WO2011055667A1

WO2011055667A1 - Coating composition and optical article

Info

Publication number: WO2011055667A1
Application number: PCT/JP2010/069097
Authority: WO
Inventors: 力宏森; 俊一郎中司
Original assignee: 株式会社トクヤマ
Priority date: 2009-11-06
Filing date: 2010-10-27
Publication date: 2011-05-12
Also published as: JP2013014636A

Abstract

Provided is a coating composition which can form, on the surface of a plastic lens base, a transparent coating layer with high hardness and excellent mar resistance, namely, a hard coat layer. Even when in contact with warm water, a transparent coating layer formed using the coating composition exhibits excellent tight adhesion to the lens base. A coating composition for the formation of a hard coat layer, characterized by containing, with respect to 100 parts by mass of (A) fine particles of an inorganic oxide such as silica or antimony pentaoxide, 50 to 350 parts by mass of (B1) an epoxy-containing silicon compound that bears both an epoxy group and a hydrolyzable group (such as ?-glycidoxypropyltrimethoxysilane) and 0.1 to 10 parts by mass of (C) a compound having a ketimine group (such as 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine); and an optical article which is laminated with a cured layer of the coating composition on the surface.

Description

Coating composition and optical article

The present invention relates to a coating composition applied to the surface of an optical substrate such as a plastic lens. Specifically, the present invention relates to a coating composition suitable for a hard coat layer formed on the surface of a plastic substrate made of urethane resin, (meth) acrylic resin, or the like.

The coating composition for an optical substrate is used for forming a hard coat layer for improving scratch resistance by applying and curing on the surface of an optical substrate such as a plastic lens. For such a coating composition, it is desired to form a cured body (hard coat layer) that maintains transparency and has high scratch resistance. For this reason, generally, a silica sol dispersed in a colloidal form, etc. A composition containing inorganic oxide fine particles and an organosilicon compound such as alkoxysilane is used (see Patent Documents 1 to 6).

On the other hand, there are a wide variety of optical base materials to which the coating composition is applied, and (meth) acrylic resins and urethane resins are typical. In particular, (meth) acrylic resins are often used as a matrix for photochromic lenses. In the present invention, the (meth) acrylic resin refers to a resin obtained by polymerizing an acrylic monomer and a methacrylic monomer {hereinafter sometimes collectively referred to as a (meth) acrylic monomer}. .

A photochromic lens is a lens that quickly colors and functions as sunglasses when exposed to light containing ultraviolet rays such as sunlight, and fades and is transparent in an indoor environment without such light irradiation. These glasses function as glasses, and their demand is increasing in recent years. As a method for producing a photochromic lens using a (meth) acrylic resin, a method of directly obtaining a photochromic lens by dissolving a photochromic compound in a (meth) acrylic monomer and polymerizing it (kneading) And a layer having photochromic properties on the surface of the plastic lens (hereinafter referred to as a photochromic coating layer) using a curable composition (hereinafter also referred to as a photochromic coating agent) comprising a photochromic compound and a (meth) acrylic monomer. Also known is a method (coating method).
When a (meth) acrylic monomer is used as the monomer, the photochromic compound existing between the resins easily moves in the resulting photochromic lens or in the photochromic coat layer, so that excellent photochromic properties can be exhibited.
Also in the photochromic lens, a hard coat layer is usually formed on the surface thereof. In recent years, the performance required for such a hard coat layer has been further enhanced not only in optical substrates made of (meth) acrylic resins but also in optical substrates made of other resins.

For example, when the coating composition disclosed in Patent Documents 1 to 3 is used for an optical substrate made of a (meth) acrylic resin, the hard coat layer may not have sufficient adhesion, or scratch resistance However, there was room for improvement.
Patent Documents 4 and 5 describe a hard coat that exhibits excellent adhesion and hardness when the amount of inorganic oxide fine particles, organosilicon compound, and water is optimized and applied to the surface of a (meth) acrylic resin layer. Forming coating compositions are shown, but these coating compositions also have the following problems. An optical article having a hard coat layer may come into contact with warm water in that application. When the coating composition is used, a part of the formed hard coat layer may be peeled off when contacting with warm water, and there is room for improvement (hereinafter, hard coat after contacting with warm water). The adhesion of the layer may be hot water resistant.)
Patent Document 6 discloses a coating composition for forming a hard coat layer containing a curing catalyst, which is suitable for an optical substrate composed of an allyl resin and a thiourethane resin. In this coating composition, too, There was room for improvement in the following points. Patent Document 6 discloses the use of an organosilicon compound having an epoxy group that functions as a binder and other organosilicon compounds. However, according to the study by the present inventors, the coating composition is a combination of specific silicon compounds, and a hard coat layer excellent in hot water resistance and scratch resistance is obtained unless they are used in a specific amount. It turned out that it cannot be formed.

JP-A-53-111336 JP-T-2001-520699 JP 2002-543235 A International Publication WO2007 / 086320 Pamphlet International Publication WO2008 / 105306 Pamphlet International Publication WO2005 / 097497 Pamphlet

The objective of this invention is providing the coating composition which can form the hard-coat layer excellent in the adhesiveness with respect to optical base materials, such as a plastics lens, and abrasion resistance, and also excellent in hot water resistance.
Another object of the present invention is to provide a coating composition suitable as a hard coat layer for an optical substrate made of urethane resin or (meth) acrylic resin, particularly an optical substrate made of the latter resin.

The present inventors have conducted intensive studies to solve the above problems. As a result, (A) inorganic oxide fine particles and (B1) an epoxy group-containing silicon compound having an epoxy group and a hydrolyzable group (hereinafter sometimes simply referred to as an epoxy group-containing silicon compound) are further included. It is possible to solve the above problems by blending a specific amount of (C) a ketimine compound having a ketimine group (hereinafter sometimes simply referred to as a ketimine compound) into a coating composition for forming a hard coat layer. The headline and the present invention have been completed.

That is, the present invention is a coating composition for forming a hard coat layer comprising (A) inorganic oxide fine particles, (B1) an epoxy group-containing silicon compound, and (C) a ketimine compound, wherein the component (A) is 100 It is the said coating composition characterized by including 50 mass parts or more and 350 mass parts or less (B1) component as a mass part, and 0.1 mass part or more and 10 mass parts or less of (C) component.

In the invention of the coating composition,
1) The (C) ketimine compound is preferably a ketimine group-containing silicon compound having a ketimine group and a hydrolyzable group (hereinafter sometimes simply referred to as a ketimine group-containing silicon compound). In the present invention, the ketimine group is

(Wherein R is an organic group).

2) Further, as the component (B2), the following formula (I)

(Where
R ¹ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms,
R ² is an alkyl group having 1 to 3 carbon atoms,
A is an integer of 0-2. )
And a silicon compound represented by the following formula (II)

(Where
R ³ is an alkylene group having 1 to 8 carbon atoms,
R ⁴ and R ⁵ are alkyl groups having 1 to 3 carbon atoms,
R ⁶ and R ⁷ are alkyl groups having 1 to 3 carbon atoms,
B is an integer of 0-2. )
It contains at least one silicon compound selected from the group consisting of silicon compounds represented by the formula (A), 100 parts by mass of the component (A2), and 10 parts by mass or more and 150 parts by mass or less of the component (B2). A coating composition is preferred. By blending the component (B2), scratch resistance can be enhanced.

The present invention further relates to an optical article having a hard coat layer obtained by curing the coating composition on a plastic optical substrate. The present invention exhibits an excellent effect when the substrate is a substrate made of a (meth) acrylic resin or a urethane resin. In particular, when the substrate is made of a (meth) acrylic resin and further includes a photochromic compound, an excellent effect is exhibited.

The coating composition of the present invention can form a hard coat layer having good adhesion and excellent scratch resistance on the surface of an optical substrate such as a plastic lens. In particular, it is possible to form a hard coat layer that hardly peels when contacted with warm water and is excellent in hot water resistance. Above all, when the optical substrate is a urethane resin or a substrate made of a (meth) acrylic resin, an excellent effect is obtained, particularly when the substrate is a (meth) acrylic resin containing a photochromic compound. Exhibits excellent effects.

The reason why the coating composition of the present invention has excellent adhesion to an optical substrate such as a plastic lens, particularly excellent hot water resistance, is that (B1) an epoxy group-containing silicon compound and (C) a ketimine compound are in a specific amount. It is thought to be in use.
(C) A ketimine compound generates an amino group by hydrolyzing a ketimine group in a coating agent obtained by mixing a coating composition. It is considered that the amino group reacts with a functional group present on the surface of the plastic substrate, and also participates in the addition reaction of the (B1) epoxy group-containing silicon compound to the epoxy group. As a result, it is considered that the adhesion between the formed hard coat layer and the plastic optical substrate, in particular, the hot water resistance is increased.
When the ketimine compound is a ketimine group-containing silicon compound, it is considered that a more excellent effect is exhibited by the following mechanism of action.
When a ketimine group-containing silicon compound is used, a silanol group is generated by hydrolyzing a hydrolyzable group, for example, an alkoxysilyl group, in addition to the amino group. The silanol group is considered to condense with other silicon compounds in the hard coat layer or react with the hydroxyl group on the surface of the inorganic oxide fine particles. As a result, in addition to the action of the amino group, the action of the silanol group also occurs. Therefore, by using the ketimine group-containing silicon compound, the adhesion between the formed hard coat layer and the plastic substrate, in particular, hot water resistance Is considered to improve more.

When a (meth) acrylic resin is used as an optical substrate, in addition to the above action, the (meth) acryloyl group remaining in the (meth) acrylic resin and the amino group are bonded by a Michael addition reaction, It is considered that the formed hard coat layer exhibits high adhesion, particularly hot water resistance. Furthermore, when a urethane-based resin is used, it is considered that the amino group interacts with the urethane bond portion such as hydrogen bond, and thus exhibits high adhesion, particularly hot water resistance.
As described above, the (C) ketimine compound can act on both the hard coat layer and the optical substrate, and is considered to contribute to the improvement of adhesion between the hard coat layer and the optical substrate, particularly hot water resistance. .
The coating composition of the present invention has high transparency, can form a hard coat layer having excellent scratch resistance, and has excellent adhesion, particularly hot water resistance. Therefore, the coating composition of the present invention is suitably used not only as the above-mentioned (meth) acrylic resin or urethane resin, but also as a coating composition for forming a hard coat layer for a substrate made of another resin. it can.

The coating composition of the present invention is a coating composition characterized by comprising (A) inorganic oxide fine particles, (B1) an epoxy group-containing silicon compound, and (C) a ketimine compound. Hereinafter, each component will be described.

<(A) Inorganic oxide fine particles>
A well-known thing can be used for (A) inorganic oxide microparticles | fine-particles used by this invention. The inorganic oxide fine particles (A) may be composed of one kind of inorganic oxide, or may be composite inorganic oxide fine particles containing two or more kinds of inorganic oxides.
From the viewpoint that the (A) inorganic oxide fine particles can be uniformly dispersed in the hard coat layer to be formed, usually, water (alcohol solvent) or other organic solvent is used as a dispersion medium. Used in the form of a sol in which fine particles are colloidally dispersed. Hereinafter, the inorganic oxide fine particles may be simply used as the component (A).

Specific examples of the dispersion medium include alcohol solvents such as methanol, ethanol, isopropanol, and ethylene glycol; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; water; and mixed solvents thereof. Among these, an alcohol solvent or water is preferable.
When these dispersion media are used, (A) the solid content concentration of the inorganic oxide fine particles {the concentration of the (A) inorganic oxide fine particles contained in the sol} is the stability of the dispersion state and the coating composition obtained. From the viewpoint of easy adjustment of the composition, it is preferably 10 to 45% by mass.

(A) As the inorganic oxide fine particles, those having a primary particle diameter of about 1 to 300 nm observed with an electron microscope (TEM) can be preferably used.
The amount of the (A) inorganic oxide fine particles used is such that the proportion of the (A) inorganic oxide fine particles in the finally formed hard coat layer is preferably 20% by mass to 70% by mass, more preferably It is preferable to set according to the amount of other components used so that it is 25 mass% to 60 mass%.
By satisfying the above range, the hard coat layer formed has high hardness and excellent heat resistance. Furthermore, it becomes easier to form a hard coat layer, and cracks can be reduced when the coating agent is cured.

The inorganic oxide fine particles (A) in the present invention are not particularly limited, and an oxide of at least one element selected from Si, Al, Fe, In, Zr, Sn, Sb, Ce, Ti and W Oxide fine particles made of Among these, oxide fine particles made of an oxide of at least one element selected from Si, Zr, Sn, Sb, and Ti are preferable. Specifically, it may be silicon oxide fine particles (silica fine particles), antimony pentoxide fine particles, or composite inorganic oxide fine particles containing a plurality of oxides of the above elements. The ratio is appropriately determined.

For example, when applied to a low refractive index plastic lens substrate having a refractive index of 1.50 or less, silica fine particles are used. The silica fine particles are not particularly limited, and known ones can be used. Specifically, a dispersion in which the solid content concentration is 10% to 45% by mass and the primary particle size is 1 to 300 nm dispersed in water, an alcohol solvent, or another organic solvent is used. Is preferred. Commercially available dispersions of these silica fine particles can be used. For example, water such as SNOWTEX OXS, SNOWTEX OS, SNOWTEX O, SNOWTEX O-40, etc. is used as a dispersion medium from Nissan Chemical Industries, Ltd. There are commercially available silica sols having a dispersion medium of alcohol such as MA-ST-MS (dispersion medium: methanol) and IPA-ST (dispersion medium: isopropanol).

When applied to a high refractive index plastic lens substrate having a refractive index exceeding 1.50, antimony pentoxide fine particles or composite inorganic oxide fine particles containing a plurality of oxides of the above elements are preferably used. Among these, when applied to a high refractive index plastic lens substrate, it is preferable to use composite inorganic oxide fine particles composed of oxides of Si, Zr, Sn, Sb, and Ti. The blending ratio of each component of the composite inorganic oxide fine particles may be appropriately determined according to the application to be used, but 50% to 96% by mass of tin oxide, 3% to 49% by mass of zirconium oxide, and oxidation. It is preferable that 1% by mass to 29.9% by mass of antimony and 0.1% by mass to 29% by mass of silicon oxide are satisfied.
The antimony pentoxide fine particles and the composite inorganic oxide fine particles are dispersed in water, an alcohol solvent, or other organic solvent, and a solid content concentration of 10% by mass to 45% by mass and a primary particle size of 1 to 300 nm are dispersed. It is preferable to use a liquid state. A commercially available dispersion of these inorganic oxide fine particles can be used. Specifically, an antimony pentoxide sol such as AMT-332S · NV (dispersion medium: methanol) manufactured by Nissan Chemical Industries, Ltd. HX series (dispersion medium: methanol), which is a composite inorganic oxide fine particle of zirconium oxide or tin oxide.
When applied to a high-refractive-index plastic lens substrate, inorganic oxide fine particles obtained by mixing antimony pentoxide fine particles or the above composite inorganic oxide fine particles and cerium oxide fine particles are preferably used in order to improve weather resistance. The content of the cerium oxide fine particles is preferably 1% by mass to 30% by mass in 100% by mass of the total inorganic oxide fine particles.

<(B1) Epoxy group-containing silicon compound>
The (B1) epoxy group-containing silicon compound (epoxy group-containing silicon compound) having an epoxy group and a hydrolyzable group of the present invention is a transparent curing that becomes a matrix when a hard coat layer is formed by curing a coating agent. It is a component that forms a body and has a function as a binder of the (A) inorganic oxide fine particles. Hereinafter, the (B1) epoxy group-containing silicon compound may be simply used as the component (B1).
The (B1) epoxy group-containing silicon compound is an organosilicon compound containing an epoxy group in the molecule and a hydrolyzable group such as an alkoxysilyl group (a group in which an alkoxy group is bonded to a Si atom). This epoxy group-containing silicon compound has the effect of increasing the adhesion of the hard coat layer to an optical substrate such as a plastic lens.

(B1) The epoxy group-containing silicon compound can be used without particular limitation as long as it is an organosilicon compound having at least one epoxy group in the molecule and having a hydrolyzable group. Specific examples of the compound include a silicon compound represented by the following formula (III).

In the formula, R ⁹ represents the following formula:

(Wherein R ¹¹ is an alkylene group having 1 to 8 carbon atoms), or a group represented by the following formula

(Wherein R ¹² is an alkylene group having 1 to 8 carbon atoms),
R ⁸ is an alkyl group having 1 to 3 carbon atoms,
R ¹⁰ is an alkyl group having 1 to 3 carbon atoms,
C is an integer of 0-2.

Examples of R ⁸ include a methyl group, an ethyl group, a propyl group, and an isopropyl group, and a methyl group and an ethyl group are particularly preferable. When a plurality of R ⁸ are present, they may be the same groups or different groups. However, C is preferably 0 or 1 in view of reactivity, adhesion, and scratch resistance.
Examples of R ¹⁰ include a methyl group, an ethyl group, a propyl group, and an isopropyl group as in R ^8, and a methyl group and an ethyl group are particularly preferable. When a plurality of R ¹⁰ are present, they may be the same groups or different groups.
R ¹¹ and R ¹² are each an alkylene group having 1 to 8 carbon atoms, and may be linear or branched. Of these, a linear alkylene group having 2 to 3 carbon atoms is preferable.

Specific examples of the component (B1) represented by the formula (III) include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, Mention may be made of γ-glycidoxypropyltriethoxysilane or β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. These may be used alone or in combination of two or more.
Among these, γ-glycidoxypropyltrimethoxysilane (GTS) and γ-glycidoxypropylmethyldimethoxysilane are considered in consideration of adhesion to a plastic optical substrate and scratch resistance in the hard coat layer to be formed. (GDS) is preferred. These GTS and GDS can be used alone or in combination. GTS exhibits excellent effects even when used alone, but when used in combination with GDS, the mass ratio of GTS to GDS (GTS / GDS) is 2.0 or more and 10.0 or less. It is preferable to do.
When one kind of epoxy group-containing silicon compound is used as the component (B1), the mass of the epoxy-containing silicon compound is the blending amount of the component (B1) described in detail below. Moreover, when using 2 or more types of epoxy group containing silicon compounds, those total amounts correspond to the compounding quantity of (B1) component.

[Amount of component (B1)]
In this invention, the compounding quantity of (B1) component is 50 to 350 mass parts by making the compounding quantity of the said (A) inorganic oxide microparticles into 100 mass parts. When the component (B1) is less than 50 parts by mass, the heat resistance and adhesion of the hard coat layer to be formed are lowered, the flexibility is further lowered, and the hard coat layer itself becomes brittle. On the other hand, when it exceeds 350 mass parts, since the hardness of a hard-coat layer falls and scratch resistance falls, it is unpreferable. Considering the hardness, heat resistance, flexibility and the like of the hard coat layer to be formed, the preferable blending amount of the component (B1) is 80 parts by mass or more and 300 parts by mass or less.
In addition, the compounding quantity of this (B1) component is the quantity of the (B1) epoxy group containing silicon compound of the state by which a hydrolysable group, for example, an alkoxysilyl group, is not hydrolyzed.

<(C) Ketimine Compound>
The (C) ketimine compound {hereinafter sometimes simply referred to as the component (C)} exhibits the effect of further improving the adhesion between the hard coat layer to be formed and the plastic optical substrate. This adhesion includes not only the adhesion immediately after forming the hard coat layer, but also the adhesion after a weather resistance test taking into account long-term actual use (hereinafter, this adhesion is assumed to be weather resistance). There is also.) Furthermore, the adhesiveness (hot water resistance) after contacting with warm water can also be improved.

In the present invention, the (C) ketimine compound is a compound having at least one ketimine group in the molecule obtained by blocking the primary amino group of an amine with a ketone. The reason why the (C) ketimine compound exhibits an excellent effect is estimated as follows.
When a ketimine compound is used, the ketimine group is hydrolyzed in the coating agent to produce an amino group (—NH ₂ ), and this amino group is a hard coat layer on a plastic optical substrate by the reaction mechanism described below. It is thought that the adhesiveness of is improved.
The generated amino group reacts with the functional group generated on the surface of the plastic optical substrate activated by pretreatment such as alkali treatment, and the (meth) acryloyl group, epoxy group, isocyanate group, etc. in the substrate. Or is considered to be involved in hydrogen bonds with urethane bonds or carbonate bonds in the substrate. The amino group is also considered to be involved in the addition reaction of the epoxy group of the (B1) epoxy group-containing silicon compound. Due to the effects of hydroxyl groups and amino groups generated by the addition reaction to this epoxy group, the bond and interaction with the plastic optical substrate can be strengthened, so the adhesion between the hard coat layer and the plastic optical substrate, In particular, it is estimated to increase the hot water resistance.

(C) The ketimine compound can be synthesized by reacting an amine compound and a ketone compound. Specifically, the (C) ketimine compound can be synthesized by reacting the amino group of the amine compound with the carbonyl group of the ketone compound.
As the amine compound, an amine compound having 2 to 15 carbon atoms, such as diethylenetriamine, triethylenetetramine, diethylaminopropylamine, m-xylylenediamine, ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, trimethylhexamethylenediamine, N -Aminoethylpiperazine, 1,2-diaminopropane. Examples of the amine compound containing a silicon compound include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyldiethoxymethylsilane, γ-aminopropyldimethoxymethylsilane, and the like.
On the other hand, examples of the ketone compound include those having 2 to 10 carbon atoms such as acetone, methyl ethyl ketone, methyl isopropyl ketone, methyl t-butyl ketone, diisopropyl ketone, and methyl isobutyl ketone.

In order for the coating composition to exhibit the above-described excellent effects, (C) a ketimine compound obtained by reacting the following amine compound with a ketone compound is particularly preferable. Suitable amine compounds include amine compounds containing silicon compounds such as γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyldiethoxymethylsilane, γ-aminopropyldimethoxymethylsilane, On the other hand, suitable ketone compounds include methyl isopropyl ketone, methyl t-butyl ketone, and methyl isobutyl ketone that can be suitably used as the water-soluble organic solvent in the coating composition of the present invention.

Reaction of an amine compound and a ketone compound can be achieved by mixing both. Since the reaction between the amine compound and the ketone compound is an equilibrium reaction in which water is generated, it is necessary to carry out the reaction while removing water. As a method for removing water, a reaction is performed in the presence of a dehydrating agent such as anhydrous sulfate or molecular sieve, or an azeotropic solvent such as toluene is added to the reaction system in advance to carry out the reaction while performing azeotropic dehydration. The method of making it progress is mentioned.
When the (C) ketimine compound used in the present invention is produced, it is preferable to use an amine compound and a ketone compound so that the number of moles of the carbonyl group is larger than the number of moles of the amino group. Specifically, it is set to be 1.5 mol or more and 3.0 mol or less of carbonyl group with respect to 1 mol of amino group. The reason why many ketone compounds are used is that when the amine compound remains unreacted, if it is added to the coating composition of the present invention, hydrolysis and condensation reaction of the organosilicon compound contained in the coating composition proceeds. This is because viscosity may increase or gelation may occur, and the appearance of the hard coat layer to be formed may be deteriorated and hardness may be decreased. On the other hand, even if the ketone compound remains, it can be used as a part of the water-soluble organic solvent of the coating composition of the present invention, so that there is no particular problem.
A ketimine compound, which is a reaction product of an amine compound and a ketone compound, can be confirmed by molecular weight analysis using GC-MASS (gas chromatograph mass spectrometer). Before conducting the analysis by GC-MASS, it is preferable to confirm that the amine compound as a raw material has disappeared.

In the present invention, when the ketimine compound is a ketimine group-containing silicon compound having a ketimine group and a hydrolyzable group (hereinafter sometimes simply referred to as “ketimine group-containing silicon compound”), the amino group In addition to the above action, the following action occurs, and it is considered that a particularly excellent effect is exhibited.
When a ketimine group-containing silicon compound is used, not only does the ketimine group hydrolyze in the coating agent to produce an amino group (—NH ₂ ), but also a hydrolyzable group such as an alkoxysilyl group hydrolyzes to form a silanol group. Arise. By producing these two functional groups, it is considered that the adhesion between the plastic optical substrate and the hard coat layer is further improved.
The silanol group (B1) undergoes a condensation reaction with a silanol group generated from a silicon compound such as an epoxy group-containing silicon compound, or reacts with a silanol group on the surface of the component (A) to form a crosslinked body (cured body). On the other hand, the amino group is considered to act as described above. As a result, the ketimine group-containing silicon compound becomes a part of the cross-linked body forming the hard coat layer, and can further strengthen the bond with the plastic optical substrate. It is presumed that the adhesiveness with the substrate, particularly the hot water resistance is increased. In particular, when a (meth) acrylic resin is used as a plastic optical substrate, it is estimated that a (meth) acryloyl group and an amino group in the resin cause a Michael addition reaction, thereby achieving particularly excellent adhesion. be able to.

For the above reasons, organosilicon compounds having amino groups such as γ-aminopropyltriethoxysilane and N-phenyl-γ-aminopropyltrimethoxysilane are also used for the plastic optical substrate and the hard coat layer to be formed. Although effective in improving adhesion, it is not preferred as a coating agent component for the following reasons.
For example, a compound having a primary amino group such as γ-aminopropyltriethoxysilane has a strong basicity, so that it is considered that the hydrolysis and condensation reaction of the organosilicon compound proceeds locally. As a result, when γ-aminopropyltriethoxysilane is used, the resulting coating agent is prone to white turbidity and spots caused by the organosilicon compound gel substance, and the appearance of the hard coat layer formed There is a risk of causing defects and a decrease in hardness.
On the other hand, since N-phenyl-γ-aminopropyltrimethoxysilane has a weak basic amino group, it must be added in an increased amount in order to improve adhesion. As a result, the hard coat layer to be formed tends to decrease in hardness.

For the above reasons, it is considered that the ketimine group-containing silicon compound exhibits a better effect than the organosilicon compound having an amino group.
As such a ketimine group-containing silicon compound, a compound represented by the following formula (IV) is suitable.

In the formula (IV), R ¹³ , R ¹⁴ , R ¹⁶ and R ¹⁷ are alkyl groups having 1 to 5 carbon atoms, R ¹⁵ is an alkylene group having 1 to 10 carbon atoms, and X is 2 or It is an integer of 3.

Examples of R ¹³ , R ¹⁴ , R ¹⁶ and R ¹⁷ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and a t-butyl group. Of these, a methyl group and an ethyl group are preferable.
Examples of R ¹⁵ include an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, and an octylene group. Among these, an ethylene group, a propylene group, a butylene group, and a pentylene group are preferable.
X is preferably 3 from the viewpoint that a hard coat layer having higher crosslinkability can be formed.

Specific examples of the ketimine group-containing silicon compound represented by the formula (IV) include 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, 3-trimethoxysilyl-N- (1, 3-dimethyl-butylidene) propylamine, 3-methyldiethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, 3-methyldimethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, 3-triethoxysilyl-N- (1,2-dimethyl-propylidene) propylamine, 3-trimethoxysilyl-N- (1,2-dimethyl-propylidene) propylamine, 3-methyldiethoxysilyl-N- ( 1,2-dimethyl-propylidene) propylamine, 3-methyldimethoxysilyl-N- (1,2-dimethyl) Propylidene) and propyl amine.
Among these, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine and 3-trimethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine are preferable. As these ketimine group-containing silicon compounds, commercially available products can be used, and specific examples include trade name “KBE-9103” manufactured by Shin-Etsu Chemical Co., Ltd.
In addition, (C) ketimine compound can also be used independently and can also use 2 or more types of things.

[Amount of component (C)]
(C) The amount of the ketimine compound is 0.1 to 10 parts by mass with respect to 100 parts by mass of the (A) inorganic oxide fine particles. When the blending amount of the (C) ketimine compound is less than 0.1 parts by mass, it is not preferable because the effect of improving the adhesion between the hard coat layer to be formed and the plastic optical substrate, in particular, the hot water resistance is not sufficient. . On the other hand, when the amount exceeds 10 parts by mass, the hardness of the hard coat layer to be formed is lowered, so that sufficient scratch resistance cannot be exhibited. Considering the balance of hardness and adhesion of the hard coat layer to be formed, the blending amount of (C) ketimine compound is more preferably 0.2 parts by mass or more and 8 parts by mass or less, and 0.4 parts by mass or more and 5.5 parts by mass. More preferably, it is 0.5 parts by mass or less, and particularly preferably 0.5 parts by mass or less.
When a plurality of ketimine compounds are used, the total amount of ketimine compounds only needs to satisfy the above range. In addition, when the ketimine compound is a ketimine group-containing silicon compound, the amount of component (C) is the amount of the ketimine group-containing silicon compound in a state where a hydrolyzable group, for example, an alkoxysilyl group is not hydrolyzed. .

The blending amount of the component (C) may satisfy the above range, but in order for the coating composition to exhibit a particularly excellent effect, the blending ratio of the component (B1) and the component (C) is in the following range. Is preferably satisfied.
The blending ratio of the component (B1) and the component (C) is preferably 0.1 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the component (B1). It is more preferable that the amount is not less than mass parts and not more than 5.5 parts by mass, and it is further preferable that the amount is not less than 0.4 parts by mass and not more than 5.5 parts by mass. (B1) The component (C) satisfies the range of 0.1 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the component, whereby the adhesion between the hard coat layer and the plastic optical substrate, particularly heat resistance Aqueous property is improved, and a hard coat layer having sufficient hardness is formed to improve scratch resistance.

The coating composition of the present invention contains the component (A), the component (B1), and the component (C) as essential components, but other components can be blended as necessary. Hereinafter, other components will be described. First, the (B2) other silicon compound that is suitably blended in addition to the silicon compound as the component (B1) and the ketimine group-containing silicon compound as the component (C) will be described.

<(B2) Other silicon compounds>
In the coating composition of the present invention, in addition to the ketimine group-containing silicon compound of the component (B1) and the component (C) for the purpose of improving the hardness of the hard coat layer to be formed, (B2) other than these The silicon compound {hereinafter sometimes simply referred to as component (B2)} can be blended.

The component (B2) used in the present invention includes the following formula (I)

(Where
R ³ is an alkylene group having 1 to 8 carbon atoms,
R ⁴ and R ⁵ are alkyl groups having 1 to 3 carbon atoms,
R ⁶ and R ⁷ are alkyl groups having 1 to 3 carbon atoms,
B is an integer of 0-2. )
Of these, at least one silicon compound selected from the group consisting of silicon compounds is preferred.

In the silicon compound represented by the formula (I), R ¹ is a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a t-butyl group, or the like. Of these, a methyl group and an ethyl group are preferable. R ² is a methyl group, an ethyl group, a propyl group, an isopropyl group or the like, and is preferably a methyl group or an ethyl group. Furthermore, since the more hydrolyzable groups tend to increase the hardness, A is preferably 0 or 1.

In the silicon compound represented by the formula (II), R ³ may be a linear or branched alkylene group, specifically, a methylene group, an ethylene group, a propylene group, a butylene group, or pentylene. Group, hexylene group, heptylene group, octylene group and the like, and a methylene group, an ethylene group, a propylene group, and a butylene group are particularly preferable. R ⁴ and R ⁵ are a methyl group, an ethyl group, a propyl group, an isopropyl group, and the like, and among them, a methyl group and an ethyl group are preferable. R ⁶ and R ⁷ are a methyl group, an ethyl group, a propyl group, an isopropyl group, and the like, and among them, a methyl group and an ethyl group are preferable.

Specific examples of the compounds represented by the formulas (I) and (II) include tetraalkoxysilanes such as tetraethoxysilane; methyltrialkoxysilanes such as methyltrimethoxysilane and methyltriethoxysilane; ethyltriethoxysilane. , Dimethyldimethoxysilane, 1,2-bis (triethoxysilyl) ethane, 1,2-bis (trimethoxysilyl) ethane, 1,6-bis (triethoxysilyl) hexane, 1,6-bis (diethoxymethyl) Silyl) hexane, 1,6-bis (trimethoxysilyl) hexane, 1,6-bis (dimethoxymethylsilyl) hexane, 1,8-bis (triethoxysilyl) octane, 1,8-bis (trimethoxysilyl) Octane, 1,8-bis (diethoxymethylsilyl) octane, 1- (triethoxysilane Le) -2-(diethoxy methyl silyl) ethane and the like.
In particular, from the viewpoint of further improving the hardness of the hard coat layer, a silicon compound having three or more hydrolyzable groups is preferable. Specifically, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane 1,2-bis (triethoxysilyl) ethane and the like are preferably used. The compounds represented by the formulas (I) and (II) can be used alone or in combination of two or more.

[Amount of component (B2)]
The blending amount of the component (B2) is preferably 10 parts by mass or more and 150 parts by mass or less with the component (A) as 100 parts by mass. When the blending amount of the component (B2) satisfies the above range, the hardness of the hard coat layer to be formed can be improved, and furthermore, cracks generated when the coating agent is cured can be reduced. . In view of the hardness of the hard coat layer to be formed and crack suppression, the blending amount of the component (B2) is more preferably 20 parts by mass or more and 120 parts by mass or less.
When a plurality of types of (B2) components are used, the total amount only needs to satisfy the above range. Moreover, the compounding quantity of this (B2) component is the quantity of the (B2) component of the state which is not hydrolyzed.

When the component (B2) is used, the component (B2) is preferably used so as to satisfy the above blending amount with respect to the component (A), but the blending ratio with the component (B1) is in the following range. Satisfying the effect is particularly excellent. That is, with respect to 100 parts by mass of component (B1), the component (B2) is preferably 1 part by mass or more and 150 parts by mass or less, more preferably 10 parts by mass or more and 120 parts by mass or less, and 15 parts by mass. More preferably, the amount is 100 parts by mass or less. In this case as well, the blending ratio of the component (B1) and the component (C) is such that the component (C) is 0.1 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the component (B1). Is more preferably 0.3 parts by mass or more and 5.5 parts by mass or less, and further preferably 0.4 parts by mass or more and 5.5 parts by mass or less.

In the coating composition of the present invention, known components used in ordinary coating compositions, specifically, water, curing catalyst, water-soluble organic solvent, additives and the like can be blended.

〔water〕
In the coating composition of the present invention, the component (B1) and the component (B2) blended as necessary are hydrolyzed, and the hydrolyzate is polymerized and cured (polycondensation) with the component (A) incorporated. ) To form a cured body to be a matrix, and a hard coat layer in which the component (A) is densely dispersed in the matrix is formed. In order to form this coat layer, it is preferable to add water in order to promote hydrolysis of the components (B1) and (B2).

The amount of such water is preferably 10 parts by mass or more and 100 parts by mass or less, more preferably 15 parts by mass or more and 90 parts by mass per 100 parts by mass of the total mass of the components (B1) and (B2) used in the present invention. It is 15 parts by mass or less and particularly preferably 80 parts by mass or less. In addition, when not using (B2) component, the compounding quantity of the said water makes the quantity of only (B1) component 100 mass parts. Moreover, the blending amount of the water is based on that in which the components (B1) and (B2) are not hydrolyzed.
If the amount of water is too small, hydrolysis of each component (B1) and (B2) does not proceed sufficiently, and the scratch resistance of the resulting hard coat layer tends to decrease. Properties such as storage stability may be reduced. If the amount of water is too large, it is difficult to form a hard coat layer having a uniform thickness, which may adversely affect optical properties. In addition, when (C) component is a ketimine group-containing silicon compound, this (C) component is also hydrolyzed, but since the blending amount of (C) component is smaller than the blending amount of (B1) component, It can be sufficiently hydrolyzed with the above amount of water.

As described above, the component (A) may be used in the form of a dispersion (sol) dispersed in water. In such a case, the amount of water used includes the amount of water used in the dispersion. For example, when the component (A) is used, if the amount of water contained in the dispersion satisfies the range of the amount of water, it is not necessary to add water to the coating composition. On the other hand, when the water content is less than the range, water is further added.

Moreover, since the water used by this invention accelerates | stimulates the hydrolysis of (B1) and (B2) component, it can also be made into acid aqueous solution. In this case, since there is little acid content, the quantity of aqueous acid solution can be made into the compounding quantity of water.
Specifically, an aqueous acid solution such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, or an organic acid such as acetic acid or propionic acid can be used. Among these, hydrochloric acid and acetic acid are preferably used from the viewpoints of storage stability and hydrolyzability of the coating composition. The concentration of the acid aqueous solution is preferably 0.001 to 0.5N, particularly 0.01 to 0.1N. In addition, when using both water and acid aqueous solution, the total mass of water and acid aqueous solution should just satisfy the compounding quantity of the said water.

[Curing catalyst]
The following curing catalyst can be mix | blended with the coating composition of this invention. The curing catalyst is used to promote condensation (polymerization curing) of each hydrolyzate of the component (B1), the (C) ketimine group-containing silicon compound, and the component (B2) to be blended as necessary. .
Specifically, an acetylacetonate complex, a perchlorate, an organic metal salt, and various Lewis acids are used, and these can be used alone or in combination of two or more. By using these curing catalysts, the hard coat layer can be made harder.

Examples of the acetylacetonate complex include those described in JP-A-11-119011, specifically, aluminum acetylacetonate, lithium acetylacetonate, indium acetylacetonate, chromium acetylacetonate, nickel acetylacetate. Examples thereof include narate, titanium acetylacetonate, iron acetylacetonate, zinc acetylacetonate, cobalt acetylacetonate, copper acetylacetonate, and zirconium acetylacetonate. Among these, aluminum acetylacetonate and titanium acetylacetonate are preferable.
Examples of the perchlorate include magnesium perchlorate, aluminum perchlorate, zinc perchlorate, and ammonium perchlorate.
Examples of the organic metal salt include sodium acetate, zinc naphthenate, cobalt naphthenate, and zinc octylate.
Examples of Lewis acids include stannic chloride, aluminum chloride, ferric chloride, titanium chloride, zinc chloride, and antimony chloride.
From the viewpoint that a hard coat layer having high scratch resistance can be obtained in a short time even at a relatively low temperature, and the storage stability of the coating composition is excellent, an acetylacetonate complex or perchlorate is used as a curing catalyst. It is preferable to do. Among them, it is preferable that 50% by mass or more of the curing catalyst, particularly 70% by mass or more, and optimally the entire amount of the curing catalyst is an acetylacetonate complex or a perchlorate.

From the viewpoint of obtaining a harder hard coat layer, the curing catalyst is 0.5 parts by mass or more and 15 parts by mass or less, particularly 1 part by mass or more and 13 parts by mass or less per 100 parts by mass of the component (A). It is preferably used in amounts in the range. In addition, when using 2 or more types of curing catalysts, the total amount should just satisfy the said range.

(Water-soluble organic solvent)
A water-soluble organic solvent can be added to the coating composition of the present invention. In the present invention, the water-soluble organic solvent means an organic solvent having a solubility in water at 25 ° C. of 10% by mass or more, preferably 50% by mass or more.
The water-soluble organic solvent serves as a solvent for the component (B1), the component (C), and the component (B2) to be blended as necessary, and a dispersion medium for the component (A). Specific examples of such water-soluble organic solvents include alcohols such as methanol, ethanol, propanol, isopropanol, t-butyl alcohol, 2-butanol and diacetone alcohol; lower alcohol esters of lower carboxylic acids such as methyl acetate. Ethers such as cellosolve, dioxane and ethylene glycol monoisopropyl ether; ketones such as acetone, methyl ethyl ketone and acetylacetone. These organic solvents can be used alone or in admixture of two or more.
From the viewpoint of easily evaporating when a coating agent is applied and cured to form a smooth hard coat layer, methanol, isopropanol, t-butyl alcohol, diacetone alcohol, ethylene glycol monoisopropyl ether, acetylacetone are particularly used. It is preferable to use it. In addition, as described above, a part of such a water-soluble organic solvent can be mixed with inorganic oxide fine particles in advance as a dispersion medium for the component (A).

The amount of the water-soluble organic solvent used is not particularly limited, but in order to obtain storage stability and sufficient scratch resistance, it is preferably 200 parts by mass or more and 1000 parts by mass per 100 parts by mass of the component (A). Hereinafter, more preferably, the range is 250 parts by mass or more and 800 parts by mass or less. In addition, the compounding quantity of this water-soluble organic solvent is the quantity which does not contain the alcohol which (B1) component, (C) ketimine group containing silicon compound, and (B2) component produced | generated by hydrolysis, respectively. Moreover, when using together 2 or more types of water-soluble organic solvents, the total amount should just satisfy the said range.

[Other additive components]
A cyclic ketone compound can also be added to the coating composition of the present invention for the purpose of improving and stabilizing the adhesion between the hard coat layer and the plastic lens substrate. Specific examples include N-methylpyrrolidone, ε-caprolactam, γ-butyrolactone, 1-vinyl-2-pyrrolidone, isophorone, cyclohexanone, methylcyclohexanone, and the like. The compounding amount of these cyclic ketone compounds is preferably 0.1 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the component (A).

Further, a quaternary ammonium salt can be added to the coating composition used in the present invention for the purpose of improving the adhesion between the plastic lens substrate and the hard coat layer. Although the mechanism of action by which the above effect is obtained by adding a quaternary ammonium salt is not clear, the function as a reaction catalyst in which the quaternary ammonium salt accelerates the reaction of the epoxy group of the (B1) epoxy group-containing silicon compound, In addition, since it has a function as a surfactant, it is considered that the adhesion is improved due to such a function.
As the quaternary ammonium salt, those in which an alkyl group having 1 to 4 carbon atoms is substituted for nitrogen are preferable, and those having a halogen atom as a counter ion are preferable. Specific examples of such quaternary ammonium salts include tetramethylammonium chloride, tetramethylammonium bromide, tetra-n-butylammonium chloride, tetra-n-butylammonium bromide, dimethyldiisopropylammonium chloride, tetra-n-butyl. Examples thereof include ammonium acetate and tetraisopropylammonium chloride. Among these, tetramethylammonium chloride, tetramethylammonium bromide, tetra-n-butylammonium chloride, and tetra-n-butylammonium bromide are preferably used from the viewpoint of easy availability and an effect of improving adhesion.
The amount of the quaternary ammonium salt is preferably 0.1 parts by mass or more and 1 part by mass or less with respect to 100 parts by mass of the component (A). The quaternary ammonium salt only needs to be contained in a trace amount in the coating composition, and when it exceeds 1 part by mass, the hard coat layer may be whitened, which is not preferable.

Furthermore, as long as the object of the present invention is not impaired, other additives that are usually blended in the coating composition for forming the hard coat layer can be blended. Examples of such additives include surfactants, antioxidants, radical scavengers, UV stabilizers, UV absorbers, mold release agents, anti-coloring agents, antistatic agents, fluorescent dyes, dyes, pigments, and fragrances. And plasticizers.

For example, as the surfactant, any of a nonionic surfactant, an anionic surfactant, and a cationic surfactant can be used, but a nonionic surfactant is preferably used from the viewpoint of wettability to a plastic lens substrate.
Specific examples of nonionic surfactants that can be suitably used include sorbitan fatty acid ester, glycerin fatty acid ester, decaglycerin fatty acid ester, propylene glycol / pentaerythritol fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbit fatty acid ester , Polyoxyethylene glycerin fatty acid ester, polyethylene glycol fatty acid ester, polyoxyethylene alkyl ether, polyoxyethylene phytosterol / phytostanol, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene castor oil / cured Castor oil, polyoxyethylene lanolin, lanolin alcohol, beeswax derivative, poly Alkoxy polyoxyethylene alkyl amine fatty acid amides, polyoxyethylene alkylphenyl formaldehyde condensates, can be mentioned a single-chain polyoxyethylene alkyl ethers. In using the surfactant, two or more kinds may be mixed and used. The addition amount of the surfactant is preferably in the range of 0.01 to 2.0 parts by mass per 100 parts by mass of the (A) inorganic oxide fine particles.

In addition, antioxidants such as hindered phenol antioxidants, radical scavengers such as phenol radical scavengers, UV stabilizers such as benzoate compounds, UV absorbers such as benzotriazole compounds and benzophenone compounds, etc. It can mix | blend suitably. The amount of these additives is preferably in the range of 0.1 to 2 parts by mass per 100 parts by mass of the (A) inorganic oxide fine particles.

Dyes and pigments are used to color optical substrates. Nitroso dyes, nitro dyes, azo dyes, stilbenzoazo dyes, ketoimine dyes, triphenylmethane dyes, xanthene dyes, acridine dyes, quinoline dyes , Methine dye, polymethine dye, thiazole dye, indamine dye, indophenol dye, azine dye, oxazine dye, thiazine dye, sulfur dye, aminoketone dye, oxyketone dye, anthraquinone dye, perinone dye, indigoid dye, phthalocyanine dye, azo series Examples thereof include pigments, anthraquinone pigments, phthalocyanine pigments, naphthalocyanine pigments, quinacridone pigments, dioxazine pigments, indigoid pigments, triphenylmethane pigments, and xanthene pigments.
When using dyes and pigments, the amount used is appropriately determined according to the color density of the substrate to be colored. Therefore, although it cannot be generally limited, the amount used is preferably in the range of 0.001 to 1 part by mass per 100 parts by mass of the (A) inorganic oxide fine particles.

Next, a method for producing a coating agent by mixing a coating composition containing the above components will be described.
<Manufacturing method of coating agent>
The coating agent obtained from the coating composition can be produced by weighing and mixing a predetermined amount of each component. The mixing order of each component is not particularly limited, and all components can be mixed at the same time. However, in order to obtain a coating agent capable of obtaining stable physical properties from the beginning of preparation without prolonged turbidity, hydrolysis is required. It is preferable to mix the components in the order in which the previous component (B1) and component (C) are not in direct contact. Specifically, a method in which the hydrolyzate of component (B1) and the component (A) are mixed in advance and the component (C) are mixed, or the component (A) and component (C) are mixed in advance. The method of mixing the mixture and the hydrolyzate of component (B1) is employed. Hereinafter, these mixing methods will be described.

[Method of Mixing Component (C1) with Mixture of Component (B1) Hydrolyzate and Component (A)]
(B1) The hydrolyzate of component and the mixture of component (A) are mixed with (B1) epoxy group-containing silicon compound with water or an aqueous acid solution, and then mixed with (A) inorganic oxide fine particles. Or (A) A dispersion obtained by dispersing inorganic oxide fine particles in water or a water-soluble organic solvent and (B1) component are mixed, and (B1) component is hydrolyzed and both components are mixed at the same time. I can.
When obtaining a mixture of the hydrolyzate of component (B1) and component (A), the physical properties of the hard coat layer are not adversely affected, and the storage stability of the resulting coating agent is not reduced. Therefore, it is preferable to perform mixing at a temperature of 10 to 40 ° C. for 5 to 72 hours. Under this condition, the component (B1) can be sufficiently hydrolyzed. The end of hydrolysis of the component (B1) may be confirmed by the amount of alcohol generated during hydrolysis.
Subsequently, a coating agent is manufactured by mixing the said mixture and (C) component. At this time, if the (B1) component is not sufficiently hydrolyzed, and if the mixing and reaction of the (A) component and the (B1) component is insufficient, white turbidity and sediment may occur. . The reason for this is not clear, but the amino group produced by the hydrolysis of component (C) locally promotes the condensation of the silanol groups produced by the hydrolysis of component (B1), so that a high molecular weight component is produced. Is presumed to be the cause. Therefore, after (B1) component is hydrolyzed, the stability at the time of coating agent manufacture can be improved by mixing (C) component. In addition, when using (B2) component, it hydrolyzes at the same timing as (B1) component.

The order of mixing water, curing catalyst, water-soluble organic solvent, and other additives added as necessary in the present invention is not particularly limited, and all components can be mixed at the same time. It is preferable to mix when the component (B1) and the component (B2) are hydrolyzed. The water-soluble organic solvent and other additives may be mixed before and after hydrolyzing the component (B1) and the component (B2), or a mixture of the hydrolyzate of the component (B1) and the component (A). May be mixed. The curing catalyst may be mixed after the hydrolysis of the component (B1) and the component (B2), or the hydrolyzate of the component (B1) and the component (B2) may be mixed with the component (A) or a water-soluble organic compound. You may mix after adding a solvent. The component (C) is most preferably mixed after all the above components are mixed.

[Method of mixing the mixture of component (A) and component (C) and the hydrolyzate of component (B1)]
The mixture of the component (A) and the component (C) can be obtained by mixing the dispersion (A) in which the inorganic oxide fine particles are dispersed in water or a water-soluble organic solvent and the component (C). In order to suppress hydrolysis of the component (C), it is preferable to use a water-soluble organic solvent as the dispersion medium of the component (A).
On the other hand, the hydrolyzate of the component (B1) can be obtained by a known method, for example, by adding and mixing the component (B1) in water (acidic aqueous solution). The completion of hydrolysis may be confirmed by the amount of alcohol generated during hydrolysis. In addition, when using (B2) component, it is preferable to hydrolyze (B1) component and (B2) component simultaneously.

The mixture of the component (A) and the component (C) thus obtained and the hydrolyzate of the component (B1) are mixed to obtain a coating agent. At this time, the order of mixing water, curing catalyst, water-soluble organic solvent, and other additives added as necessary is not particularly limited, but water is (B1) component, (B2 It is preferable to mix when hydrolyzing the component. The water-soluble organic solvent and other additives can be mixed before and after hydrolyzing the component (B1) and the component (B2), or mixed before and after the components (A) and (C) are mixed. Alternatively, the mixture of the component (A) and the component (C) and the hydrolyzate of the component (B1) may be mixed and then mixed. The water-soluble organic solvent is used as a dispersion medium for the component (A) and mixed with the component (C), or after the components (A) and (C) are mixed, the water-soluble organic solvent is added thereto. It is preferable to do. Moreover, it is preferable that a curing catalyst mixes, after mixing the mixture of (A) component and (C) component, and the hydrolyzate of (B1) component.

By adopting the above method, the physical properties of the hard coat layer are not adversely affected, and the stability of the coating agent itself can be improved. In particular, considering that the coating agent is continuously produced, it is preferable to mix the diluted component (C) with the hydrolyzate of component (B1), so that component (A) and component (C) A method of mixing a mixture in which components are mixed in advance and a hydrolyzate of component (B1) is preferably employed.

The solid content concentration in the coating agent obtained by mixing in this way is not particularly limited, but is 15% by mass to 50% by mass, preferably 20% by mass to 40% by mass in the total mass of the coating agent. It is below mass%.

<Optical substrate made of plastic>
Next, an optical substrate such as a plastic lens on which the obtained coating agent is applied will be described.
The coating composition of the present invention is applied to the formation of a hard coat layer on the surface of a plastic optical substrate such as an eyeglass lens, a camera lens, or a liquid crystal display, and is particularly preferably used for an eyeglass lens.

The type of plastic used for plastic lenses such as eyeglass lenses is not particularly limited, and examples thereof include (meth) acrylic resins, epoxy resins, polycarbonate resins, allyl resins, urethane resins, and thioepoxy resins. Known resins can be mentioned. The coating composition of the present invention can be applied without any limitation as a hard coat layer formed on the resin surface.
Especially the coating agent obtained from the coating composition of this invention can improve more adhesiveness with (meth) acrylic-type resin and urethane type resin. The reason for this is that, as described above, the amino group generated by hydrolysis of the (C) ketimine compound added in the present invention is a functional group generated on the surface of a plastic lens substrate activated by pretreatment such as alkali treatment. It is estimated that high adhesion can be obtained by the reaction. In particular, for plastic optical substrates containing (meth) acrylic resins, the (meth) acryloyl group remaining in the (meth) acrylic resin and the amino group generated from the (C) component are bonded by the Michael addition reaction By doing so, it is considered that high adhesion is expressed.

[(Meth) acrylic resin]
The coating composition of the present invention can suitably form a hard coat layer on a plastic optical substrate made of a (meth) acrylic resin containing a photochromic compound.
Conventionally, it is known that a hard coat layer is hardly adhered to a (meth) acrylic resin. Conventionally, there has been a method of adding 2-hydroxyethyl (meth) acrylate, glycidyl methacrylate, γ-methacryloyloxypropyltrimethoxysilane, or the like to a (meth) acrylic resin in order to improve the adhesion of the hard coat layer. Are known.
However, the addition of 2-hydroxyethyl (meth) acrylate increases the hygroscopicity of the resulting plastic optical substrate, and causes problems such as long-term storage stability of the lens substrate. In addition, when glycidyl methacrylate is added to a (meth) acrylic resin containing a photochromic compound (particularly a chromene compound), there may be a problem that the plastic lens substrate is colored by interacting with the photochromic compound. Further, when γ-methacryloyloxypropyltrimethoxysilane is added, it is difficult to peel from the glass mold when releasing the cured product of the (meth) acrylic resin obtained in the glass mold. There is a problem that cracks occur in the cured body of the (meth) acrylic resin.
The coating composition of the present invention is a component that improves the adhesion of a coating composition such as 2-hydroxyethyl (meth) acrylate, glycidyl methacrylate, and γ-methacryloyloxypropyltrimethoxysilane in a (meth) acrylic resin. Can also be suitably used for plastic lens substrates that do not contain any of the above.

The (meth) acrylic resin used in the present invention is not particularly limited, but has a polyfunctional acrylate having a (meth) acrylate group having three or more functional groups and an alkylene glycol chain having 2 to 15 repeating units. A (meth) acrylic resin obtained by curing a composition containing di (meth) acrylate is preferable. The polymers of these (meth) acrylate compounds provide a photochromic lens having a high color density and a fast fading speed because there are many free spaces where the photochromic compound is likely to undergo structural changes when the photochromic compound coexists. I can do it.
Specific examples of such a polyfunctional acrylate having a tri- or higher functional (meth) acrylate group include trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, tetramethylolmethane trimethacrylate, and tetramethylolmethane triacrylate. It is done.
Examples of the di (meth) acrylate having an alkylene glycol chain having 2 to 15 repeating units include polyethylene glycol dimethacrylate having an average molecular weight of 536, polytetramethylene glycol dimethacrylate having an average molecular weight of 736, and polypropylene glycol dimethacrylate having an average molecular weight of 536. Methacrylate, polyethylene glycol diacrylate having an average molecular weight of 258, polyethylene glycol diacrylate having an average molecular weight of 308, polyethylene glycol diacrylate having an average molecular weight of 522, polyethylene glycol methacrylate acrylate having an average molecular weight of 272, polyethylene glycol methacrylate acrylate having an average molecular weight of 536, 2,2 -Bis [4-methacryloxy polyethoxy) phenyl] propane, 2,2-bis [4-actyl Proxy-diethoxy) phenyl] propane, 2,2-bis [4- acryloxy polyethoxy) phenyl] propane.
Further, the composition containing the polyfunctional acrylate having a tri- or higher functional (meth) acrylate group and the di (meth) acrylate having an alkylene glycol chain having 2 to 15 repeating units includes other polymerizable monomers. For example, a (meth) acrylate monomer such as urethane acrylate can also be added.

A plastic lens base material (photochromic lens base material) containing a photochromic compound is a base material in which a photochromic compound is dispersed inside the base material, or a base material in which a photochromic coating layer in which a photochromic compound is dispersed is formed on the surface of the base material. There may be.
Specifically, the coating composition of the present invention is suitably used for forming a hard coat layer of a base material using a polymerization curable composition containing the (meth) acrylate monomer and a photochromic compound as a photochromic lens by a kneading method. it can. Further, the surface of the plastic lens substrate is coated with a polymerization curable composition containing the (meth) acrylate monomer and the photochromic compound, and then cured to form a photochromic coating layer of the hard coating layer of the substrate. It can also be suitably used for forming.

[Urethane resin]
The coating agent obtained from the coating composition of the present invention has excellent adhesion to urethane resins. The reason is that the urethane bond part contained in the urethane-based resin and the amino group produced by hydrolysis of the component (C) interact with each other such as hydrogen bonds, thereby presuming high adhesion. .

The urethane-based resin used in the present invention is a resin obtained by reacting a thiol compound and an isocyanate compound.
Examples of the thiol compound include 1,2-ethanedithiol, 1,6-hexanedithiol, 1,2,3-propanetrithiol, propanetris (2-mercaptoacetate), 1,3-propanedithiol, tetrakis (mercapto) Methyl) methane, petaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (2-mercaptopropionate), tetrakis (2-mercaptoethylthiomethyl) propane, 2-mercaptoethanol, 2,3-dimercaptopropanol, 3-mercapto-1,2-propanediol, di (2-mercaptoethyl) sulfide, 2,5-dimercapto-1,4-dithiane, 2,5-dimercaptomethyl-1,4-dithiane, tris (mercaptomethyl) ) Isocyan 1,4-dimercaptocyclohexane, 4-mercaptophenol, 1,2-benzenedithiol, 1,3,5-benzenetrithiol, 1,2-dimercaptomethylbenzene, 1,3-dimercaptomethylbenzene, 1,4-dimercaptomethylbenzene, 1,3,5-trimercaptomethylbenzene, bismercaptoethyl sulfide, 1,2-bis {(2-mercaptoethyl) thio} -3-mercaptopropane, 1,2-bis (Mercaptomethylthio) ethane, tetrakis (mercaptoethylthiomethyl) methane and the like can be mentioned.

Examples of the isocyanate compound include methylene diphenyl diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,2-diisocyanate benzene, 1,3-diisocyanate benzene, 1,4-diisocyanate. Isocyanate benzene, 1,2-diisocyanate methylbenzene, 1,3-diisocyanate methylbenzene, 1,4-diisocyanate methylbenzene, 4,4'-diphenylene diisocyanate, 3,3'-dimethyl- 4,4'-diphenylene diisocyanate, xylylene diisocyanate, naphthylene 1,5-diisocyanate, tetramethylxylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate Tetramethyl xylylene diisocyanate, 1,3,5-isocyanatomethyl cyclohexane and the like.

Next, a method for producing an optical article having a hard coat layer by applying the coating agent obtained by the above method on an optical substrate such as a plastic lens will be described.

<Optical article manufacturing method, optical article>
The produced coating agent is filtered to remove foreign substances as necessary, and then applied to the surface of the plastic lens substrate, dried and cured to form a hard coat layer. Note that the plastic optical substrate may be subjected to various surface treatments. Examples of such surface treatment include chemical treatment using a basic aqueous solution or acidic aqueous solution, polishing treatment using an abrasive, plasma treatment using atmospheric pressure plasma and low-pressure plasma, corona discharge treatment, and the like. it can.

The coating agent can be applied by dipping, spin coating, dip spin coating, spraying, brushing or roller coating.
After drying, the coating is first preliminarily cured at 60 to 80 ° C. for about 5 to 30 minutes, and then cured at a temperature of 90 to 120 ° C. for about 1 to 3 hours, depending on the substrate. Is good. In particular, since the coating agent obtained from the coating composition of the present invention exhibits excellent adhesion, the temperature after preliminary curing can be made relatively low. Specifically, the temperature after pre-curing can be 95 to 115 ° C., more preferably 100 to 110 ° C. Since it can be cured at a relatively low temperature in this way, it is possible to prevent yellowing and thermal deformation of the plastic lens.

The hard coat layer to be formed may have a thickness of about 0.1 to 10 μm. In general, a thickness of 1 to 5 μm is suitable for a spectacle lens. By adopting the above method, an optical article in which a hard coat layer is formed on a plastic lens substrate can be obtained.
According to the coating composition of the present invention, not only a hard coat layer having excellent scratch resistance can be provided, but also appearance defects such as peeling of the hard coat layer can be prevented even when used for a long period of time.

In the plastic lens substrate of the present invention, an antireflection film is further formed on the hard coat layer by vapor deposition of a thin film made of a metal oxide such as SiO ₂ , TiO ₂ , ZrO _2, or coating of a thin film of an organic polymer. May be formed. Further, an impact resistant primer such as a urethane primer may be provided between the plastic lens substrate and the hard coat layer. Furthermore, the antireflection film can be subjected to processing such as antistatic treatment, water repellent treatment and antifogging treatment, and secondary treatment.

EXAMPLES Hereinafter, although an Example and a comparative example are hung up and this invention is demonstrated, this invention is not limited to these Examples. In addition, not all combinations of features described in the embodiments are essential to the solution means of the present invention.
The optical base material (lens base material) used in this example and each component of the coating composition will be described.

(1) Plastic optical substrate (lens substrate)
CR: Allyl resin plastic lens, refractive index = 1.50
MRA: Thiourethane resin plastic lens, refractive index = 1.60
MRB: Thiourethane resin plastic lens, refractive index = 1.67
MA1: Methacrylic resin photochromic lens produced as follows: 43 parts by mass of polypropylene glycol dimethacrylate having an average molecular weight of 328, 10 parts by mass of trimethylolpropane trimethacrylate, and 5 parts by mass of methoxypolyethylene glycol methacrylate having an average molecular weight of 394. A polymerizable composition is prepared using 16 parts by mass of polyethylene glycol diacrylate having an average molecular weight of 522, 1 part by mass of glycidyl methacrylate, 1 part by mass of α-methylstyrene dimer, and 25 parts by mass of urethane acrylate (EBECRYL4858 manufactured by Daicel Chemical Industries). Then, with respect to 100 parts by mass of the polymerizable composition, 0.1 part by mass of bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and the following photochromic compound (1) 0.03 part by mass, 1.0 part by mass of t-butylperoxyneodecanate as a radical polymerization initiator, and 0.1 part by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) may be added. The mixture was mixed to prepare a photochromic polymerization curable composition. Next, the obtained composition was poured into a mold composed of a glass plate and a gasket made of an ethylene-vinyl acetate copolymer, and cast polymerization was performed. The polymerization was carried out using an air furnace, gradually raising the temperature from 33 ° C. to 90 ° C. over 17 hours, and then maintained at 90 ° C. for 2 hours. After completion of the polymerization, the mold was taken out from the air furnace and allowed to cool, and then the cured product was removed from the glass of the mold, and then placed in an oven and heated at 110 ° C. for 3 hours.

MA2: Methacrylic resin lens produced as follows: 43 parts by mass of polypropylene glycol dimethacrylate having an average molecular weight of 328, 10 parts by mass of trimethylolpropane trimethacrylate, 5 parts by mass of methoxypolyethylene glycol methacrylate having an average molecular weight of 394, which are radical polymerizable monomers A polymerizable composition is prepared using 16 parts by mass of polyethylene glycol diacrylate having an average molecular weight of 522, 1 part by mass of α-methylstyrene dimer, and 26 parts by mass of urethane acrylate (EBECRYL4858 manufactured by Daicel Chemical Industries) as a raw material. 100 parts by mass, 0.1 part by mass of bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, 0.03 part by mass of photochromic compound (1), t- Butylpa 1.0 part by mass oxy neodecanate, and 2,2'-azobis (2,4-dimethylvaleronitrile) were mixed well with the addition of 0.1 part by mass, to prepare a photochromic polymerizable curable composition. Next, the obtained composition was poured into a mold composed of a glass plate and a gasket made of an ethylene-vinyl acetate copolymer, and cast polymerization was performed. The polymerization was carried out using an air furnace, gradually raising the temperature from 33 ° C. to 90 ° C. over 17 hours, and then maintained at 90 ° C. for 2 hours. After completion of the polymerization, the mold was taken out from the air furnace and allowed to cool, and then the cured product was removed from the glass of the mold, and then placed in an oven and heated at 110 ° C. for 3 hours.

MA3: Photochromic lens having a photochromic layer on the surface produced as described below 2,2-bis (4-acryloyloxypolyethylene glycol phenyl) propane / polyethylene glycol diacrylate having an average molecular weight of 776, which is a radical polymerizable monomer (average molecular weight 532) / Trimethylolpropane trimethacrylate / polyester oligomer hexaacrylate / glycidyl methacrylate were blended in a blending ratio of 49 parts by mass / 15 parts by mass / 25 parts by mass / 10 parts by mass / 1 part by mass, respectively. Next, 3 parts by mass of the photochromic compound (2) was added to 100 parts by mass of the radical polymerizable monomer mixture, and ultrasonic dissolution was performed at 70 ° C. for 30 minutes. Thereafter, a mixture of CGI 1870: 1-hydroxycyclohexyl phenyl ketone and bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide as a polymerization initiator (weight ratio 3) was added to the obtained composition. 7) 0.35 parts by mass, stabilizer bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate 5 parts by mass, triethylene glycol-bis [3- (3-t -Butyl-5-methyl-4-hydroxyphenyl) propionate 3 parts by weight, silane coupling agent γ-methacryloyloxypropyltrimethoxysilane 7 parts by weight, and leveling agent Toray Dow Corning Silicone Of 0.1% by weight of a surfactant L-7001 and mixed well to produce photochromic Polymerizable curable composition (photochromic coating agent) was prepared.

MRA (thiourethane resin plastic lens, refractive index = 1.60) was used as an optical substrate made of plastic, and this optical substrate made of plastic was thoroughly degreased with acetone and washed with a 5% aqueous sodium hydroxide solution at 50 ° C. After washing for 4 minutes, washing with running water for 4 minutes, and washing with distilled water at 40 ° C. for 4 minutes, it was dried at 70 ° C. Next, as a primer coating solution, a moisture curing type primer “Takeseal PFR402TP-4” manufactured by Takebayashi Chemical Industry Co., Ltd. and ethyl acetate are prepared to be 50 parts by mass, respectively. A liquid obtained by adding 0.03 part by mass of a leveling agent FZ-2104 manufactured by company and sufficiently stirred under a nitrogen atmosphere until uniform was used. This primer solution was spin-coated on the surface of lens B using a spin coater 1H-DX2 manufactured by MIKASA. By leaving this lens at room temperature for 15 minutes, a lens substrate having a primer layer with a thickness of 7 μm was prepared.
Next, about 1 g of the above-described photochromic polymerization curable composition (photochromic coating agent) was spin-coated on the surface of the lens substrate having the primer layer. Fusion UV adjusted so that an output at 405 nm of the lens surface is 150 mW / cm ² in a nitrogen gas atmosphere on a lens coated with a coating film made of the photochromic polymerization curable composition (photochromic coating agent). Using F3000SQ equipped with a D valve manufactured by Systems, light irradiation was performed for 3 minutes to cure the coating film. Then, the photochromic coating layer was formed by performing heat processing for 1 hour with a 110 degreeC thermostat further. The film thickness of the resulting photochromic coating layer can be adjusted depending on the spin coating conditions. The film thickness of the photochromic coat layer was adjusted to be 40 ± 1 μm.

(2) Coating composition component [component A; inorganic oxide fine particles]
SOL1: methanol-dispersed silica sol. (Manufactured by Nissan Chemical Industries, Ltd.), solid content (silica fine particle concentration) = 30% by mass.
SOL2: a methanol-dispersed sol of composite metal oxide fine particles containing 11.7% by mass of zirconium oxide, 77.6% by mass of tin oxide, 7.0% by mass of antimony oxide, and 3.7% by mass of silicon dioxide. Solid content concentration (concentration of composite metal oxide fine particles); 40% by mass.
SOL3: Methanol-dispersed antimony pentoxide fine particles (Sun Colloid AMT-332S / NV manufactured by Nissan Chemical Industries), solid content (concentration of antimony pentoxide fine particles) = 30% by mass
SOL4: Water-dispersed silica fine particles. (Snowtex O-40 manufactured by Nissan Chemical Industries, Ltd.), solid content (silica fine particle concentration) = 40% by mass.
SOL5: Water-dispersed cerium oxide fine particles. (Nydral U-15 manufactured by Taki Chemical Co., Ltd .; solid content 15% by mass, acetic acid 2% by mass, water 83% by mass).

[B1 component; epoxy group-containing silicon compound]
GTS: γ-glycidoxypropyltrimethoxysilane.
GDS: γ-glycidoxypropylmethyldimethoxysilane.

[C component; ketimine compound]
K1: 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine (“KBE-9103” manufactured by Shin-Etsu Chemical Co., Ltd.).
K2: The following reaction product of 3-aminopropyl trimethoxysilane and methyl isobutyl ketone [ketimine compound represented by the formula (K2)].

In a four-necked flask equipped with a stirrer, thermometer, and distillation tube, 17.6 g (0.1 mol) of γ-aminopropyltrimethoxysilane (molecular weight 176), 20.0 g (0 molecular weight) of methyl isobutyl ketone (molecular weight 100) 2 mol), and 100 ml of toluene, the toluene was distilled at a reaction temperature of 85 to 100 ° C., and the dehydration reaction was performed until γ-aminopropyltrimethoxysilane disappeared while measuring the water content of the distillate. I did it. The remaining amount of γ-aminopropyltrimethoxysilane was analyzed by gas chromatography, and the reaction was continued until the remaining amount disappeared. Thereafter, a vacuum pump was connected, and the remaining methyl isobutyl ketone and toluene were distilled off to obtain a reaction product. The obtained reaction product was identified by measuring the mass spectrum with GC-MASS (Gas Chromatograph Mass Spectrometer: JMS-K9, manufactured by JEOL Ltd.) and determining the molecular weight. The molecular weight of the obtained reaction product was 261. From the molecular weight determined by analysis and the raw materials used for the reaction, it was confirmed that the reaction product was a ketimine compound represented by the formula (K2).

K3: The following reaction product of ethylenediamine and diethyl ketone [ketimine compound represented by the following formula (K3)].

In a four-necked flask equipped with a stirrer, thermometer, and distillation tube, 6.0 g (0.1 mol) of ethylenediamine (molecular weight 60), 34.4 g (0.4 mol) of diethyl ketone (molecular weight 86), and toluene 100 ml was charged, toluene was distilled at a reaction temperature of 85 to 100 ° C., and the dehydration reaction was performed until ethylenediamine disappeared while measuring the water content of the distillate. The remaining amount of ethylenediamine was analyzed by gas chromatography, and the reaction was continued until the remaining amount disappeared. Then, the vacuum pump was connected and the remaining diethyl ketone and toluene were distilled off, and the reaction product was obtained. The obtained reaction product was identified by measuring the mass spectrum with GC-MASS (Gas Chromatograph Mass Spectrometer: JMS-K9, manufactured by JEOL Ltd.) and determining the molecular weight. The molecular weight of the obtained reaction product was 212. From the molecular weight determined by analysis and the raw materials used for the reaction, it was confirmed that the reaction product was a ketimine compound represented by the formula (K3).

K4: The following reactive organism [ketimine compound represented by the following formula (K4)] of isophoronediamine and diethyl ketone.

In a four-necked flask equipped with a stirrer, a thermometer, and a distillation tube, 17.0 g (0.1 mol) of isophoronediamine (molecular weight 170), 34.4 g (0.4 mol) of diethyl ketone (molecular weight 86), and 100 ml of toluene was charged, toluene was distilled at a reaction temperature of 85 to 100 ° C., and the dehydration reaction was performed until isophoronediamine disappeared while measuring the water content of the distillate. The remaining amount of isophoronediamine was analyzed by gas chromatography, and the reaction was continued until the remaining amount disappeared. Then, the vacuum pump was connected and the remaining isophorone diamine and toluene were distilled off, and the reaction product was obtained. The obtained reaction product was identified by measuring the mass spectrum with GC-MASS (Gas Chromatograph Mass Spectrometer: JMS-K9, manufactured by JEOL Ltd.) and determining the molecular weight. The molecular weight of the obtained reaction product was 306. From the molecular weight determined by analysis and the raw materials used for the reaction, it was confirmed that the reaction product was a ketimine compound represented by the formula (K4).

[B2 component; other silicon compound]
MTEOS: methyltriethoxysilane.
TEOS: Tetraethoxysilane.
BSE: 1,2-bis (triethoxysilyl) ethane.
(Water-soluble organic solvent)
MeOH: methanol.
TBA: t-butanol.
IPA: isopropyl alcohol.
EGPE: ethylene glycol monoisopropyl ether.
AcAc: acetylacetone.
DAA: diacetone alcohol.
[Other additives]
Silicone surfactant L1: Silicone surfactant L7001 manufactured by Toray Dow Corning Co., Ltd.
Cyclic ketone compound NMP: N-methylpyrrolidone.
-Quaternary ammonium salt TMAC: Tetramethylammonium chloride.
-Organosilicon compound having an amino group AM1: γ-aminopropyltriethoxysilane.
AM2: N-phenyl-γ-aminopropyltrimethoxysilane.
-Dye D1: Dialresin Blue J (manufactured by Diachemical Co., Ltd.)

Production of coating agent 1 (coating agent 1 obtained from composition 1):
(B1) component γ-glycidoxypropyltrimethoxysilane 118 g, (B2) component methyltrimethoxylane 95 g, solvent t-butyl alcohol 165 g, acetylacetone 50 g, methanol 28 g, ethylene glycol monoisopropyl ether 95 g, silicone 0.5 g of a surfactant (trade name “L-7001” manufactured by Toray Dow Corning Co., Ltd.) was mixed in. While stirring this solution, 49 g of 0.05N hydrochloric acid aqueous solution was added. Stirring was continued for about 1 hour, and then 0.3 g of tetramethylammonium chloride, 396 g of methanol-dispersed silica sol (SOL1) containing component (A), and tris (2,4-pentanedionato) aluminum (III) 4. After adding 4 g, the mixture was stirred at room temperature for 48 hours. Finally, 2.1 g of 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine (K1) is mixed as the component (C), stirred at room temperature for 3 hours, and aged for 24 hours. A coating agent 1 was obtained, and this coating agent 1 could be produced without clouding and without generation of a gelled product.
Table 1 shows the amount of each component (the amount of coating composition 1) before the coating agent 1 was prepared. In addition, what mixed the thing of the compounding ratio of the coating composition 1 in Table 1 by the said method corresponds to the coating agent 1. FIG.

Production of coating agents 2-11 and comparative coating agents 1-6 (coating agents 2-11 obtained from coating compositions 2-11) and (comparative coating agents 1-6 obtained from comparative coating compositions 1-6):
(A) inorganic oxide fine particles shown in Table 1, (B1) epoxy group-containing silicon compound, (C) ketimine group-containing compound, (B2) silicon compound, water, curing catalyst, water-soluble organic solvent, additive; silicone system It was produced by the same method as coating agent 1 except that a surfactant, a cyclic ketone compound, and a quaternary ammonium salt were used. Coating agents 2 to 11 were able to be produced without clouding and without gelation. The composition of the formulation is shown in Tables 1 and 2. In addition, the mixture of the coating compositions 2 to 11 in Table 1 mixed by the above method corresponds to the coating agents 2 to 11. Further, those obtained by mixing the comparative coating compositions 1 to 6 in Table 2 in the above ratio correspond to the comparative coating agents 1 to 6.
Comparative coating compositions 3 and 4 consist of (C) an organosilicon compound having an amino group instead of using a ketimine compound (AM1: γ-aminopropyltriethoxysilane, AM2: N-phenyl-γ-aminopropyltrimethoxysilane) ). The order in which AM1 and AM2 were blended was the same as (C) ketimine compound.

Example 1
MA1 was immersed in a 20% by mass aqueous sodium hydroxide solution at 60 ° C. as a plastic optical substrate, and alkali etching was performed for 5 minutes using an ultrasonic cleaner. After alkali etching, the substrate was washed successively with tap water and distilled water at 50 ° C., the remaining alkali was removed, and left for about 10 minutes until the temperature reached room temperature. This lens substrate was dip coated with the coating agent 1 at 25 ° C. at a pulling rate of 30 cm / min. Then, after pre-curing for 15 minutes in an oven at 70 ° C., curing was performed at 110 ° C. for 2 hours, and a hard coat layer having a thickness of 1.5 μm was formed on both surfaces of the plastic lens substrate MA1. An article (hard coat lens) was obtained.

(Evaluation results of optical articles)
This optical article (hard coat lens) was evaluated for appearance evaluation, hot water resistance test, weather resistance test, Bayer test, and steel wool scratch resistance. Appearance: ○, hot water resistance: 100 (5 hours), weather resistance Property test: 100, Bayer value: 5.3, steel wool scratch resistance: B. The results are shown in Table 2. About each evaluation, it performed by the following method.
(Appearance evaluation)
The appearance of the plastic lens substrate having a hard coat layer was evaluated by visual inspection of the transparency of the coating film and the presence or absence of irregularities. A film having a transparent coating film and having no appearance and having a good appearance was evaluated as ◯, and a film having whitening and a coating having a appearance was evaluated as a poor appearance.

(Heat resistance test)
In the test method, the obtained optical article (hard coat lens) was put in boiled distilled water, the adhesion of the hard coat layer was evaluated every 1 hour, and the test time was 5 hours. For the evaluation of adhesion, the adhesion between the hard coat film and the plastic lens was measured by a cross-cut tape test according to JISD-0202. That is, using a cutter knife, cuts are made at intervals of about 1 mm on the lens surface to form 100 squares. A cellophane pressure-sensitive adhesive tape (cello tape (registered trademark) manufactured by Nichiban Co., Ltd.) was strongly pasted thereon, and then pulled and peeled from the surface in a direction of 90 ° at a stretch, and the squares on which the coating film remained were measured. The evaluation result was expressed as (number of remaining cells) / 100. Here, the adhesiveness evaluates the adhesiveness of all the layers laminated on the lens substrate. The evaluation was performed on the convex surface of the lens.
(Weather resistance test)
As the test method, the following deterioration promotion test was performed in order to evaluate the durability of the cured product layer by light irradiation of the obtained optical article (hard coat lens). That is, the obtained optical article having a cured product layer was accelerated and deteriorated for 300 hours by a Xenon weather meter X25 manufactured by Suga Test Instruments Co., Ltd., and then the adhesion was evaluated in the same manner as in the hot water resistance test.

(Bayer test)
Based on the Bayer test method (ASTM D-4060 or ASTM F735-81), the surface of the lens substrate (non-coated lens) on which the hard coat layer is not formed and the surface of the hard coat layer formed on the lens substrate (hard The surface of the coated lens was scratched by the following method.
That is, an uncoated lens and a hard-coated lens were mounted on an abrasive holding body having two holes of Φ50 mm from the bottom of the holes with the convex surfaces thereof facing up. Next, 500 g of a commercially available abrasive (SAINT-GOBAIN CERAMIC MATERIALS CANADA INC., Made of alumina-zirconia) was placed in an abrasive holder, and the two lenses mounted in this state were stroked 150 strokes per minute. The surface of the two lenses was scratched by being vibrated with a stroke width of 4 inches for a total of 2 minutes at a frequency of.
Next, for these lenses, the haze was measured with a spectrometer (Haze meter manufactured by Suga Test Instruments Co., Ltd.), and the difference between the haze values before and after scratching was obtained. Was calculated.
Bayer value = ΔHaze (non-coated) / ΔHaze (hard-coated)
In the formula, ΔHaze (non-coated) is a value obtained by subtracting the Haze value before the test from the Haze value after the test for the non-coated lens, and ΔHaze (hard coat) is a test from the Haze value after the test in the hard-coated lens. The value obtained by subtracting the previous Haze value. A larger value means higher surface hardness and better scratch resistance.

(Steel wool scratch resistance)
Using steel wool (Bonster # 0000 manufactured by Nippon Steel Wool Co., Ltd.), the surface of the optical article (hard coat film surface) was rubbed 10 times while applying a load of 3 kg, and the degree of damage was visually evaluated. The evaluation criteria are as follows.
A: No flaws (when no flaws can be confirmed visually).
B: Scratches hardly occur (when there are 1 or more and less than 5 scratches visually).
C: Slightly scratched (when there are 5 or more and less than 10 scratches visually).
D: Scratches (when there are 10 or more scratches visually).
E: Peeling of the hard coat film has occurred.
Regarding the scratch resistance, an evaluation result of B or higher means that there is no practical problem and that the surface hardness is excellent.
The above results are shown in Table 3.

Examples 2 to 16
Using the coating agents 1 to 11 obtained from the coating composition shown in Table 1 and a plastic lens substrate, a hard coat lens having a hard coat layer was prepared in the same manner as in Example 1, and the evaluation was performed. went. The evaluation results are shown in Table 3.

Comparative Examples 1-10
Using the comparative coating agents 1 to 6 obtained from the comparative coating composition shown in Table 2 and a plastic lens substrate, a hard coat lens having a hard coat layer was produced in the same manner as in Example 1, Evaluation was performed. The evaluation results are shown in Table 4. In Comparative Example 10, no cracks were generated in the hard coat layer obtained from the beginning, and the hard coat layer was not in close contact with the plastic lens substrate, and thus no further evaluation was performed.

Production of coating agent 12 (coating agent 12 obtained from composition 12):
While stirring 500 g of methanol-dispersed antimony pentoxide sol (SOL3) containing component (A), a mixed solution of 30 g of t-butyl alcohol, 200 g of diacetone alcohol, and 2.0 g of (C component) ketimine compound (K2) was added. Added. To the resulting solution, 170 g of γ-glycidoxypropyltrimethoxysilane as component (B1) and 18 g of γ-glycidoxypropyldimethoxymethylsilane, 100 g of tetraethoxysilane as component (B2), 50 g of water, And a solution hydrolyzed with 50 g of 0.05N hydrochloric acid was added. Next, 1.0 g of a silicone surfactant (trade name “L-7001” manufactured by Toray Dow Corning Co., Ltd.) was added to the resulting solution, and the mixture was stirred for 12 hours at room temperature. 2,4-pentanedionato) aluminum (III) 10 g was added and the mixture was further stirred at room temperature for 1 hour to obtain the coating agent 12 of the present invention. It was possible to produce without causing.
Table 5 shows the blending amounts of the respective components (the blending amount of the coating composition 12) before making the coating agent 12. In addition, what mixed the thing of the mixture ratio of the coating composition 12 in Table 5 by the said method corresponds to the coating agent 12. FIG.

Production of coating agents 13-17 (coating agents 13-17 obtained from coating compositions 13-17):
(A) inorganic oxide fine particles, (B1) epoxy group-containing silicon compound, (C) ketimine group-containing compound, (B2) silicon compound, water, curing catalyst, water-soluble organic solvent, additive shown in Table 5; silicone system It was produced by the same method as coating agent 12 except that a surfactant, a cyclic ketone compound, and a quaternary ammonium salt were used. Coating agents 13 to 17 were able to be produced without clouding and without gelation. The composition of the formulation is shown in Table 5. Note that a mixture of the coating compositions 13 to 17 in Table 5 mixed by the above method corresponds to the coating agents 13 to 17.

Examples 17-22
Using a coating agent 12 to 17 obtained from the coating composition shown in Table 5 and a plastic lens substrate, a hard coat lens having a hard coat layer was prepared in the same manner as in Example 1, and the evaluation was performed. went. The evaluation results are shown in Table 6.

As is apparent from the above examples, by blending the (C) ketimine compound, it was possible to form a hard coat layer having excellent adhesion and excellent hardness such as Bayer value and scratch resistance. In particular, the adhesion to (meth) acrylic resins and urethane resins was improved. On the other hand, as shown in Comparative Examples 1 to 8, when (C) a ketimine compound was not included or a silicon compound having a secondary amino group was used, the adhesion was not sufficiently improved. Moreover, when the compounding quantity of (C) ketimine compound was too much, or when the silicon compound which has a primary amino group was used, hardness fell. Further, as shown in Comparative Examples 9 and 10, when the blending amount of the component (B1) is too large, the scratch resistance is lowered, and when the blending amount of the component (B1) is small, the adhesion is lowered. .

Claims

(A) inorganic oxide fine particles,
(B1) An epoxy group-containing epoxy compound and a hydrolyzable group-containing silicon compound, and (C) a hard coat layer forming coating composition containing a ketimine compound having a ketimine group,
The said coating composition characterized by including (A) component as 100 mass parts, (B1) component at 50 mass part or more and 350 mass parts or less, and (C) component at 0.1 mass part or more and 10 mass parts or less.
The coating composition according to claim 1, wherein the (C) ketimine compound is a ketimine group-containing silicon compound having a ketimine group and a hydrolyzable group.
The coating composition further comprises the following formula (I) as component (B2):

(Where
R 1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms,
R 2 is an alkyl group having 1 to 3 carbon atoms,
A is an integer of 0-2. )
And a silicon compound represented by the following formula (II)

(Where
R 3 is an alkylene group having 1 to 8 carbon atoms,
R 4 and R 5 are alkyl groups having 1 to 3 carbon atoms,
R 6 and R 7 are alkyl groups having 1 to 3 carbon atoms,
B is an integer of 0-2. )
Including at least one silicon compound selected from the group consisting of silicon compounds represented by:
The coating composition according to claim 1, wherein the component (A) is 100 parts by mass and the component (B2) is 10 parts by mass or more and 150 parts by mass or less.
An optical article, wherein a coating layer obtained by curing the coating composition according to any one of claims 1 to 3 is laminated on a surface of a plastic optical substrate.
The optical article according to claim 4, wherein the plastic optical substrate is an optical substrate made of a (meth) acrylic resin.
6. The optical article according to claim 5, wherein the plastic optical substrate is a substrate containing a photochromic compound.
The optical article according to claim 4, wherein the plastic optical base material is a base material made of urethane resin.