JP5819743B2 - Hard coat composition - Google Patents

Description

  The present invention relates to a composition for hard coat. This is particularly suitable for an optical element formed of an organic glass having a high refractive index. Here, the “optical element” is a concept including a lighting fixture cover, a reflecting mirror, a prism, and a filter in addition to optical components such as a spectacle lens and a camera lens.

  In the following description, the blending (composition) unit, the mixing ratio, and the like are mass units. The refractive index is at 25 ° C. using mercury E-rays.

  Further, the numerical range indicating the composition or the like is not an absolute value having a critical meaning, but exemplifies a preferable range considered practically possible.

  The particle size of the colloidal particles is based on the dynamic light scattering method.

  In the following description, the spectacle lens will be mainly described as an example, but the present invention is not limited thereto.

  Organic glass used as an optical lens has been widely used because it has advantages such as light weight, impact resistance, dyeability and easy processing as compared with conventional inorganic glass.

  However, in the state of organic glass, it has a drawback that it has low scratch resistance and is easily scratched as compared with inorganic glass. On the other hand, a silicone-based hard coat film (cured coating film) is generally applied to the surface of an optical substrate made of organic glass for the purpose of improving scratch resistance.

  For example, the applicant of the present application has previously proposed a dyeable coating composition comprising an epoxy group-containing silane compound, a carboxylic acid, and a curing agent, and has partially put it into practical use (Patent Document 1).

  On the other hand, an eyeglass lens made of organic glass has a low refractive index when compared to an inorganic glass eyeglass lens, and when used for an eyeglass lens, the lens end face becomes thick, so that it does not look good for correcting visual acuity. Therefore, it was not suitable.

  However, in recent years, even organic glass having a refractive index of 1.60 or more has been put on the market due to technological innovation, and currently occupies 60% on the market scale and tends to increase in the future.

  An optical plastic molding coating composition (hard coat composition) applicable to such a high refractive index organic glass lens has been proposed and partially put into practical use (Patent Document 2).

  On the other hand, as a recent trend, the fashionability of eyeglasses has become more important and it has become necessary to deal with a wider variety of coloring lenses. However, the organic glass lens having a high refractive index has relatively poor dyeability. For this reason, problems are likely to occur in the productivity of the coloring lens.

  The composition for hard coat described in Patent Document 2 has excellent properties of suppressing the optical interference between the coating film and the organic glass having a refractive index of 1.60 or less and maintaining the optical function of the organic glass lens body. Yes.

  However, when a spectacle lens to which the hard coat composition is applied is used for a long time, the iron oxide portion in the fine particles of the iron oxide / titanium oxide composite oxide used as a coating film component is blackened by ultraviolet rays. Wake up and detract from aesthetics.

  Further, due to the photocatalytic action of titanium oxide in the iron oxide / titanium oxide composite oxide fine particles, when exposed to ultraviolet rays, the hard coat layer is deteriorated or discolored or decolored.

  Therefore, the applicant of the present application can suppress the blackening phenomenon against ultraviolet rays while maintaining the property of suppressing the optical interference of the hard coat composition of Patent Document 2 with respect to the organic glass lens having a high refractive index. In addition, a hard coat composition having the following constitution, which can suppress discoloration and discoloration (fading) of a color lens and does not impair the aesthetics even when used for a long period of time, is proposed in Patent Document 3 and partially put into practical use. Yes.

“A composition for hard coating in which nanoparticles of Nb ₂ O ₅ are dispersed in a colloidal state in a hydrolyzate mixture of glycidoxyalkyltrialkoxysilane and tetraalkoxysilane.”

Japanese Examined Patent Publication No. 57-42665 (Claims) Japanese Patent No. 2577670 (Claims etc.) Japanese Patent No. 4589115 (Claims etc.)

  However, in the composition for hard coat proposed in Patent Document 3 above, excellent performance is obtained for organic glass having a high refractive index up to a refractive index of 1.67. When applied to a refractive index of 1.70 to 1.74), it has been found that blue discoloration due to light interference and ultraviolet rays occurs in the hard coat.

In view of the above, when the present invention is applied to an ultrahigh refractive organic glass lens having a refractive index exceeding 1.67, the coating refractive index of the hard coat can be approximated to the refractive index of the organic glass, and the optical interference It is an object (problem) to provide a composition for hard coat that does not generate a blue color change due to ultraviolet rays and that has practical scratch resistance.

  As a result of diligent development in order to solve the above-mentioned problems (objectives), the present inventors have come up with a hard coat composition having the following constitution.

（但し、Ｒ¹はＨ又はＣＨ₃、Ｒ ² は炭素数１〜４のアルキレン基、Ｒ ³ は炭素数１〜４のアルキル基。）
で示されるトリアルコキシシラン、及び
(Ｂ)成分：
示性式 Ｓｉ(ＯＲ⁴)₄（但しＲ⁴は炭素数１〜４のアルキル基。）で示されるテトラアルコキシシラン
との所定比混合物の加水分解物であり、かつ、
金属酸化物コロイドが配合されてなるハードコート用組成物において、
前記金属酸化物コロイドが、アミン分散剤をコロイド粒子100質量部に対して0.3〜5.0質量部含有するルチル系コロイドであるとともに、
前記低温硬化触媒が有機カルボン酸であり、さらに、
前記(Ａ)成分に対する前記(Ｂ)成分の混合質量比が(Ａ)／(Ｂ)＝１０／２〜１０／８であり、また、
前記アミン分散剤が、アンモニア及びアンモニアＮＨ₃の水素原子１個、２個又は３個を炭化水素基Ｒ⁵(炭素数１〜５）で置換した脂肪族アミン、脂肪族ジアミン又は環状アミン及びそれらの誘導体から選択されるものである、ことを特徴とする。 A hard coat composition applied to an optical element body formed of organic glass,
As a coating film-forming component, it contains a hydrolyzate of alkoxysilane and a low-temperature curing catalyst for the hydrolyzate,
The hydrolyzate of the alkoxysilane is
Component (A):
Indication formula

(However, R ¹ is H or CH ₃ , R ² is an alkylene group having 1 to 4 carbon atoms, and R ³ is an alkyl group having 1 to 4 carbon atoms.)
And a trialkoxysilane represented by
(B) component:
A hydrolyzate of a mixture of a predetermined ratio with tetraalkoxysilane represented by the formula Si (OR ⁴ ) ₄ (wherein R ⁴ is an alkyl group having 1 to ⁴ carbon atoms);
In a hard coat composition comprising a metal oxide colloid,
The metal oxide colloid is a rutile colloid containing 0.3 to 5.0 parts by mass of an amine dispersant with respect to 100 parts by mass of colloidal particles,
The low-temperature curing catalyst is an organic carboxylic acid, and
The mixing mass ratio of the component (B) to the component (A) is (A) / (B) = 10/2 to 10/8,
The amine dispersant is an aliphatic amine, aliphatic diamine, or cyclic amine in which one, two, or three hydrogen atoms of ammonia and ammonia NH ₃ are substituted with a hydrocarbon group R ⁵ (C 1-5), and It is selected from these derivatives.

That is, the present inventors paid attention to a rutile colloid in which rutile ( rutile titania) having the highest refractive index and the low photocatalytic activity among the metal oxides is used as the colloidal particles.

  Conventionally, the addition of a rutile colloid to a hard coat composition using an alkoxysilane hydrolyzate as a coating film forming element has not been performed by those skilled in the art. The rutile colloid usually contains an amine dispersant and reacts with the organic carboxylic acid, which is a low-temperature curing agent of the alkoxysilane hydrolyzate, to produce an amide, thereby inhibiting the action of the low-temperature curing agent. It is done.

  However, by configuring the hard coat composition as described above, as shown in the examples to be described later, even if the hard coat is formed by applying it to an organic glass lens with an ultrahigh refractive index, light interference or ultraviolet light is applied to the hard coat. No blue discoloration due to.

The reason why optical interference does not occur is that colloidal particles of rutile ( rutile titania) colloid (less than 100 nm) have a refractive index of 2.616 (ordinary ray), which is higher than the refractive index of Nb ₂ O ₅ of 2.33 (around 500 nm). This is because it is well dispersed.

  The reason why blue discoloration does not occur is considered as follows.

As low-temperature curing catalyst, the metal organic compound such as Al (metal chelate compound), the excited electrons of rutile (TiO ₂₎ becomes blue trapped in the metal atom (Al) in rutile (TiO ₂₎ is reduced . On the other hand, when an organic carboxylic acid is used, the excited electrons of titanium oxide are not captured and the excited electrons return to Ti and do not turn blue.

It is a schematic sectional drawing which shows the laminated constitution of the spectacle lens to which this invention is applied.

  Hereinafter, a mode (configuration) for carrying out the present invention will be described in detail. In the following description, blending units, mixing ratios, and the like are based on “mass” unless otherwise specified.

<1> Hydrolyzate of alkoxysilane as a coating film component (coating film main component):
In the present invention, the hydrolyzate of alkoxysilane consists of a hydrolyzate of a mixture of a predetermined ratio of the component (A) which is the trialkoxysilane exemplified below and the component (B) which is the tetraalkoxysilane exemplified below. To do.

（但し、Ｒ^１はＨ又はＣＨ₃、Ｒ^２は炭素数１〜４のアルキレン基、Ｒ^３は炭素数１〜４のアルキル基。）で示されるものであり、具体的には、
グリシドキシメチルトリアルコキシシラン類、α−（β−）グリシドキシエチルトリアルコキシシラン類、α−（β−，γ―，δ）グリシドキシブチルトリアルコキシシラン類、α−（β−，γ―，δ）グリシドキシプロピル類、及びそれらの誘導体を挙げることができる。これらは単独でも又２種以上併用することも可能である。 (A) component: trialkoxysilane Basically, the formula:

(However, R ¹ is H or CH ₃ , R ² is an alkylene group having 1 to 4 carbon atoms, and R ³ is an alkyl group having 1 to 4 carbon atoms.) Specifically,
Glycidoxymethyltrialkoxysilanes, α- (β-) glycidoxyethyltrialkoxysilanes, α- (β-, γ-, δ) glycidoxybutyltrialkoxysilanes, α- (β-, γ-, δ) glycidoxypropyls and their derivatives can be mentioned. These can be used alone or in combination of two or more.

(B) Component: Tetraalkoxysilane Basically, it is represented by the formula: Si (OR ⁴ ) ₄ (where R ⁴ is an alkyl group having 1 to ⁴ carbon atoms), specifically ,
Examples thereof include tetraethoxysilane, tetramethoxysilane, tetrapropoxysilane, and tetrabutoxysilane. These can be used alone or in combination of two or more.

  The hydrolyzate of each of the above alkoxysilanes can be obtained by subjecting a silane compound to hydrolysis by dropwise addition of 0.01-0.1N dilute acid in the presence of a lower alcohol. Specific examples of the dilute acid include hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, formic acid, oxalic acid, and sulfonic acid.

  The mixing ratio of the component (A) and the component (B) is such that the required coating film hardness (abrasion resistance (sand erase 200 g) AB or more) is obtained for the coating film.

  The mixing ratio of the component (A) and the component (B) varies slightly depending on the types of the components (A) and (B). For example, (A) / (B) = 10/1 to 10/10, Desirably, it sets suitably from the range of 10/2-10/8.

  That is, the lower the numerical value of (A) / (B), the higher the ratio of the tetraalkoxysilane that is the component (B), and the easier it is to obtain the coating film hardness. However, when the numerical value of (A) / (B) is high, there is a possibility that appearance defects due to cracks occur during coating polymerization, and when it is low, there is a possibility that practical coating hardness cannot be obtained.

This mixing ratio is (A) / (B) = 10 / 0.52 to 10 / 3.3 (9.5 / in the case of Patent Document 3 using niobium pentoxide (Nb ₂ O ₅ ) colloid. 0.5-7.5 / 2.5), which is relatively high. This is because the coating composition of the present invention contains an amine to reduce the coating film hardness.

<2> Rutile colloid as a high refractive index imparting agent:
The greatest feature of the present invention is that “rutile colloid containing an amine dispersant” is added as a metal oxide colloid to the alkoxysilane hydrolyzate.

  Here, the “rutile colloid” is composed of only rutile titania (rutile), or colloidal dispersion fine particles or composite oxide fine particles mainly composed of rutile and mixed with other high refractive index metal oxides. Say something.

  Here, the size of the colloidal particles varies slightly depending on the type of rutile colloid (difference in the production method and materials of the colloidal particles), but the average particle diameter (median diameter): 5 to 60 nm, further 6 to 20 nm Furthermore, it is desirable to select from the range of 8 to 10 nm.

  If the average particle size of the colloidal particles is small, it may be difficult to impart scratch resistance to the coating film, or rutile microparticles may be easily aggregated, resulting in a poor appearance due to coating film nonuniformity. On the other hand, when the colloidal particles are large, there is a possibility that appearance defects accompanying whitening of the coating film may occur.

Examples of the amine dispersant include aliphatic amines, aliphatic diamines, cyclic amines in which one or two or three hydrogen atoms of ammonia and ammonia NH ₃ are substituted with a hydrocarbon group R ⁵ (having 1 to ⁵ carbon atoms). Their derivatives can be mentioned. These are suitably used as a mixture of one type or two or more types.

Here, the addition amount of the amine dispersant varies depending on the type of the amine dispersant, but is desirably 0.3 to 5.0 parts, preferably 100 to 100 parts of colloidal particles (rutile fine particles: solid content) in the rutile colloid. Is 0.45 to 4.0 parts.

  Examples of the rutile colloid medium (dispersion medium) include monohydric lower alcohols (1 to 3 carbon atoms) such as methanol, ethanol and IPA; ethylene glycol (1,2-dioxyethane); and 2-methoxyethanol. , 2-ethoxyethanol, 1,2-dioxyethane, 2-butoxyethanol, 1-methoxy-2-propanol, and other polyhydric alcohols and ethers thereof can be suitably used. Other esters may be used.

  At this time, the mixing ratio of the colloidal particles and the medium is set within a range in which the dispersion of the colloidal particles can be maintained. That is, although it depends on the type of colloidal particles (material / particle size), the type of medium, the type of amine-based dispersant, and the dispersion method, for example, the former: the latter = 10: 15-40 is appropriately set. .

  When the ratio of the medium is small, agglomeration phenomenon is likely to occur in the colloidal particles, and when the ratio of the medium is large, it is difficult to secure a sufficient ratio of the colloidal particles in the coating film. It becomes difficult to obtain scratch resistance.

  The method for producing the rutile colloid is not particularly limited, and can be produced by a conventional method, for example, 1) an ion exchange method, 2) a peptization method, or the like.

  1) Ion exchange method: A method of treating the acidic salt of the metal with a hydrogen ion exchange resin, or a method of treating the basic salt of the metal with a hydroxyl type anion exchange resin.

  2) Peptization: A method in which the gel obtained by neutralizing the acidic salt of titanium with a salt or neutralizing the basic salt of titanium with an acid is washed with an acid or a base ( (Japanese Patent Publication No. 4-27168), a method of hydrolyzing an alkoxide of titanium (Patent No. 3878113), a method of hydrolyzing the above basic salt of titanium (Patent No. 4069330), and the like.

  The rutile colloid can be used as a composite fine particle by mixing one or more other metal oxide colloids.

Examples of other metal oxides include Fe ₂ O ₃ , ZrO ₂ , SnO ₂ , Ta ₂ O ₅ , Nb ₂ O ₅ , Y ₂ O ₃ , MoO ₃ , WO ₃ , PbO, In ₂ O ₃ , Bi ₂ O ₃ , SrO and the like.

Examples of composite oxides include the _{TiO 2 -SnO 2, TiO 2 -ZrO} 2, TiO 2 -ZrO 2 -SnO 2, TiO 2 -ZrO 2 -CeO 2 , and the like.

  These rutile colloids have high transparency, and the colloidal particle diameter is preferably about 8 to 60 nm as a dynamic light scattering particle diameter, and the refractive index is preferably about 1.9 to 2.1.

  The rutile colloid can also be used after being treated with other oxides, composite oxides, organosilicon compounds, or organometallic compounds.

Examples of the treatment with the oxide or composite oxide include a method of growing SiO ₂ fine particles on the surface of colloidal particles in a rutile colloid medium by a known method (Japanese Patent Laid-Open No. 2000-063119 / 2007). -Ref. -246351 etc.).

  The amount of addition of rutile colloidal solid content to alkoxysilane (total amount: the same applies hereinafter) is within a range in which the effect of adding rutile fine particles (required characteristics) can be obtained.

  That is, it varies depending on the type of rutile colloid or alkoxysilane, but for example, it is appropriately selected from the range of 15 to 150 parts, preferably 25 to 100 parts of rutile colloid solids with respect to 100 parts of alkoxysilane.

  If the addition amount of rutile colloidal solids is small, it is difficult to obtain the addition effect (refractive index increase) and the coating film hardness tends to decrease. Conversely, if the addition amount is large, the whitening phenomenon of the coating film or thermal polymerization after coating the organic lens film Sometimes the tendency of appearance defects due to cracks increases.

<3> Organic carboxylic acid as a curing catalyst:
The organic carboxylic acid is not particularly limited as long as it is a polyvalent carboxylic acid having a curing action. For example, trimellitic acid, trimellitic anhydride, itaconic acid, pyromellitic acid, pyromellitic anhydride and the like can be suitably used.

  The addition amount of the organic carboxylic acid is 5 to 40 parts, preferably 10 to 30 parts, relative to 100 parts of alkoxysilane. These numerical ranges have no critical significance. This is because those skilled in the art appropriately set the composition depending on the composition of the alkoxysilane ((A) / (B)) and the type of the organic carboxylic acid.

  At this time, the organic carboxylic acid and a small amount of a nitrogen-containing organic compound can be used in combination as an adhesion improver.

  Examples of the nitrogen-containing organic compound include methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenyl. Imidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,4 -Diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- (1')]- Ethyl-s-triazine, dicyandiamide, β-aminocrotonate, di From among Eniruchio urea, it can be used by selecting one or two or more.

  The addition amount of the nitrogen-containing organic compound is 1 to 20 parts, preferably 5 to 10 parts with respect to 100 parts of alkoxysilane.

<4> Other auxiliary materials:
Furthermore, in order to improve the coating film performance and appearance performance, a trace amount of an ultraviolet absorber, an antioxidant, a disperse dye, an antistatic agent, a surfactant and the like are added to the hard coat composition of the present invention as necessary. May be.

  -A benzotriazole type, a benzophenone type, etc. can be used as an ultraviolet absorber, and a hindered amine type is preferably used in combination with an antioxidant.

  -As a disperse dye, a water disperse dye is usually used.

  As the surfactant, for the purpose of improving smoothness and antistatic properties, a nonionic type in which the hydrophobic group is composed of dimethyl silicone oil and the hydrophilic group is composed of polyether can be used.

  These characteristics can also be obtained with a fluorosurfactant, etc., but in the case of a fluorosurfactant, particularly a polymer, when used in combination with the rutile microparticle (C), the rutile microparticles aggregate. Care must be taken when using this product because it may be easily damaged.

  The amount of the surfactant used is 0.01 to 0.5 part, preferably 0.03 to 0.3 part, based on 100 parts of the hard coat composition (the total of (A) component + (B) component + colloid particles). If the amount is too small, it is difficult to obtain smoothness and antistatic properties on the coating film. If the amount is too large, spiders are likely to occur during film formation even if a silicone surfactant is used.

<5> High refractive index organic glass lens as an optical substrate:
Examples of the high refractive index organic glass lens include commercially available organic glass materials having the following refractive indexes.

(a) Polythiourethane resin: Refractive index 1.61 (ne value)
(b) Urethane acrylic resin: Refractive index 1.61 (ne value)
(c) Polythiourethane resin: Refractive index 1.67 (ne value)
(d) Polythioepoxy resin: Refractive index 1.71 (ne value)
(e) Polythioepoxy resin: Refractive index 1.74 (ne value)

<6> Application method of composition for hard coat (object to be coated):
Examples of the coating method for the optical substrate (lens substrate) include conventional brush coating, dip coating, roller coating, spray coating, and spin coating. The coating amount is appropriately set so that the cured coating thickness is in the range of 0.5 to 20 μm.

  Moreover, dry hardening conditions are 80-150 degreeC normally, Preferably you may be 100-120 degreeC x 1-5h.

  A pretreatment such as degreasing cleaning with an acid-alkali cleaning solvent, plasma processing, or ultrasonic cleaning is appropriately performed on the object to be coated.

<7> Lens treatment film configuration:
Usually, it is desirable to form a primer for the purpose of improving impact resistance and adhesion between the hard coat and the lens substrate.

  As a specific primer composition (paint), a thermoplastic polyurethane type (TPU) or a thermoplastic ester type (TPEE) primer composition containing the rutile colloid can be preferably used.

  Furthermore, a conventional antireflection film made of only an inorganic substance can be laminated on the upper surface of the hard coat.

  As the antireflection film, an inorganic powder such as a metal, a metal oxide, or a metal fluoride can be formed by a dry plating method such as vacuum deposition, sputtering, or ion plating.

  For example, silicon dioxide, titanium oxide (IV), tantalum oxide (V), antimony (III) oxide, zirconium oxide, aluminum oxide, etc. are listed as metal oxides, and magnesium fluoride, etc. are listed as metal fluorides. Can do.

  Specific examples of the optical film thickness design of the reflective multilayer film include the following.

_{(α) SiO 2 / ZrO 2} : 1/4 λ, ZrO 2: 1/2 λ, SiO 2: 1/4 λ
_{(β) SiO 2 / TiO 2} : 1/4 λ, TiO 2: 1/2 λ, SiO 2: 1/4 λ

Hereinafter, the present invention will be described in more detail based on examples.
(1) Commercially available products having the following specifications were used as the metal oxide colloids of the examples and comparative examples.

    “Rutyl colloid I”: a colloid containing 0.5% diisopropylamine and having colloidal particles (median diameter 10 nm) dispersed in methanol; non-volatile content 31%.

    "Rutyl colloid II"-"rutile colloid I" with diisopropylamine changed to 2.0%; nonvolatile content 31%.

    "Rutyl colloid III" ... "Rutyl colloid I" with diisopropylamine changed to 3.5%; nonvolatile content 31%.

“Titania composite fine particle colloid”: a colloid in which titania composite fine particles (SiO ₂ / TiO ₂ = 0.235, Fe ₂ O ₃ / TiO ₂ = 0.008) (median diameter 11 nm) are dispersed in methanol; nonvolatile content 30%.

“Niobium oxide colloid”: colloid in which Nb ₂ O ₅ fine particles (median diameter 5 nm) are dispersed in ethanol; nonvolatile content 25%

Moreover, the lens base material (plastic lens for spectacles) was made of the following resin material, and a commercially available product having the following refractive index was used.
(a) Polythiourethane resin: Refractive index 1.61 (ne value)
(b) Urethane acrylic resin: Refractive index 1.61 (ne value)
(c) Polythiourethane resin: Refractive index 1.67 (ne value)
(d) Polythioepoxy resin: Refractive index 1.71 (ne value)
(e) Polythioepoxy resin: Refractive index 1.74 (ne value)

(2) The hard coat and primer compositions (paints) in each of the examples and comparative examples were prepared according to the following formulation.

<Example 1>
(i) Hard coat composition
(1) Preparation of hydrolyzed organoalkoxysilane γ-glycidoxypropyltrimethoxysilane: 200 parts and tetramethoxysilane: 140 parts and methyl alcohol: 200 parts A mixture of 0.01N hydrochloric acid: 60 parts was added dropwise with stirring. Then, the mixture is stirred for a whole day and night to perform hydrolysis to obtain a hydrolyzate.

(2) Preparation of composition for hard coat The hydrolyzate prepared in (1) above contains rutile colloid I: 300 parts, 1-methoxy-2-propanol: 100 parts, trimellitic anhydride: 51 parts, nitrogen-containing organic compound : 15 parts were added and stirred for a whole day and night, and filtered through a 1 μm filter. The coating film refractive index of this hard coat composition was 1.61.

(ii) Preparation of primer composition (a) Preparation of TPU primer composition A mixture of non-volatile 33% water-based emulsion type TPU (commercial product): 120 parts, methyl alcohol: 500 parts and pure water: 150 parts While adding 60 parts of rutile colloid I, the mixture was stirred for 2 hours and filtered through a 1 μm filter. The coating film refractive index of the primer composition was 1.60.

(b) Preparation of TPEE-based primer composition While stirring a mixture of non-volatile content 27% water-based emulsion type TPEE: 100 parts, methyl alcohol: 400 parts and pure water: 150 parts, add 100 parts of rutile colloid II. And stirred for 2 h and filtered through a 1 μm filter. The coating film refractive index of this primer composition was 1.66.

<Example 2>
(1) Preparation of hydrolyzate of organoalkoxysilane After stirring 60 parts of 0.01N hydrochloric acid while stirring a mixture of 160 parts of γ-glycidoxypropyltrimethoxysilane, 80 parts of tetramethoxysilane and 100 parts of methyl alcohol, the whole is stirred overnight. Then, hydrolysis is performed to obtain a hydrolyzate.

(2) Preparation of hard coat composition To the hydrolyzate prepared in (1) above, rutile colloid II: 460 parts, 1 methoxy 2-propanol: 100 parts, itaconic acid: 40 parts, nitrogen-containing organic compound: 15 Part was added, stirred for a whole day and night, and filtered through a 1 μm filter. The coating film refractive index of this hard coat composition was 1.67.

<Example 3>
(1) Preparation of hydrolyzate of organoalkoxysilane γ-glycidoxypropyltrimethoxysilane: 150 parts, tetramethoxysilane: 45 parts, methyl alcohol: 80 parts while stirring a mixture of 0.01N hydrochloric acid: 50 parts. To hydrolyze to obtain a hydrolyzate.

(2) Preparation of hard coat composition To the hydrolyzate prepared in (1) above, rutile colloid III: 620 parts, 1 methoxy 2-propanol: 100 parts, pyromellitic anhydride: 40 parts, nitrogen-containing organic compound: 15 parts were added, stirred for a whole day and night and filtered through a 1 μm filter. The coating film refractive index of this composition was 1.71.

<Comparative Example 1>
To a mixture of γ-glycidoxypropyltrimethoxysilane: 125 parts, ethyl silicate: 110 parts, methanol: 92 parts and methyl ethyl ketone: 200 parts, composite fine particle colloid: 180 parts is added and stirred with 54 parts of 0.01N hydrochloric acid. Is added dropwise to carry out hydrolysis overnight to obtain a hydrolyzate.

  To the above hydrolyzate, 1.5 parts of a surfactant and 12 parts of itaconic acid and 5 parts of a nitrogen-containing organic compound as a low-temperature curing catalyst are added and stirred for 24 hours to obtain a hard coat composition. The coating film refractive index of this hard coat composition was 1.61.

<Comparative Example 2>
While stirring a mixture of γ-glycidoxypropyltrimethoxysilane: 200 parts, ethyl silicate: 40 parts and methyl alcohol: 50 parts, 70 parts of 0.01N hydrochloric acid was added dropwise and stirred for one day to hydrolyze the hydrolyzate. Get.

  Niobium oxide colloid: 480 parts, 2-ethoxyethanol: 100 parts and trimellitic anhydride: 48 parts, nitrogen-containing organic compound: 15 parts as a low-temperature curing catalyst were added to the hydrolyzate, and the mixture was stirred overnight and filtered through a 1 μm filter. The coating film refractive index of this hard coat composition was 1.61.

<Comparative Example 3>
The low temperature curing catalyst used in Example 1 was prepared by changing the trimellitic anhydride to 51 parts and the nitrogen-containing organic compound: 15 parts to acetylacetone aluminum: 2 parts, stirring all day and night, filtering through a 1 μm filter, and hard coating A composition for use is obtained. The coating film refractive index of this hard coat composition was 1.61.

(3) Preparation of eyeglass lens for evaluation test Each of the above compositions is applied to the lens substrate 12 of the above-described display (a) to (e), which has been subjected to pretreatment by immersion, washing and drying in an aqueous caustic soda solution. Using the primer 16, the hard coat 14, and the antireflection film 18 were sequentially formed under the following conditions to produce spectacle lenses for each test example (see FIG. 1).

1) Primer formation:
It is immersed in each primer composition, pulled up at 160 mm / min, applied, and then pre-dried at 90 ° C. for 20 minutes.

2) Hard coat formation:
The sample on which the primer is formed is immersed in each hard coat composition, pulled up at 130 mm / min, and preliminarily dried at 100 ° C. for 20 minutes, and further heated at 120 ° C. for 3 hours. The coating was cured.

3) Formation of antireflection film Subsequently, the antireflection film of the multilayer film design example (α) was formed on the hard coat by a vacuum deposition method.

(4) Test method The plastic lens (test body) having the laminated composite film thus obtained was subjected to the following evaluation tests for the following characteristics.

1) Evaluation of optical physical properties Measurement was performed using a reflectance measuring machine manufactured by Olympus, model USPM-RU-2, and a hard film thickness and a refractive index were obtained.

2) Appearance Investigate interference fringes, transparency, coloring, and surface condition by visual observation. The judgment criteria are as follows.

Interference fringes: ◎: None at all, ○: Little noticeable, △: Some noticeable,
×: Very conspicuous ・ Transparency ... ○: Clear, good
×: Slightly spidered (transmittance drops by 1% with respect to ○)

3) Adhesiveness (initial, after immersion in warm water)
The initial adhesion is 100 rubbed lines that reach a 1mm base material on the coating surface with a steel knife, and the cellophane tape (made by Nichiban) is firmly attached to the coating surface. Evaluation is based on the following criteria. The judgment criteria are as follows.

A: No peeling 10 times or more
AB: Dot or linear peeling along the knurled line
B: Surface peeling along the scratched line (20% or less), but 1/2 or less of the first grid C: Surface peeling along the scratched line (20% or more) However, the 1st of the peeling area 1/2 or less D: Exfoliation along the scratched line, but the entire surface of the first peeling area The adhesion after immersion in warm water is determined by the same method as above after immersion in warm water at 80 ° C. for 10 minutes.

4) Scratch resistance For those with a hard coat, the sand eraser (JIS # 502) is loaded with a 200g load.

  The result is judged and evaluated with the naked eye. The judgment criteria are as follows. In addition, the determination which rubbed in the state without a coating film was C.

3A: scratch area is 0%
2A: Scratch area exceeds 1% and less than 2% A: Scratch area exceeds 3% and less than 10% AB: Scratch area exceeds 10% and less than 30% B: Scratch area exceeds 30% and 60 Less than% C: The area of the scratch is 60% or more D: The area of the scratch is the entire surface

5) Dyeability
Seiko-Brown disperse dye 2 parts Dispersant: Diapon T 0.5 part is dissolved in 1 liter of pure water, and a lens coated with a hard coat composition only at a liquid temperature of 92 ° C. is immersed for 5 minutes for coloring. The degree is measured by transmittance.

6) Weather resistance test Exposed for 200 hours in the accelerated weather resistance test ("Sunshine Super Long Life Weather Meter" manufactured by Suga Test Instruments Co., Ltd.), and the peel condition is judged by the same method as the adhesion test in 3) above. . At the same time, investigate transparency, coloration, and surface condition after exposure.

7) Light resistance test
Using a Q-PANEL Q-SUN / Xe-1 xenon accelerated light resistance tester, UVA 340 nm is continuously irradiated at a temperature of 60 ° C. for 40 hours.

  As a test lens, a hard coat composition was applied and dyed to 50% coloration (same as 5 above dyeing test dye) and then an antireflection film was applied. The transmittance before and after UV irradiation Measure.

8) Impact resistance A 16.2 g steel ball is dropped from the height of 1.27 m into the center of the test sample to determine whether or not to penetrate. A test lens having a spherical surface with a center thickness of 2 mm and an edge thickness of 8 mm was used, and the test was performed at room temperature of 25 ° C. and humidity of 45%.

  Judgment criteria were ○: no penetration and x: penetration.

(5) Test result and consideration The test result of each said Example and a comparative example is shown to Tables 1-5. From the results, the following could be confirmed.

  (a) In the first to third embodiments, the structure of the present invention has practical characteristics such as scratch resistance and the property of suppressing optical interference, and also maintains black for ultraviolet rays while maintaining the high refractive lens. It was confirmed that the coloration phenomenon and film peeling phenomenon can be suppressed, and color lenses can be prevented from being discolored and discolored (see Tables 2 to 4).

That is, with respect to the point that the hard coat composition obtains an organic optical lens having a refractive index of 1.60 to 1.74, in Examples 1 to 3, (A) / (B) is a predetermined range = 10/2 to 10/8. It was confirmed that excellent spectacles performance was obtained in the range of all alkoxysilanes / colloid particles = 100: 25 to 100, and that the range of 0.3 to 5.0% of the content of the amine dispersant in the colloid was effective.

  In addition, when a rutile colloid is used by using 10 to 30 parts of an organic carboxylic acid as a low-temperature curing catalyst with respect to 100 parts of all alkoxysilanes, blue discoloration due to ultraviolet rays is suppressed and high transparency, weather resistance and light resistance are achieved. It was confirmed that a hard coat having

  (b) Comparative Example 1 corresponds to the conventional technique using the titania-based composite oxide colloid described in Patent Document 2, and was performed to determine what kind of quality difference is present in the ultrahigh refractive index lens. Is. In Comparative Example 1, decolorization, browning, and film removal of the dye that did not appear in Examples 1 to 3 were confirmed.

  (c) Comparative Example 2 corresponds to the prior art using the niobium oxide colloid described in Patent Document 3, and was performed to determine what kind of quality difference there is in the ultrahigh refractive index organic glass lens. It is. Compared with Example 3, it was not possible to cope with an ultrahigh refractive index organic glass lens, and optical interference was confirmed.

  (d) Comparative Example 3 was carried out for comparison between the case where the organic carboxylic acid according to the claim was used as the low temperature curing catalyst and the case where another metal chelate catalyst was used. If the rutile colloid and the organic carboxylic acid as a low-temperature curing catalyst were not combined, it was confirmed that the transparency as an organic glass lens was impaired by changing the color to blue due to ultraviolet irradiation and reducing the transmittance.

12 Lens substrate 14 Hard coat 16 Primer 18 Antireflection film

Claims (6)

A hard coat composition applied to an optical element body formed of organic glass,
As a coating film-forming component, it contains a hydrolyzate of alkoxysilane and a low-temperature curing catalyst for the hydrolyzate,
The hydrolyzate of the alkoxysilane is
Component (A):
Indication formula

(However, R ¹ is H or CH ₃ , R ² is an alkylene group having 1 to 4 carbon atoms, and R ³ is an alkyl group having 1 to 4 carbon atoms.)
And a trialkoxysilane represented by
(B) component:
A hydrolyzate of a mixture of a predetermined ratio with tetraalkoxysilane represented by the formula Si (OR ⁴ ) ₄ (wherein R ⁴ is an alkyl group having 1 to ⁴ carbon atoms);
In a hard coat composition comprising a metal oxide colloid,
The metal oxide colloid is a rutile colloid containing 0.3 to 5.0 parts by mass of an amine dispersant with respect to 100 parts by mass of colloidal particles,
The low-temperature curing catalyst is an organic carboxylic acid, and
The mixing mass ratio of the component (B) to the component (A) is (A) / (B) = 10/2 to 10/8,
The amine dispersant is an aliphatic amine, aliphatic diamine, or cyclic amine in which one, two, or three hydrogen atoms of ammonia and ammonia NH ₃ are substituted with a hydrocarbon group R ⁵ (C 1-5), and A derivative of
A hard coat composition characterized by the above.   The colloidal particle diameter of the rutile colloid is in the range of 5 to 60 nm, the mixing ratio of the amine dispersant to 100 parts by mass of the colloidal particles is 0.3 to 5.0 parts by mass, and the component (A) The blending ratio of the colloidal particles (solid content) and the organic carboxylic acid to 100 parts by mass of the total alkoxysilane, which is the total amount of the component (B), is the former: 25-100 parts by mass and the latter: 10-30 parts by mass. The hard coat composition according to claim 1, wherein the composition is a hard coat composition.   A hard coat formed of the hard coat composition according to claim 1 or 2 is provided on one or both sides of an optical substrate formed of an organic glass having a refractive index of 1.60 to 1.74. An optical element.   The optical element according to claim 3, wherein the organic glass has a refractive index of 1.70 to 1.74.   The optical element according to claim 3, further comprising a primer film between the optical substrate and the hard coat.   6. The optical element according to claim 5, further comprising an optical inorganic thin film (including an antireflection film, a reflection increasing film, and an interference filter) on the surface side of the hard coat.

Images