloxane portion has a property of bleeding on the surface of the coating film, the slip property is improved, and better scratch resistance can be expected. In addition, those modified with polyether and those bound with silsesquioxane are excellent in solubility.

  The content ratio of the component (E) is 0.01% by weight or more, more preferably 0.1% by weight or more with respect to 100 parts by weight of the total of the components (A) to (C). Thereby, repelling can be prevented or the smoothness of the coating film can be improved. Moreover, content of a component (E) is 10 weight part or less with respect to a total of 100 weight part of a component (A)-(C), More preferably, it is 5 weight part or less. Thereby, the fall of sclerosis | hardenability can be suppressed and a surface state can be made favorable.

  Specific examples of the component (E) may be commercially available, and examples of the dimethylsiloxane derivative whose side chain is polyether-modified include BYK-306, BYK-307, BYK-333, BYK-375 (both BYK-Chemie Co., Ltd. product name). Oxetanylsilsesquioxane (OX-SQSI20) (trade name, manufactured by Toagosei Co., Ltd.) may be mentioned as one in which silsesquioxane is bonded to the main chain or side chain.

  In addition, the viscosity of the composition of the present invention is adjusted by adding a solvent. Preferred solvents include lower alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, polyethylene glycol methyl ether, polyethylene glycol methyl ether acetate, dimethylformamide, N, N'-dimethylacetamide, N- Examples include methyl-2-pyrrolidone, tetrahydrofuran, dioxane, toluene and the like.

  In addition, a silane coupling agent other than the component (C) may be added within a range of 5 parts by weight or less with respect to 100 parts by weight of the composition of the present invention, specifically, 3-chloropropyltrimethoxysilane, Vinyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyl Trimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-cyanopropyltrimethoxysilane, 3-morpholinopropyltrimethoxysilane, N-phenylaminopropyl Such as trimethoxysilane Functional silanes, and further bifunctional silanes, that is, bifunctional silanes in which a part of the trifunctional silane is substituted with an alkyl group, phenyl group, vinyl group, etc., such as dimethyldimethoxysilane, phenylmethyldimethoxysilane, vinylmethyldimethoxysilane , 3-chloropropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and the like.

  Antistatic agent, ultraviolet absorber, antioxidant, disperse dye / oil-soluble dye / fluorescent dye / pigment, photochromic compound, hindered amine, in the range of 5 parts by weight or less based on 100 parts by weight of the hard coat agent composition of the present invention -Light-resistant and heat-resistant stabilizers such as hindered phenols can be added to improve the coating properties of the hard coat solution and the coating performance after curing. In particular, it is possible to impart weather resistance to the hard coat film by adding one or more selected from light-resistant and heat-resistant stabilizers such as ultraviolet absorbers, antioxidants, hindered amines and hindered phenols.

  Other resin components, specifically polyurethane, polystyrene, acrylic resin, etc., within a range where the performance is not impaired, specifically within 5 parts by weight or less with respect to 100 parts by weight of the hard coat agent composition of the present invention. May be added.

[Method for preparing hard coat agent composition]
The preparation method may be performed by a known method, and is not particularly limited. For example, it is as follows. First, a desired amount of the components (A) to (C) are mixed in a light-shielding brown glass container or a plastic container, and the composition is warmed (approximately 50 ° C. or lower) as required to be completely mixed. In a state where the mixture is at room temperature (23 ° C.), components (D) and (E) and, if necessary, other components are added and mixed thoroughly. Furthermore, it left still sufficient deaeration and was set as the composition. For the mixing, a magnetic stirrer or a stirrer was used, but a mixer, a shaker, etc. may be selected according to the amount and viscosity.

[Coating method, curing method]
As a coating (coating) method and a curing method of the hard coat agent composition prepared as described above, the hard coat composition is applied to the substrate by a dipping method, a spinner method, a spray method, or a flow method, and then 100 to It can be cured by heating and baking at a temperature of 200 ° C. for several hours to form a film (hard coat layer) in which the hard coat agent composition is cured.

[Formation of antireflection film]
An antireflection film can be formed on the surface of the hard coat layer formed on the plastic lens substrate by the above method. The antireflection film is composed of a single layer or multiple layers of an inorganic coating or an organic coating on the hard coat layer. The material of the inorganic _{film, SiO 2, SiO, ZrO 2} , TiO 2, TiO, Ti 2 O 3, Ti 2 O 5, Al 2 O 3, Ta 2 O 5, CeO 2, MgO, Y 2 O 3, Examples include inorganic substances such as SnO ₂ , MgF ₂ , and WO ₃ , and these can be used alone or in combination of two or more. For plastic lens, _SiO 2 which can be vacuum deposited at a low _{temperature, ZrO 2, TiO 2, Ta} 2 O 5 is preferred.

  As a method for forming the inorganic film, for example, a vacuum deposition method, an ion plating method, a sputtering method, a CVD method, a method of depositing by a chemical reaction in a saturated solution, or the like can be employed. In the vacuum vapor deposition method, an ion beam assist method in which an ion beam is simultaneously irradiated during vapor deposition may be used.

  The material of the organic coating is selected in consideration of the refractive index of the plastic lens and hard coat layer, and it can be formed by a coating method with excellent mass productivity such as spin coating and dip coating in addition to vacuum deposition. it can.

  Further, when the antireflection film is formed, the surface treatment of the hard coat layer can be performed in advance in order to improve the adhesion at the hard coat-antireflection interface. Specific examples of the surface treatment include acid treatment, alkali treatment, ultraviolet irradiation treatment, plasma treatment by high frequency discharge in an argon or oxygen atmosphere, ion beam irradiation treatment of argon, oxygen, nitrogen, or the like.

  Furthermore, a water repellent film can be formed on the surface of the antireflection film using a fluorine-containing silane compound containing a perfluoroalkyl group or the like in order to make the surface of the antireflection film difficult to stain or to easily wipe off the dirt. In addition, a hydrophilic film can be formed on the surface of the antireflection film by using a surfactant having a hydrophilic group such as sulfonic acid Na or sulfonic acid K in order to impart antifogging properties.

[Evaluation method of hard coating agent composition and cured film]
-Adhesion evaluation method of cured film (hardened coating composition):
JIS-K5600-5-6: 1999 adhesion test (cross-cut method).
Preferred conditions are as follows: Category 0 (the edges of the cut are completely smooth and no peeling to the eye of any grid) or category 1 (small peeling of the coating film at the intersection of the cuts) with the film cured. Is clearly not affected by 5%). Further, in the state after the weather resistance test described later, classification 0 to classification 2 (the coating film is peeled along the edge of the cut and / or at the intersection. It is clearly 5% that the cross-cut portion is affected. Exceeding 15% but not exceeding 15%).
-Evaluation method of scratch resistance of cured film:
A rubbing test with steel wool (# 0000) can be mentioned, and it is preferably scratch-free with a load of 500 g and 10 reciprocations.
・ Method for evaluating impact resistance of cured film:
A steel ball with a weight of 16 g (16 g: FDA (Food and Drug Administration) standard value, which is a practical index for spectacle lenses), 33 g, 45 g, 68 g, 114 g, 229 g, and 540 g of steel balls with a height of 1270 mm The sample was dropped in order, and the destruction of the sample was confirmed. The weight of the previous hard sphere where the fracture occurred was taken as the impact resistance value. A preferable state is a state where there is no change even when a 229 g hard sphere is dropped, or there is no scattering of fragments even if a crack occurs. A more preferable state is a state where there is no change even when a 540 g hard ball is dropped, or there is no debris scattering even if a crack occurs.
・ Measurement of viscosity of hard coat agent composition:
Measured by E-type viscosity at 25 ° C. Preferably it is 0.1-500 mPa * s, More preferably, it is 0.5-100 mPa * s, More preferably, it is 1-50 mPa * s.
-Storage stability of hard coat agent composition:
It was stored at room temperature for one month and examined for the presence of gelation.
・ Measurement of refractive index of cured film:
Measured with an Abbe refractometer manufactured by Atago.
・ Evaluation of appearance of cured film:
It was confirmed by visual observation that the film after coating / curing was free of defects such as repellency, discontinuity, non-smoothness, and generation of distorted skin.

[Use of hard coat agent composition of the present invention]
The hard coat agent composition of the present invention is excellent in scratch resistance, impact resistance and adhesion when applied and cured on a substrate such as a resin, and has very high transparency, so it can be used in a wide range. In particular, since only one layer of coating is required, there is an advantage that work efficiency is improved.

  Hereinafter, although the present invention will be described in more detail based on production examples, analysis examples, and examples, the present invention is not limited to the production examples, analysis examples, and examples.

<< Preparation and Evaluation of Hard Coat Agent Containing Hard Coat Agent Composition of Present Invention >>
[Production Example 1]
<Production of thiourethane resin (1)>
50.6 g of norbornene diisocyanate represented by the formula (7), 25.5 g of 1,2-bis (2-mercaptoethyl) thio-3-mercaptopropane represented by the formula (8), As shown, 23.9 g of pentaerythritol tetra (3-mercaptopropionate), 0.02 g of dibutyltin dichloride, and 0.125 g of ZelecUN (STEPAN) as an internal mold release agent were added and stirred for 1 hour under reduced pressure. Defoamed. After filtration through a 1 μm Teflon (registered trademark) filter, it was poured into a molding mold comprising a glass mold and a gasket. While this mold was gradually heated from 20 ° C. to 130 ° C., polymerization was performed in 30 hours to synthesize a resin. After completion of the polymerization, the resin synthesized by gradually cooling was taken out from the molding mold. The obtained resin was annealed at 130 ° C. for 2 hours to obtain a lens having a center thickness of 1.15 mm.

[Production Example 2]
<Production of thiourethane resin (2)>
36.4 g of m-xylylene diisocyanate represented by the formula (10), 33.6 g of 1,2-bis (2-mercaptoethyl) thio-3-mercaptopropane represented by the formula (8) and dibutyltin dichloride 0.01 g and 0.07 g of ZelecUN (STEPAN) as an internal mold release agent were added and stirred, and degassed for 1 hour under reduced pressure. After filtration through a 1 μm Teflon (registered trademark) filter, it was poured into a molding mold comprising a glass mold and a gasket. While this mold was gradually heated from 20 ° C. to 130 ° C., polymerization was performed in 30 hours to synthesize a resin. After completion of the polymerization, the resin synthesized by gradually cooling was taken out from the molding mold. The obtained resin was annealed at 130 ° C. for 2 hours to obtain a lens having a center thickness of 1.15 mm.

[Production Example 3]
<Production of thioepoxy resin (1)>
70.0 g of bis (2,3-epithiopropyl) disulfide represented by the formula (11), 0.014 g of N, N-dimethylcyclohexylamine and 0.07 g of N, N-dicyclohexylmethylamine were added and stirred. For 1 hour under reduced pressure. After filtration through a 3 μm Teflon (registered trademark) filter, the solution was injected into a molding mold composed of a glass mold and a gasket over 4 hours. While this mold was gradually heated from 20 ° C. to 120 ° C., polymerization was performed in 30 hours to synthesize a resin. After completion of the polymerization, the resin synthesized by gradually cooling was taken out from the molding mold. The obtained resin was annealed at 120 ° C. for 3 hours to obtain a lens having a center thickness of 1.15 mm.

Example 1
As a silane compound represented by the following formula (2) or a compound in which it is partially condensed, 13.2 g of 0.1N hydrochloric acid water is added to 36.0 g of 3-glycidoxypropyltrimethoxysilane with stirring, Stir for 2 hours. 70 g of methyl cellosolve and 7.8 g of methanol were added, and then 6.0 g of 1,3,5-N-tris (3-trimethoxysilylpropyl) isocyanurate as a silane compound represented by the following formula (1), metal Methanol-dispersed tin oxide-titanium dioxide-zirconium oxide-antimony pentoxide composite oxide sol HIT30M1 (manufactured by Nissan Chemical Co., Ltd., solid content concentration 30% by weight, product name) 70.0 g (solid content weight: 21) 0.0 g), and after sufficiently stirring, 1.9 g of Al (III) acetylacetonate as the metal chelate compound and polyether-modified polydimethylsiloxane BYK333 (product name: BYK Chemie, product name) 0 as the compound having a dimethylsiloxane skeleton. 0.06 g was added and stirred for 4 hours, then aged for a whole day and night. The coating composition was evaluated by the method described later.

(Example 2)
As a silane compound represented by the above formula (2) or a partially condensed compound thereof, 13.2 g of 0.1N hydrochloric acid water was added to 36.0 g of 3-glycidoxypropyltrimethoxysilane with stirring, and Stir for 2 hours. 70 g of methyl cellosolve and 0.8 g of methanol were added, and then 6.0 g of 1,3,5-N-tris (3-trimethoxysilylpropyl) isocyanurate as a silane compound represented by the above formula (1), metal Methanol-dispersed zirconium oxide-tin oxide-antimony pentoxide-silicon dioxide composite oxide sol HZ-307M6 (manufactured by Nissan Chemical Co., Ltd., solid content concentration 30% by weight, product name) 80.0 g (solid weight) : 24.0 g) and after sufficient stirring, 1.9 g of Al (III) acetylacetonate as a metal chelate compound, and polyether-modified polydimethylsiloxane BYK333 (product of BYK Chemie, product name) as a compound having a dimethylsiloxane skeleton ) Add 0.06g and stir for 4 hours. Evaluation was performed by the method described later as a hard coat agent composition.

(Examples 3 to 5)
By the composition shown in Table 1, the hard-coat agent composition for coating was prepared similarly to Examples 1-2, and it evaluated by the method of the below-mentioned.

(Comparative Example 1)
As a silane compound represented by the above formula (2) or a compound in which it is partially condensed, 13.2 g of 0.1N hydrochloric acid water is added to 42.0 g of 3-glycidoxypropyltrimethoxysilane while stirring, Stir for 2 hours. Methyl cellosolve 70 g and methanol 7.8 g were added, and methanol dispersed tin oxide-titanium dioxide-zirconium oxide-antimony pentoxide composite oxide fine particle sol HIT30M1 (manufactured by Nissan Chemical Co., Ltd., solid content concentration 30% by weight) as metal oxide fine particles ) After adding 76.0 g and sufficiently stirring, 1.9 g of Al (III) acetylacetonate as a metal chelate compound, and polyether-modified polydimethylsiloxane BYK333 (product name) manufactured by BYK Chemie as a compound having a dimethylsiloxane skeleton. 0.06 g was added and stirred for 4 hours, and then aged for a whole day and night to obtain a coating composition, which was evaluated by the method described later.

(Comparative Examples 2 to 5)
By the composition shown in Table 1, the hard-coat agent composition for coating was prepared similarly to Examples 1-2, and it evaluated by the method of the below-mentioned.

  The hard coat agent composition and the cured film thereof were evaluated as follows. The evaluation results are shown in Tables 1 and 2.

[Formation of hard coat layer]
Each of Examples 1 to 5 and Comparative Examples 1 to 5 was applied to the resin plates of Preparation Examples 1 to 4 by dip coating, air-dried at 80 ° C. for 30 minutes, and then baked at 120 ° C. for 120 minutes. The film thickness of the cured film thus obtained was 1.9 to 2.5 μm. This sample was stored and cured at a temperature of 23 ° C. and a relative humidity of 40 to 50%. Then, confirmation of thickness was performed with a stylus type surface shape measuring device (DekTakIII ULVAC).

[1] Viscosity of hard coating agent composition The viscosities (25 ° C) of the compositions of Examples 1 to 5 and Comparative Examples 1 to 5 were measured with an E-type viscometer (manufactured by Tokyo Keiki Co., Ltd.). The evaluation results are shown in Table 1.

[2] Storage stability of hard coat agent composition The compositions of Examples 1 to 5 and Comparative Examples 1 to 5 were stored at room temperature for a week and evaluated as follows. The evaluation results are shown in Table 1.
A: Not gelled.
B: Gelled.

[3] Film-formability (smoothness)
About the composition of Examples 1-5 and Comparative Examples 1-5, it formed into a film by the dip coating on the resin board shape | molded in Preparation Example 1, and performed the following evaluation.
A: The film after coating and curing is smooth, and there are no defects such as repellency, discontinuity, and generation of distorted skin.
B: The film after coating / curing is free from defects such as repellency, discontinuity, and generation of distorted skin, but is slightly inferior in smoothness.
C: Defects in appearance such as non-smooth film after curing, repelling, discontinuity, and generation of distorted skin are observed.
The evaluation results are shown in Table 1.

[4] Refractive index Each of Examples 1 to 5 and Comparative Examples 1 to 5 was measured with an Abbe refractometer manufactured by Atago Co., Ltd. on a sample in which a cured film (hard coat layer) was formed on the resin plate of Preparation Example 1.
The measured values of the refractive index are shown in Table 1.

[5] Transparency Each of Examples 1 to 5 and Comparative Examples 1 to 5 was obtained by visually observing the appearance of a sample in which a hard coat film was formed on the resin plate of Preparation Example 1, and the transmittance was measured with a film transmittance meter (Shimadzu UV2200). ) To measure the transmittance between 400 nm and 600 nm.
A: Transmittance is 90% or more between 400 nm and 600 nm B: Transmittance between 80 nm and less than 90% between 400 nm and 600 nm C: Transmittance between 400 nm and 600 nm is less than 80% Evaluation results are shown in Table 1.

[6] Curability For confirmation of curing, a film having no tack on the film surface and having no film peeling even when scratched with a nail was regarded as complete curing.
A: Completely cured by baking at 120 ° C. for 2 hours.
B: Not completely cured by baking at 120 ° C. for 2 hours.
(Completely cured by post-baking at 130 ° C for 2 hours)
C: Not completely cured Table 1 shows the evaluation results.

[7] Adhesion test For each sample of Examples 1 to 5 and Comparative Examples 1 to 5 on which the cured film (hard coat layer) was formed on the resin plate of Production Examples 1 to 3, JIS-K5600 adhesion test ( The cross-cut method was carried out. First, a sample is cut at intervals of 1 mm using an equally spaced spacer, and 25 squares of 1 mm ² are formed. A transparent pressure-sensitive adhesive tape was affixed thereon, peeled off at an angle of 60 ° C., and squares having a coating film remaining were counted.

The evaluation was as follows: AA for classification 0, A for classification 1-2, B for classification 3, and C for classification 4-5.
Classification 0: The edge of the cut is completely smooth, and there is no peeling to the eyes of any lattice.
Classification 1: Small peeling of the coating film at the intersection of cuts. It is clearly not more than 5% that the crosscut is affected.
Classification 2: The coating is peeled along the edge of the cut and / or at the intersection. The cross-cut portion is clearly affected by more than 5% but not more than 15%.
Classification 3: A cross-cut portion in which the coating film is partially or completely peeled along the edge of the cut, and / or various parts of the eye are partially or completely peeled off. The impact is clearly over 15% but not over 35%.
Classification 4: A cross-cut portion in which the coating is partially or completely peeled along the edge of the cut and / or various parts of the eye are partially or completely peeled off. The impact is clearly over 35% but not over 65%.
Category 5: The degree of peeling exceeds Category 4.
The evaluation results are shown in Table 2.

[8] Scratch resistance test For each of Examples 1 to 5 and Comparative Examples 1 to 5, a cured film (hard coat layer) formed on the resin plate of Production Example 1 was used for # 0000 steel wool (Japan Steel). A load of 1000 g and 500 g was applied with Wool Co., Ltd., and the surface was rubbed for 10 reciprocations, and the degree of scratching was visually judged at the next stage.
AA: There is no scratch in the range rubbed with a load of 1000 g.
A: There is no scratch at all in the range rubbed with a load of 500 g.
B: 1 to 9 scratches are in the range rubbed with a load of 500 g.
C: 10 to 30 scratches are attached within the range rubbed with a load of 500 g.
D: Innumerable (more than 30) scratches are within the range rubbed with a load of 500 g.
The evaluation results are shown in Table 2.

[9] Impact resistance Each of Examples 1 to 5 and Comparative Examples 1 to 5 was evaluated for impact resistance on samples in which a cured film (hard coat layer) was formed on the resin plate of Preparation Example 1. A steel ball having a mass of 16 g (16 g: FDA (US Food and Drug Administration) standard value, which is a practical index for spectacle lenses), 33 g, 45 g, 68 g, 114 g, 229 g, and 540 g of steel balls with a height of 1270 mm Drop them in order, and confirm the destruction of the sample. The weight of the previous hard sphere where the fracture occurred was taken as the impact resistance value.
The evaluation results are shown in Table 2.

[10] Warm water resistance Each of Examples 1 to 5 and Comparative Examples 1 to 5 was immersed in warm water at 80 ° C. for 15 minutes for a sample in which a cured film (hard coat layer) was formed on the resin plate of Preparation Example 1. The change in appearance was examined.
A: No change in appearance is seen.
B: Changes such as swelling are observed in the film.
C: Cracks are observed in the film.
The evaluation results are shown in Table 2.

  In Examples 1 to 5, good results were obtained in the above evaluations [1] to [10]. By using 1,3,5-N-tris (3-trimethoxysilylpropyl) isocyanurate as the component (A), the impact resistance was improved. Other evaluations were also good. In Comparative Examples 1 and 2, since 1,3,5-N-tris (3-trimethoxysilylpropyl) isocyanurate as component (A) was not added, the impact resistance was insufficient. In Comparative Example 3, the adhesion and scratch resistance were insufficient, in which the silane compound of component (B) was not added. In Comparative Example 4, since the metal oxide fine particles of component (C) were not added, the scratch resistance and hot water resistance were insufficient. In Comparative Example 5, since Al (III) acetylacetonate as component (D) was not added, the curability was insufficient, and therefore evaluation was impossible.

The hard coat agent composition of the present invention is excellent in scratch resistance by heat-curing a specific silane compound and / or a compound in which it is partially condensed, metal oxide fine particles, and metal chelate compound as essential components. Since the coating layer can be formed, the field of coating agents and optical materials, more specifically, anti-reflection applications such as hard coating of eyeglass lenses, plasma displays, liquid crystal displays, EL displays, reading of high-density recording optical media, It is useful for applications such as surface coating agents for the purpose of improving the design properties of optical members such as optical filters, plastic materials, metal materials, ceramic materials, and glass materials.
In addition, the hard coat agent composition of the present invention has the advantage that the working efficiency is improved because the scratch resistance and impact resistance can be obtained only once with respect to the substrate.

  Especially as a hard coating agent, especially for thiourethane resin and thioepoxy resin surface, it has excellent adhesion, scratch resistance, and impact resistance, so it is suitable for spectacle lenses, camera lenses, optical recording / reproducing equipment. It can be widely applied to hard coating agents such as pickup lenses.

Claims (7)

It contains at least the following components (A) to (D), and 5 to 60 parts by weight of component (A) and 35 to 90 parts by weight of component (B) in a total of 100 parts by weight of components (A) to (C). Part, component (C) is 5 to 60 parts by weight, and component (D) is 0.01 to 10 parts by weight with respect to 100 parts by weight as a total of components (A) to (C). Agent composition.
Component (A): Silane compound represented by formula (1)

Component (B): Silane compound represented by general formula (2), a compound in which it is partially condensed, or a mixture thereof

(In the above formula, R ¹ is an organic group having a cationic polymerizable group represented by the general formulas (5) and (6) , R ² and R ³ are each independently hydrogen or an alkyl group, and n ₁ represents an integer of ₁ to 3.)

(In the above formula, R ⁶ represents hydrogen or a methyl group, and R ⁷ represents a methyl group or an ethyl group.
n ₇ and n ₈ each independently represents an integer of 1 to 10. )
Component (C): Si, Al, Sn, Sb, Ta, Ce, La, Fe, Zn, W, Zr, In, Ti, one or more kinds of oxide fine particles or composite fine particles Metal oxide fine particle component (D): Cu (II), Zn (II), Co (II), Ni (II), Be (II), Ce (III), Ta (III), Ti (III), Mn Centered on (III), La (III), Cr (III), V (III), Co (III), Fe (III), Al (III), Ce (IV), Zr (IV) or V (IV) Metal chelate compound which is at least one selected from metal acetate, acetylacetonate, amino acid, Lewis acid, or organic acid metal salt The component (E) further contains a compound having a dimethylsiloxane skeleton represented by the general formula (3), and the component (E) is contained with respect to a total of 100 parts by weight of the components (A) to (C). The hard coat agent composition according to claim 1, wherein the amount is 10.0 parts by weight or less.

(In the above formula, n ₂ is an integer of ₁ to 10,000.) The hard coat agent composition according to claim 2, wherein the compound having a dimethylsiloxane skeleton is a polyether-modified polydimethylsiloxane represented by the general formula (4).

(In the above formula, R ⁴ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ⁵ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a cationic polymerizable group, or an ethylenically unsaturated group, n ₃ and n ₄ are integers of 1 to ₅ , n ₅ is an integer of 1 to 30, n ₆ is an integer of 1 to 70, and n ₅ / n ₆ is 1 or less.   A molded article having a cured film obtained by applying the hard coat agent composition according to any one of claims 1 to 3 to a surface of a substrate and then curing the hard coat agent composition.   The molded article according to claim 4, wherein the base material comprises at least one selected from a thiourethane resin or a thioepoxy resin.   A lens having a cured coating film obtained by applying the hard coating agent composition according to any one of claims 1 to 3 to a surface of a substrate and then curing the hard coating agent composition.   The lens according to claim 6, further comprising an antireflection film provided on the cured coating film.