JP4737401B2 - Antireflection film, coating composition for forming antireflection film, and article provided with antireflection film - Google Patents

Description

  The present invention relates to an antireflective film excellent in alkali resistance, scratch resistance and antifouling property made of a fluorine-containing silicone comprising a specific crosslinked product, a bissilane compound containing F atoms having a specific structure for forming the antireflective film, and The present invention relates to a coating composition for forming a protective film containing a (partial) hydrolyzate of perfluoroalkylsilane as a main component, and a coated optical article having a film formed by curing it.

  In recent years, antireflection films have been applied to optical articles such as various displays such as computers, televisions, plasma displays, liquid crystal display devices, transparent plastic lenses, various instrument covers, automobiles, train window glass, etc. for the purpose of improving visibility. It is used in the outermost layer. From the principle of antireflection, the antireflection film needs to have a low refractive index.

  Since the fluororesin is a material having a low refractive index and excellent alkali resistance, it is also applied to antireflection applications such as displays. However, a fluororesin is often used as a rubber material because of its molecular structure, and it is difficult to obtain a hard protective coating agent having excellent scratch resistance.

  In recent years, hydrolyzable silane compounds having a perfluoroalkyl group have been developed, and various coating agents with excellent alkali resistance, water repellency, oil repellency, antifouling properties, antireflection properties, etc. have been developed taking advantage of the properties. Yes. However, because the perfluoroalkyl groups that provide the properties are bulky and inert, the cured coating has a lower crosslink density, and as a result, it is considerably harder than fluoropolymers, but still has no scratch resistance. It is insufficient.

  For the purpose of enhancing the scratch resistance, a method of co-hydrolyzing a perfluoroalkyl group-containing silane and various silane compounds such as tetraalkoxysilane has been proposed (see Patent Document 1: Japanese Patent Application Laid-Open No. 2002-53805). In addition, for the purpose of achieving both scratch resistance and antifouling properties, a system in which a perfluoroalkyl group-containing silane and a tetraalkoxysilane or a silane coupling agent are used in combination with a bissilane compound containing a perfluoroalkylene group as a spacer ( Patent Documents 2 and 3: Japanese Patent Laid-Open Publication No. 61-40845 and Japanese Patent Publication No. 6-29332 have been proposed. In a system using tetraalkoxysilane, the Q unit portion is weak against alkali, and there is a risk that the film may deteriorate when washed with a strong alkaline detergent at home, which is not preferable. In addition, a system in which a bissilane compound containing a perfluoroalkylene group as a spacer and an epoxy functional silane is used in combination (see Patent Document 4: Japanese Patent No. 2629813) has also been proposed. Although the target antifouling property, scratch resistance, adhesion and antireflection properties have been secured at a relatively good level, the fluorine content is lowered and the epoxy group is hydrophilic, so alkali resistance is high. Insufficient and practically problematic.

  Moreover, in the said patent document 4, the combination which consists of the bissilane compound and perfluoroalkyl group containing silane which contain a perfluoroalkylene group as a spacer on the surface of the transparent plastic base material which has a scattering uneven surface is described in an Example. Has been. Since the chain length of the perfluoroalkylene group of the bissilane compound used is long and the distance between cross-linking points of the resulting cured film is long, there is a drawback that sufficient scratch resistance cannot be obtained. There was no description about the alkali resistance, and the necessary characteristics for satisfying the good alkali resistance could not be grasped. Further, there is a similar system in which alkali resistance is evaluated with a hard glass substrate (see Patent Document 5: Japanese Patent No. 3210045). In the Examples, the alkali resistance is evaluated by immersing the whole test piece in a 1% NaOH aqueous solution for 24 hours, and immediately washing it to evaluate the appearance change and the water drop removal property. The film being evaluated is a ternary film composed of a perfluoroalkyl group-containing silane alone film, a bissilane compound containing a perfluoroalkylene group as a spacer, a perfluoroalkyl group-containing silane, and a tetraalkoxysilane. There are two types. The present inventor also evaluated the appearance after confirming the appearance change after wiping off a droplet after 30 minutes had passed, and the ternary coating film was slightly clouded and colorless and transparent at the portion where the water droplet was placed. A difference was observed in appearance from the portion where no droplet was placed, and the alkali resistance was insufficient. In the method of immersing the entire test piece, since the whole deteriorates uniformly, a change in appearance cannot be confirmed, which is insufficient as an evaluation method, and it is considered that the alkali resistance is practically insufficient. Moreover, when the coating film of the perfluoroalkyl group-containing silane alone was applied to a synthetic resin substrate, the scratch resistance was insufficient as described above. As described above, the conditions found by the present inventor that satisfy both good alkali resistance, scratch resistance and antifouling properties cannot be grasped in any system.

  Thus, an antireflection coating agent excellent in chemical resistance (particularly alkali resistance), scratch resistance and antifouling properties has not been found so far.

JP 2002-53805 A JP 61-40845 A Japanese Patent Publication No. 6-29332 Japanese Patent No. 2629813 Japanese Patent No. 3210045

  The present invention has been made in view of the above circumstances, and contains an F atom and an Si atom excellent in alkali resistance, scratch resistance and antifouling property, and has an antireflection film having a three-dimensional crosslinked structure, and the antireflection film is formed. An object of the present invention is to provide a coating agent composition, an optical article on which the antireflection film is formed, and a multilayer laminate of the optical article.

  As a result of intensive studies on anti-reflection coatings excellent in scratch resistance and alkali resistance, the present inventors have obtained an anti-reflection film satisfying the following conditions, a coating agent composition for forming the film, and the same It has been found that an optical article coated with a coating can simultaneously satisfy the scratch resistance, alkali resistance and antifouling properties.

That is, in the three-dimensional cross-linked antireflection film containing (F atoms and Si atoms) provided in the outermost layer of the synthetic resin transparent substrate,
(I) Si—C ₂ H ₄ — (CF ₂ ) _n —C ₂ H ₄ —Si bond having a short chain spacer containing an Si—O—Si bond and an F atom (where n is 4). Or 6), it is possible to obtain good scratch resistance by increasing the crosslinking density.
(II) When the ratio of F atoms to Si atoms in the antireflection film satisfies the range of F / Si = 8.0 to 10.0 (molar ratio),
(III) Perfluoroalkyl group —C ₂ H ₄ — (CF ₂ ) _a F represented by the following structure among all organic substituents bonded to Si (where a is 4, 6, 8, 10 or 12) .)
Is contained in the cured film, thereby imparting excellent water repellency, oil repellency and lubricity to the cured film. As a result, the composite effect of (I) to (III) results in 1 on the antireflection film. The appearance after wiping off a water droplet of a mass% NaOH aqueous solution after 30 minutes shows alkali resistance that is the same as the initial appearance, and gives the antireflection film good alkali resistance, scratch resistance and antifouling properties. I found that I can do it.

  Since the refractive index of the coating film obtained by the present invention is lowered, it is possible to form a coating film having excellent antireflection properties by setting the coating film alone or further by setting a layer having a high refractive index in the lower layer as an optical film thickness. it can.

  In addition, it contains substantially no Q units that are vulnerable to attack by alkaline substances, and the network is composed of siloxane bonds and short-chain rigid fluorine-containing alkylene groups, thereby increasing the crosslink density and at the same time increasing the F atoms to a specific ratio or more. It has been newly found that when it is made into a coating film, it exhibits strong alkali resistance. When cleaning surface contamination, it is safe to use a strong alkaline cleaning agent.

  By shortening the fluorine-containing alkylene chain length, the crosslink density is increased, and by adding F atoms in a specific ratio or more to impart lubricity to the surface, the cured film has excellent scratch resistance and antifouling properties. I also found out.

  And from the above, it is also effective as a protective coating for plastic substrates and the like lacking in these characteristics, and since this cured coating is also excellent in transparency, various displays such as computers, televisions, plasma displays, and liquid crystal display devices Applicable to anti-reflective optical articles or films with excellent water repellency, anti-fouling properties, anti-fingerprint resistance, and scratch resistance, such as polarizing plates, transparent plastic lenses, covers for various instruments, window windows for automobiles, trains, etc. The inventors have found that the present antireflection film or plate can be adhered and used on a substrate by providing a pressure-sensitive adhesive layer or an adhesive layer on the back surface, and the present invention has been completed.

  In addition, the present inventor has proposed a coating mainly composed of a bissilane compound containing a perfluoroalkylene group as a spacer as a protective coating agent excellent in chemical resistance in JP-A-2004-315712. As the performance of household cleaning agents has improved, the level of alkali resistance required has been increasing. For this reason, antireflective agents with higher alkali resistance have been demanded. The present invention responds to this demand.

Accordingly, the present invention provides lower Kiko computing compositions, optical articles, the multilayer stack.
Claim 1 :
(1) a bissilane compound (A) and / or its (partial) hydrolyzate and / or its condensate;
_{X m R 3-m Si-} C 2 H 4 (CF 2) n C 2 H 4 -SiR 3-m X m (A)
(Wherein R is the same or different monovalent hydrocarbon group selected from an alkyl group having 1 to 6 carbon atoms and a phenyl group, X is an OH group, a halogen atom, an alkoxy group having 1 to 4 carbon atoms, acyloxy A group, an alkenoxy group, a ketoxime group, an alkoxyalkoxy group or an —NCO group, m is 2 or 3, and n is 4 or 6.)
(2) Organosilicon compound (B) containing a perfluoroalkyl group and / or its (partial) hydrolyzate and / or its condensate F (CF ₂ ) _a C ₂ H ₄ —SiR _3-b X _b ( B)
(In the formula, R and X have the same meanings as described above, a is 4, 6, 8, 10 or 12, and b is 2 or 3.)
Or a mixture of components (1) and (2) that is co- (partially) hydrolyzed / condensed as a main component, with respect to the total mass of components (1) and (2), content of 42-70% by mass of 2) is, further, (3) an organosilicon compound represented by the following average composition formula (C)
[R ₃ Si— (O—R ₂ Si—) _c —Y—] _p R _q SiX _r O _{(4-pqr) / 2} (C)
(In the formula, R and X have the same meanings as described above, Y is —O— or an alkylene group having 2 to 10 carbon atoms, and 0.01 ≦ p <1, 0 ≦ q <1, 0.5. ≦ r <3, 1 <p + q + r <4, c is 1 to 100)
An antireflection film-forming coating agent composition having excellent alkali resistance, characterized by comprising
Claim 2 :
Further, the silicon-based or fluorine-based surfactant characterized in that the addition of claim 1 for forming an antireflective film coating composition.
Claim 3 :
Alkyl silicates, epoxy functional silanes, (meth) acryl functional silanes, mercapto functional silanes, amino functional silanes and their (partial) hydrolysates, mixtures of organosilicon compounds of components (1) and (2) The coating composition for forming an antireflective film according to claim 1 or 2 , wherein the composition is not contained in 1% by mass or more in or in a co- (partial) hydrolysis / condensate thereof.
Claim 4 :
The coating agent composition for forming an antireflection film excellent in alkali resistance according to any one of claims 1 to 3 , wherein the solvent is contained in an amount of 50 to 99% by mass in the coating agent composition.
Claim 5 :
The coated optical article which formed in the outermost layer of the synthetic resin transparent base material the cured film of the coating agent composition for antireflection film formation of any one of Claims 1 thru | or 4 as an antireflection film.
Claim 6 :
6. The coated optical article according to claim 5, wherein a coating film and / or a scratch-resistant protective layer having a higher refractive index than the base material is provided between the synthetic resin transparent base material and the antireflection film.
Claim 7 :
7. The coated optical article according to claim 6, wherein the high refractive index film contains a metal oxide sol containing atoms selected from at least Ti, Sn, Ce, Al, Zr, In, and Fe.
Claim 8 :
Synthetic resin, polycarbonate resin, polyalkylene terephthalate resin, either an acrylic resin, triacetyl cellulose resin, polystyrene resin, according to claim 5 to 7, characterized in that those selected from the polyolefin resin The coated optical article according to claim 1.
Claim 9 :
The coated optical article according to any one of claims 5 to 8 , wherein the transparent substrate is in the form of a film or a plate.
Claim 10 :
A multilayer laminate comprising a coated optical article according to any one of claims 5 to 9 further provided with a pressure-sensitive adhesive or adhesive layer on the transparent substrate side, and a release film further laminated thereon.

  In the present invention, (partial) hydrolysis indicates partial hydrolysis or complete hydrolysis.

  The antireflection film of the present invention and the article on which the antireflection film is formed have excellent alkali resistance, scratch resistance and antifouling properties. According to the coating composition according to the present invention, such antireflection A film can be formed satisfactorily.

The antireflection film according to the present invention is a three-dimensionally cross-linked antireflection film containing (F atoms and Si atoms) provided on the outermost layer of a synthetic resin transparent substrate,
(I) The crosslinked structure is composed of Si—O—Si bonds and Si—C ₂ H ₄ — (CF ₂ ) _n —C ₂ H ₄ —Si bonds (where n is 4 or 6). And
(II) The ratio of F atoms to Si atoms in the antireflection coating is F / Si = 8.0 to 10.0 (molar ratio),
(III) the total monovalent organic substituents attached to Si, -C ₂ H ₄ containing 90 to 100 mol% of the perfluoroalkyl group represented by the following structural - (CF _{2) a} F (provided that, a 4 , 6, 8, 10 or 12.)
It is characterized by that. This anti-reflective film is excellent in alkali resistance, and in particular, the appearance after wiping off a water droplet of 1% by weight NaOH aqueous solution on the anti-reflective film after 30 minutes has shown alkali resistance that is the same as the initial appearance. obtain.

The crosslinked structure is composed of a Si—O—Si bond and a Si—C ₂ H ₄ — (CF ₂ ) _n —C ₂ H ₄ —Si bond (where n is 4 or 6). As the moiety (—C ₂ H ₄ — (CF ₂ ) _n —C ₂ H ₄ —), —C ₂ H ₄ — (CF ₂ ) ₄ —C ₂ H ₄ —, —C ₂ H ₄ — (CF ₂ ) Any of _6- C ₂ H _4- is preferable. As a result, when the chain length becomes long, the crosslink density becomes sparse, and as a result, the coating film cannot obtain sufficient strength, so that good scratch resistance cannot be obtained. On the other hand, when a fluorinated polyether chain is used, the spacer portion is not rigid, and conversely, the scratch resistance is lowered.

  The ratio (molar ratio) between F atoms and Si atoms in the antireflection coating should satisfy the range of F / Si = 8.0 to 10.0, preferably 8.0 to 9.8. If it is smaller than the lower limit of this range, the fluorine content is too low to obtain good alkali resistance, and if it is larger than the upper limit of this range, the organic substituent or the spacer part containing F atoms becomes longer, so that the cured film Becomes soft and good scratch resistance cannot be obtained.

Further, among all monovalent organic substituents bonded to Si, perfluoroalkyl represented by —C ₂ H ₄ — (CF ₂ ) _a F (where a is 4, 6, 8, 10 or 12). When the group is contained in an amount of 90 to 100 mol%, the cured film can be provided with excellent water repellency and lubricity, so that excellent alkali resistance, scratch resistance and antifouling properties can be obtained. If it is less than this lower limit, the alkali resistance is insufficient. The value of a that determines the chain length of the perfluoroalkyl group should satisfy the range of 4-12. If it is smaller than this, sufficient water repellency cannot be obtained, and good alkali resistance cannot be achieved. If the chain length is longer than this, the cured film becomes flexible and good scratch resistance cannot be obtained. Further, the boiling point of the silane compound is remarkably increased, so that purification becomes difficult and economically disadvantageous. Examples of the organic substituent other than the perfluoroalkyl group bonded to Si include an alkyl group having 1 to 20 carbon atoms, a phenyl group, and a perfluoropolyether group.

  If the above circumstances are satisfied, the obtained antireflection film exhibits excellent alkali resistance even when the following alkali resistance test is performed. That is, a water droplet of a 1% by weight NaOH aqueous solution is placed on the antireflection film, and after 30 minutes, the appearance after wiping is not formed with a faint white spot, which is the same as the initial appearance. Further, if the conditions of the F / Si range and the F-containing substituent content ratio are satisfied, the refractive index of the antireflection film becomes 1.40 or less, and good antireflection performance can be obtained.

  Furthermore, when one end-capped diorganopolysiloxane chain-containing component, which will be described later, is added to the antireflection film, the siloxane chain portion having poor compatibility moves to the surface before curing and is fixed at the time of curing. Excellent lubricity and antifouling properties can be imparted, and the anti-scratch and antifouling properties of the antireflection film can be improved.

Further, when the antireflection film contains Q (SiZ ₄ unit) units, it is difficult to obtain good alkali resistance because the Q units are weak against alkali components. From this point, the content of the Q unit should be reduced as much as possible, and should not be substantially contained. Even when it is contained, it is preferable to stop the amount to 0 to less than 1 mol% with respect to all Si atoms.

In SiZ ₄ , Z represents an OH group, an alkoxy group having 1 to 4 carbon atoms, an acyloxy group, an alkenoxy group, or a siloxane residue. Here, the siloxane residue means an end of a crosslinked structure bonded by a siloxane bond.

Next, the coating agent for forming the antireflection film will be described.
(1) a bissilane compound (A) and / or its (partial) hydrolyzate and / or its condensate;
_{X m R 3-m Si-} C 2 H 4 (CF 2) n C 2 H 4 -SiR 3-m X m (A)
(Wherein R is the same or different monovalent hydrocarbon group selected from an alkyl group having 1 to 6 carbon atoms and a phenyl group, X is an OH group, a halogen atom, an alkoxy group having 1 to 4 carbon atoms, acyloxy A group, an alkenoxy group, a ketoxime group, an alkoxyalkoxy group or an —NCO group, m is 2 or 3, and n is 4 or 6.)
(2) Organosilicon compound (B) containing a perfluoroalkyl group and / or its (partial) hydrolyzate and / or its condensate F (CF ₂ ) _a C ₂ H ₄ —SiR _3-b X _b ( B)
(In the formula, R and X have the same meanings as described above, a is 4, 6, 8, 10 or 12, and b is 2 or 3.)
Or a mixture of components (1) and (2) that is co- (partially) hydrolyzed / condensed as a main component, with respect to the total mass of components (1) and (2), The content of 2) is 42 to 70% by mass.

Here, it is the bissilane compound (A) of the component (1).
_{X m R 3-m Si-} C 2 H 4 (CF 2) n C 2 H 4 -SiR 3-m X m (A)
In the formula, R represents a monovalent hydrocarbon group which may be the same or different and is selected from an alkyl group having 1 to 6 carbon atoms and a phenyl group. Specific examples include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a cyclohexyl group, and a phenyl group. X represents an OH group, a halogen atom, an alkoxy group having 1 to 4 carbon atoms, an acyloxy group, an alkenoxy group, a ketoxime group, an alkoxyalkoxy group or an —NCO group. Specifically, halogen atoms such as OH group and Cl, alkoxy groups such as methoxy group, ethoxy group, propoxy group, isopropoxy group and butoxy group, alkenoxy groups such as isopropenoxy group, acyloxy groups such as acetoxy group, methyl ethyl ketoxime Examples thereof include a ketoxime group such as a group, an alkoxyalkoxy group such as a methoxyethoxy group, and a —NCO group. A methoxy group or an ethoxy group silane compound is preferable because it is easy to handle and can easily control the reaction during hydrolysis. M indicating the number of siloxane crosslinkable groups X is preferably 2 or 3. In order to increase the crosslink density and achieve a good level of scratch resistance, m = 3 is preferable.

As a specific example of the bissilane compound satisfying the above,
_{(CH 3 O) 3 Si-} C 2 H 4 - (CF 2) 4 -C 2 H 4 -Si (OCH 3) 3,
_{(CH 3 O) 3 Si-} C 2 H 4 - (CF 2) 6 -C 2 H 4 -Si (OCH 3) 3,
_{(C 2 H 5 O) 3} Si-C 2 H 4 - (CF 2) 4 -C 2 H 4 -Si (OC 2 H 5) 3,
_{(C 2 H 5 O) 3} Si-C 2 H 4 - (CF 2) 6 -C 2 H 4 -Si (OC 2 H 5) 3,
_{(C 3 H 7 O) 3} Si-C 2 H 4 - (CF 2) 4 -C 2 H 4 -Si (OC 3 H 7) 3,
_{(C 3 H 7 O) 3} Si-C 2 H 4 - (CF 2) 6 -C 2 H 4 -Si (OC 3 H 7) 3,
_{(CH 3 O) 2 (CH} 3) Si-C 2 H 4 - (CF 2) 4 -C 2 H 4 -Si (CH 3) (OCH 3) 2,
_{(CH 3 O) 2 (CH} 3) Si-C 2 H 4 - (CF 2) 6 -C 2 H 4 -Si (CH 3) (OCH 3) 2,
_{(CH 3 O) 2 (C} 6 H 5) Si-C 2 H 4 - (CF 2) 4 -C 2 H 4 -Si (C 6 H 5) (OCH 3) 2,
_{(CH 3 O) 2 (C} 6 H 5) Si-C 2 H 4 - (CF 2) 6 -C 2 H 4 -Si (C 6 H 5) (OCH 3) 2
Among these, preferably,
_{(CH 3 O) 3 Si-} C 2 H 4 - (CF 2) 4 -C 2 H 4 -Si (OCH 3) 3,
_{(CH 3 O) 3 Si-} C 2 H 4 - (CF 2) 6 -C 2 H 4 -Si (OCH 3) 3
These bissilane compounds are preferably used.

  Moreover, the partial hydrolyzate of these bissilane compounds and those condensates can also be used.

Next, the organosilicon compound (B) containing the perfluoroalkyl group of the component (2) used in combination with the bissilane compound (A) will be described.
F (CF ₂ ) _a C ₂ H ₄ —SiR _3-b X _b (B)
It is preferable that a which determines the chain length of the perfluoroalkyl group takes a value of 4, 6, 8, 10 or 12. If it is shorter than this value, the content of F atoms in the coating becomes low and the alkali resistance is lowered, which is not preferable. B representing the number of siloxane crosslinkable groups X is preferably 2 or 3. In order to increase the crosslink density and achieve a good level of scratch resistance, b = 3 is preferable.

As a specific example of the organosilicon compound containing the F atom-substituted organic group satisfying the above,
_{CF 3 (CF 2) 3 C} 2 H 4 -Si (OCH 3) 3,
_{CF 3 (CF 2) 3 C} 2 H 4 -Si (OC 2 H 5) 3,
_{CF 3 (CF 2) 3 C} 2 H 4 -Si (CH 3) (OCH 3) 2,
_{CF 3 (CF 2) 5 C} 2 H 4 -Si (OCH 3) 3,
_{CF 3 (CF 2) 7 C} 2 H 4 -Si (OCH 3) 3,
_{CF 3 (CF 2) 7 C} 2 H 4 -Si (OC 2 H 5) 3,
_{CF 3 (CF 2) 7 C} 2 H 4 -Si (CH 3) (OCH 3) 2,
_{CF 3 (CF 2) 9 C} 2 H 4 -Si (OCH 3) 3,
CF ₃ (CF ₂ ) ₁₁ C ₂ H ₄ —Si (OCH ₃ ) ₃
Among these, the following are particularly preferable.
CF ₃ (CF ₂ ) ₇ C ₂ H ₄ —Si (OCH ₃ ) ₃

  In addition, (partial) hydrolysates and (partial) condensates of these organosilicon compounds can also be used.

  In this invention, it is necessary to make content rate of a component (2) into 42-70 mass% with respect to the total mass of a component (1) and a component (2). When the content of the component (2) is less than 42% by mass, the fluorine content in the cured film is lowered, and the alkali resistance may be insufficient. If it exceeds 70% by mass, the crosslink density may decrease, and good scratch resistance may not be obtained. More preferably, the content rate of a component (2) is 43-60 mass%.

  In addition to the bissilane compound and the perfluoroalkyl group-containing organosilicon compound, the following compounds can be used in combination as long as they do not affect the required properties. Specifically, silicates such as tetraethoxysilane, epoxy functional silanes such as γ-glycidoxypropyltrimethoxysilane, 3,4-epoxycyclohexyltrimethoxysilane, and amino such as γ-aminopropyltriethoxysilane. Functional silanes, (meth) acrylic functional silanes such as γ- (meth) acryloxypropyltrimethoxysilane, mercaptofunctional silanes such as γ-mercaptopropyltrimethoxysilane, methyltrimethoxysilane, hexyltrimethoxy Examples thereof include alkylsilanes such as silane and decyltrimethoxysilane, phenylsilanes such as phenyltrimethoxysilane, and derivatives thereof. However, it is necessary that the alkyl silicate is not contained in 1% by mass or more in the total organosilicon compound. The content of hydrophilic silane compounds such as epoxy functional silane, (meth) acryl functional silane, mercapto functional silane, amino functional silane, etc. is 10% by mass or less, particularly preferably 1% by mass in the total organosilicon compound. It is as follows. Since water-soluble alkaline substances are likely to get wet, are subject to alkaline attack and cause deterioration, it is not good to add more. Alkyl silanes or phenyl silanes can be used within a range that satisfies the above conditions such as F / Si ratio.

  The bissilane compound (A) and the perfluoroalkyl group-containing organosilicon compound (B) may be mixed and used as they are, or (partially) hydrolyzed or in the following solvent (partially) hydrolysis / condensation You may use it in the form. From the standpoint of increasing the curing rate after coating, it is preferable to use in a (partial) hydrolyzed / condensed form.

  In this case, the (part) hydrolyzate or condensate of each of the compounds (A) and (B) may be mixed and used, and the compounds (A) and (B) may be used together (partially). It may be hydrolyzed and condensed.

The amount of water used in the hydrolysis, it is preferable to use a molar ratio of 0.1 to 10 ratio of _{(H 2 O / Si-X} ).

  For the hydrolysis / condensation, a conventionally known method can be applied. As a hydrolysis catalyst or hydrolysis / condensation curing catalyst, acids such as hydrochloric acid, nitric acid, acetic acid, maleic acid, NaOH, ammonia, triethylamine, Amine compounds such as butylamine, hexylamine, octylamine, dibutylamine, and salts of amine compounds, bases such as quaternary ammonium salts such as benzyltriethylammonium chloride and tetramethylammonium hydroxide, potassium fluoride, sodium fluoride Organic carboxylic acids such as fluoride salts, solid acidic catalysts or solid basic catalysts (such as ion exchange resin catalysts), iron-2-ethylhexoate, titanium naphthate, zinc stearate, dibutyltin diacetate Metal salts, tetrabutoxy titanium, tetra-i Organic titanium esters such as propoxytitanium, dibutoxy- (bis-2,4-pentanedionate) titanium, di-i-propoxy (bis-2,4-pentanedionate) titanium, tetrabutoxyzirconium, tetra-i-propoxy Organic zirconium esters such as zirconium, dibutoxy- (bis-2,4-pentanedionate) zirconium, di-i-propoxy (bis-2,4-pentanedionate) zirconium, and alkoxyaluminum compounds such as aluminum triisopropoxide , Organometallic compounds such as aluminum chelate compounds such as aluminum acetylacetonate complex, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxy Silane, aminoalkyl-substituted alkoxysilanes such as N- (β-aminoethyl) -γ-aminopropyltriethoxysilane, etc. may be used alone or in combination.

  The addition amount of this catalyst is 0.01-10 mass parts with respect to 100 mass parts of compounds (A) or (B), Preferably it is 0.1-5 mass parts. If this amount is less than 0.01 parts by mass, it may take too long to complete the reaction or the reaction may not proceed. On the other hand, when the amount is more than 10 parts by mass, it is disadvantageous in cost, and the resulting composition or cured product may be colored or side reactions may increase.

  This composition can be diluted with a solvent and used. As this solvent, alcohols such as methanol, ethanol, propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol, t-butyl alcohol, diacetone alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl Ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, glycol ethers such as propylene glycol monomethyl ether acetate, ethers such as dioxane and tetrahydrofuran, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and acetyl acetone, ethyl acetate , Esters such as butyl acetate and ethyl acetoacetate, xylene, Etc. The.

  The addition amount of the solvent is arbitrary, but considering the ease of painting, the ease of controlling the coating film thickness, and the stability of the coating solution, the content of the solvent in the coating solution is 50 to 99. It is preferable that it is mass%, Most preferably, it is 70-98 mass%.

  Furthermore, a silicon-containing or fluorine-containing surfactant may be added to the coating agent composition of the present invention. Specifically, various polyether-modified silicone compounds and products manufactured by Sumitomo 3M Co., Ltd. (trade name: Fluorard), DuPont (fluoroalkyl polyether), and Asahi Glass Co., Ltd. (trade name: Surflon) are sold. And various fluorine-containing surfactants. The addition amount may be in the range of 0.01 to 10% by mass with respect to the solid content in the coating agent. The surfactant is effective for ensuring leveling properties during coating.

In the coating agent composition of the present invention, the following average composition formula (C)
[R ₃ Si— (O—R ₂ Si—) _c —Y—] _p R _q SiX _r O _{(4-pqr) / 2} (C)
(In the formula, R and X have the same meanings as described above, Y is —O— or an alkylene group having 2 to 10 carbon atoms, and 0.01 ≦ p <1, 0 ≦ q <1, 0.5. ≦ r <3, 1 <p + q + r <4, c is 1 to 100)
It is preferable to add a one-end-capped polydialkylsiloxane chain-containing organosilicon compound represented by:

This compound is not completely compatible with the coating agent main body containing a high amount of F atoms, phase separation occurs when the solvent in the coating agent volatilizes, bleeds out to the surface, and a reactive silyl group is formed at one end. Since it contains, it is fixed to the cured surface and can impart durable leveling, antifouling or lubricating properties. Here, Y represents a spacer group for bonding one end-capped diorganopolysiloxane group to an oligomeric organosilicon compound having a hydrolyzable group. Specific examples of Y include etheric oxygen (in this case, meaning a siloxane bond), — (CH ₂ ) ₂ —, — (CH ₂ ) ₆ —, — (CH ₂ ) ₈ —, — (CH ₂ ). _{10 -, - (CH 2)} 2 -C 6 H 4 - (CH 2) 2 -, - (CH 2) 2 -C 6 H 10 - , and the like. Etheric oxygen or — (CH ₂ ) ₂ — is preferable from the economical advantage, and particularly when light resistance is required, etheric oxygen in which all basic skeletons are formed by siloxane bonds is preferable.

  P representing the degree of substitution of the one-end blocked diorganopolysiloxane group should satisfy the range of 0.01 ≦ p <1. If p is less than 0.01, sufficient lubricity and antifouling properties may not be obtained, and if it is 1 or more, curability may be deteriorated. Particularly preferably, 0.02 ≦ p ≦ 0.7 is satisfied.

  q represents the degree of substitution of the substituent R, and preferably satisfies the range of 0 ≦ q <1. When the number is 1 or more, the number of crosslinkable groups X in the cured coating film is decreased, and durability may be inferior. Particularly preferably, 0 ≦ q ≦ 0.7 is satisfied.

  r represents the degree of substitution of the OH group or hydrolyzable group, and preferably satisfies the range of 0.5 ≦ r <3. If it is less than 0.5, the number of crosslinkable groups X decreases, and durability may be inferior. When it is 3 or more, it means substantially a monomer of an organosilicon compound, and the one-end-capped diorganopolysiloxane group is not well oriented outward on the treated surface, and good antifouling properties may not be obtained. Particularly preferably, 1 ≦ r ≦ 2.5 is satisfied.

  Further, p + q + r is 1 <p + q + r <4, preferably 2 <p + q + r ≦ 3, and particularly preferably 2.1 ≦ p + q + r ≦ 2.7.

C representing the degree of polymerization of the diorganosiloxy unit should satisfy the range of 1-100. If c is less than 1, the diorganosiloxane chain length is short and sufficient antifouling property cannot be obtained. When c exceeds 100, the orientation on the surface does not proceed well at the time of processing, so that satisfactory antifouling properties cannot be obtained, surface fixing is not sufficient, and durability is insufficient. More preferably, c satisfies the range of 1-50.
The addition amount of this material should just be the range of 0.01-10 mass% with respect to solid content in a coating agent.

  Further, the coating agent composition of the present invention is blended with inorganic oxide fine particles, particularly silica dispersed in water or an organic solvent, or a hollow silica sol for the purpose of improving the hardness and scratch resistance of the film. May be. Among these, those having an average primary particle diameter of 0.001 to 0.1 μm are preferable, and more preferably 0.001 to 0.08 μm. When the average primary particle diameter exceeds 0.1 μm, the transparency of the cured film formed by the prepared composition tends to decrease. As these inorganic oxide fine particles, those whose surfaces are treated with an organometallic compound such as a silane-based, titanium-based, aluminum-based, or zirconium-based coupling agent may be used. As addition amount of inorganic oxide fine particles, it is 0-30 mass parts in conversion of solid content per 100 mass parts of total amounts of the said component (1), (2), Preferably it is 0.1-10 mass parts. .

  The coating agent composition of the present invention obtained by the above method, further includes an organic and inorganic ultraviolet absorber, and a buffer for controlling the pH in the system to pH 2 to 7 where silanol groups are likely to exist stably. For example, optional components such as acetic acid-sodium acetate and disodium hydrogen phosphate-citric acid may be contained.

  The film thickness of the antireflection film formed on the substrate surface by the coating agent composition according to the present invention is usually preferably controlled to 0.01 to 0.5 μm. Particularly, when the optical film thickness is adjusted to about 0.1 μm, good antireflection properties can be obtained. The method for coating the surface of the composition with the composition is not particularly limited, such as a dipping method, a spin coating method, a flow coating method, a roll coating method, a spray coating method, or a screen printing method. Therefore, it is preferable to carry out the film thickness to a predetermined thickness by a dipping method, a spray method and a roll coating method.

  In addition, hardening of the coating agent composition of this invention can be made into room temperature-150 degreeC x 1 minute-10 hours, Preferably it is 60 degreeC-120 degreeC x 10 minutes-2 hours as conditions to heat-harden.

  The coating agent is applied to a transparent base made of synthetic resin. In this case, as specific examples of the synthetic resin, any resin having excellent optical characteristics can be applied. Alkylene terephthalate resin, cellulose resin such as diacetyl cellulose, acetate butyrate cellulose, triacetyl cellulose, acrylic resin, polystyrene resin, polyimide resin, polyester resin, polyether sulfone resin, polyarylate liquid crystal resin, polyurethane resin Polyolefin resins such as polysulfone resin, polyether ketone resin, trimethylpentene, and polyvinyl norbornene, and composite resins thereof can be exemplified, but are not limited thereto. Particularly preferred are polycarbonate resins, polyalkylene terephthalate resins such as PET, triacetyl cellulose resins, and acrylic resins. The transparent substrate may be a molded part, a plate shape, or a film shape. From the viewpoint of ease of painting work, a film-like one is more preferable.

  With the coating composition according to the present invention, various oil-repellent antifouling coatings may be further laminated on the cured coating formed on the substrate surface. In particular, an oil-repellent antifouling coating can be provided for the purpose of preventing adhesion of oil stains such as fingerprints attached when using the antireflective component according to the present invention and for easily removing the attached stains.

  When using a transparent base material coated and coated with the coating agent of the present invention as an anti-reflective part with excellent scratch resistance and chemical resistance, it is also possible to attach it to another transparent base material. It is. In order to use it by sticking it to other base materials, a conventionally known acrylic, epoxy, polyimide, or silicone adhesive or pressure sensitive adhesive is applied to the side opposite to the side coated with the coating agent. It may be provided. Particularly preferred are acrylic and silicone materials.

  The film thickness of the adhesive layer may be in the range of 1 to 500 μm. If it is too thin, good adhesive strength cannot be obtained, and if it is too thick, it may be economically disadvantageous. Further, a protective plastic sheet for surface protection may be provided thereon as a release layer.

  In the optical article of the present invention, a high refractive index film and / or a scratch-resistant protective layer can be provided between the synthetic resin transparent substrate and the antireflection film, but the antireflection property is improved. The high refractive index layer that can be provided between the antireflection layer and the transparent substrate will be described.

  The high refractive index layer is required to have high hardness and a refractive index as high as possible. As a result of various studies by the present inventors, it is preferable that the high refractive index layer is mixed with a metal oxide sol having a high refractive index so that the refractive index is 1.60 or more. As the metal oxide sol to be blended for the purpose of increasing the refractive index, high refractive index ultrafine particles having a refractive index of 1.6 or more are preferably used. The high refractive index metal oxide sol is preferably a high refractive index metal oxide sol having an average particle diameter of 1 to 100 nm, particularly 1 to 50 nm. When the high refractive index metal oxide sol is blended, the blending amount is not particularly limited. However, in order to sufficiently achieve the blending purpose, the amount of the curable component of the composition forming the high refractive index layer is 100 parts by weight. 5 to 500 parts by mass is preferable. Most preferably, it is 70-250 mass parts. When the blending amount is more than 500 parts by mass, problems such as the occurrence of haze in the cured film tend to occur, which is not preferable. On the other hand, when the amount is less than 5 parts by mass, the refractive index is not high, which is not preferable.

The high refractive index metal oxide sol is preferably higher than the cured product refractive index of the cured layer and has a refractive index of 1.6 or more in terms of increasing the refractive index of the high refractive index cured product layer. In this case, a metal oxide sol containing at least an atom selected from Ti, Sn, Ce, Al, Zn, In, and Fe is preferable. Specific examples include ZnO (n = 1.90), TiO ₂ ( n = 2.3-2.7), Sb ₂ O ₅ (n = 1.71), Y ₂ O ₃ (n = 1.87), La ₂ O ₃ (n = 1.95), ZrO ₂ ( n = 2.05), Al ₂ O ₃ (n = 1.63), metal oxides such as ITO (n = 1.95) which is a mixed oxide of In and Sn, and composite oxidation containing these components A high refractive index metal oxide sol made of a material is preferred.

In addition, metal oxide sols such as In ₂ O ₃ , SnO ₂ , CeO ₂ , and Fe ₂ O ₃ can also be used. In particular, it is preferable to use those containing Ti atoms that have a high refractive index. These high-refractive-index metal oxide sols are modified with a silane compound, a silane coupling agent containing an organic functional group, a titanium coupling agent, an organic functional group-containing acrylic polymer or the like in order to improve dispersion stability. It may be done.

  Examples of the dispersion medium for dispersing the high refractive index metal oxide sol include water, alcohols such as methanol and ethanol, esters such as ethyl acetate and butyl acetate, ethers such as propylene glycol monomethyl ether, methyl ethyl ketone and methyl isobutyl ketone. These ketones can be applied.

  As the curable resin for forming the high refractive index cured layer, a conventionally known thermoplastic resin and / or moisture curable, thermosetting, or photocurable organic resin or silicone resin can be applied. . Examples of moisture curable, thermosetting, or photocurable resins include thermosetting acrylic resins, moisture curable acrylic resins, thermoplastic acrylic resins, UV / EB curable acrylic resins, acrylic resins modified with silane and siloxane, Examples include urethane resins, UV / EB curable epoxy resins, thermosetting silicone resins, moisture curable silicone resins, and UV / EB curable silicone resins. In particular, a silicone resin obtained by hydrolyzing or further (partially) condensing various hydrolyzable silane compounds has a high hardness of the resulting film and is excellent in adhesion to the antireflection film according to the present invention. preferable. Further, UV curable acrylic resin, epoxy resin, or silicone resin is also preferable from the viewpoint of high productivity and excellent adhesion of the resulting film.

  In a system in which polymerization is performed by irradiation with light / radiation such as ultraviolet rays and electron beams, it is preferable to add a photopolymerization initiator and perform photopolymerization. Examples of the photopolymerization initiator include aryl ketone photopolymerization initiators (for example, acetophenones, benzophenones, alkylaminobenzophenones, benzyls, benzoins, benzoin ethers, benzyl dimethyl ketals, benzoylbenzoates, α-acylose). Oxime esters), sulfur-containing photopolymerization initiators (eg, sulfides, thioxanthones, etc.), acylphosphine oxide photopolymerization initiators, and other photopolymerization initiators. The photopolymerization initiator can be used in combination with a photosensitizer such as amines. Specific examples of the photopolymerization initiator include the following compounds. 4-phenoxydichloroacetophenone, 4-t-butyldichloroacetophenone, 4-t-butyltrichloroacetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) ) -2-Hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl) -2-methylpropan-1-one, 1- {4- (2-hydroxyethoxy) phenyl} -2-hydroxy 2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- {4- (methylthio) phenyl} -2-morpholinopropan-1-one, benzyl, benzoin, benzoin methyl ether, benzoin Ethyl ether, benzoin isopropyl ether Benzoin isobutyl ether, benzyl dimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 3,3'-dimethyl-4-methoxybenzophenone, 3,3 ', 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 9,10-phenanthrenequinone, camphorquinone, dibenzosuberone, 2-ethylanthraquinone, 4 ′, 4 ″ -diethylisophthalophenone, α-acilo Ximeme ester, methyl phenylglyoxylate, 4-benzoyl-4'-methyldiphenyl sulfide, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, Sopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, benzoyldiphenylphosphine oxide, 2,6-dimethylbenzoyldiphenylphosphine Oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, and the like.

  The high refractive index curable composition may be used after diluted with a solvent. Examples of the solvent include methanol, ethanol, diacetone alcohol, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, isobutyl alcohol, isopropyl alcohol, n-butyl alcohol, and n-propyl alcohol. , Acetone, methyl ethyl ketone, methyl isobutyl ketone, acetyl acetone, ethyl acetoacetate, ethyl acetate, butyl acetate, xylene, toluene and the like.

  Furthermore, if necessary, a known additive used in a conventional coating agent, such as a leveling agent, may be blended.

  The film thickness of the cured film of the high refractive index layer to be formed must be a thin film according to the refractive index in order to maintain optical properties such as antireflection properties, but is usually 0.02 to 3 μm, preferably The thickness is set to 0.05 to 0.5 μm.

Next, a scratch-resistant protective layer that may be provided between the transparent substrate and the antireflection layer or between the transparent substrate and the high refractive index layer in order to obtain good scratch resistance will be described. This protective layer has excellent adhesion to various transparent substrates such as polycarbonate resin, polyalkylene terephthalate resin such as PET, cellulose resin such as triacetyl cellulose, acrylic resin, etc., and is a film having a certain thickness or more. When it is thick, it must exhibit good hardness. Thermoplastic acrylic resins, UV / EB curable acrylic resins, epoxy resins, or silicone resins containing organic functional groups such as acrylic groups and epoxy groups should be used as the protective layer. Then, the acrylic resin is preferable. Specific examples thereof include the following.
(A) a radiation-polymerizable composition, in particular, a layer obtained by radiation-polymerizing and curing a composition containing an organosilicon compound having a (meth) acryl functional group;
(B) a layer obtained by curing a composition containing an acrylic polymer, particularly a composition containing an acrylic polymer containing a hydrolyzable silyl group,
(C) A layer made of an acrylic polymer, particularly a thermoplastic acrylic resin that has excellent heat resistance and high hardness, and has methyl methacrylate as a main component as a copolymerization component.

  Furthermore, for the purpose of adjusting physical properties such as hardness, scratch resistance, and conductivity of the coating, silica, aluminum oxide, titanium oxide, zinc oxide, zirconium oxide, cerium oxide, tin oxide, indium oxide, or a composite thereof You may mix | blend inorganic oxide fine particles, such as an oxide. Of these, colloidal silica is particularly preferable. As these inorganic oxide fine particles, those whose surfaces are treated with an organometallic compound such as a silane-based, titanium-based, aluminum-based, or zirconium-based coupling agent may be used.

  When blending inorganic oxide fine particles, the addition amount is 0.1 to 80 parts by mass in terms of solid content per 100 parts by mass of the acrylic polymer containing the hydrolyzable silyl group, preferably 1 to 1 part by mass. 50 parts by mass. When the added amount of the inorganic oxide fine particles exceeds 80 parts by mass, the transparency of the cured film formed by the prepared composition tends to decrease.

  A normal ultraviolet absorber may be added to the protective layer for the purpose of suppressing photodegradation of the substrate. Inorganic ultraviolet absorbers such as titanium oxide fine particles and zinc oxide fine particles and the following organic ultraviolet absorbers are preferred. The organic ultraviolet absorber is preferably a compound derivative whose main skeleton is hydroxybenzophenone, benzotriazole, cyanoacrylate, or triazine. Furthermore, a polymer such as vinyl polymer containing these ultraviolet absorbers in the side chain may be used. Specifically, 2,4′-dihydroxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy-4-n-benzyloxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy Benzophenone, 2,2′-dihydroxy-4,4′-diethoxy-benzophenone, 2,2′-dihydroxy-4,4′-dipropoxybenzophenone, 2,2′-dihydroxy-4,4′-dibutoxybenzophenone, 2,2'-dihydroxy-4-methoxy-4'-propoxybenzof Non, 2,2′-dihydroxy-4-methoxy-4′-butoxybenzophenone, 2,3,4-trihydroxybenzophenone, 2- (2-hydroxy-5-tert-butylphenyl) benzotriazole, 2- (2 -Hydroxy-5-t-octylphenyl) benzotriazole, 2- (2-hydroxy-3,5-di-t-butylphenyl) benzotriazole, ethyl-2-cyano-3,3-diphenyl acrylate, 2-ethylhexyl 2-cyano-3,3-diphenyl acrylate, 2- (2-hydroxy-4-hexyloxyphenyl) -4,6-diphenyltriazine, 4- (2-acryloxyethoxy) -2-hydroxybenzophenone polymer 2- (2′-hydroxy-5′-methacryloxyethylphenyl) -2H-be Polymers, etc. Zotoriazoru are exemplified. Two or more of these organic ultraviolet absorbers may be used in combination.

  The thickness of the protective layer is not particularly limited as long as good scratch resistance is obtained, and may be in the range of 0.1 to 10 μm. If it is too thin, good scratch resistance cannot be obtained, and if it is too thick, cracks are likely to occur. More preferably, the range of 0.2 to 5 μm is satisfied.

  Hereinafter, although a synthesis example, an Example, and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. In addition, in the following example,% is mass%, a part is mass part, and the average molecular weight in this specification shows the number average molecular weight of polystyrene conversion by gel permeation chromatography (henceforth GPC).

[Synthesis Example 1]
In a 3 liter flask equipped with a stirrer, a condenser and a thermometer, 49.8 g (0.10 mol) of the following bissilane compound (A)-(1) and 56.8 g of the following fluorine-containing silane (B)-(1) ( 0.10 mol) and 400 g of t-butanol were added, and 18 g (1.0 mol) of 0.1N acetic acid aqueous solution was added dropwise over 10 minutes while stirring at 25 ° C.

Further, the mixture was stirred at 25 ° C. for 48 hours to complete the hydrolysis. Add 1 g of aluminum acetylacetonate as a condensation catalyst, 1 g of fluorosurfactant Fluorard FC-4430 as a leveling agent, 1,700 g of ethanol and 100 g of diacetone alcohol, and further stir for 30 minutes to give an antireflection coating agent. Solution (I) was obtained.
Content ratio of (B)-(1) = 53 mass%
[Content of (B)-(1)
= {(B)-(1) / ((A)-(1) + (B)-(1))} × 100]
F / Si = 8.3 (molar ratio)
Perfluoroalkyl group bonded to Si / all monovalent organic substituents bonded to Si = 100 mol%
_{(CH 3 O) 3 Si-} C 2 H 4 -C 4 F 8 -C 2 H 4 -Si (OCH 3) 3 (A) - (1)
_{(CH 3 O) 3 Si-} C 2 H 4 -C 8 F 17 (B) - (1)

[Synthesis Example 2]
In Synthesis Example 1, 59.8 g (0.10 mol) of the bissilane compound (A)-(2) was used instead of the bissilane compound (A)-(1), and the fluorine-containing silane (B)-(1) The amount was changed to 45.4 g (0.08 mol), and the same procedure was followed to obtain an antireflection coating solution (II).
Content ratio of (B)-(1) = 43% by mass
F / Si = 9.1 (molar ratio)
Perfluoroalkyl group bonded to Si / all monovalent organic substituents bonded to Si = 100 mol%
_{(CH 3 O) 3 Si-} C 2 H 4 -C 6 F 12 -C 2 H 4 -Si (OCH 3) 3 (A) - (2)

[Synthesis Example 3]
In Synthesis Example 1, the amount of the bissilane compound (A)-(1) is 39.8 g (0.08 mol) and the amount of the fluorine-containing silane (B)-(1) is 68.2 g (0.12 mol). Thereafter, the same procedure was followed to obtain an antireflection coating solution (III).
Content ratio of (B)-(1) = 63 mass%
F / Si = 9.6 (molar ratio)
Perfluoroalkyl group bonded to Si / all monovalent organic substituents bonded to Si = 100 mol%

[Synthesis Example 4]
In Synthesis Example 1, instead of fluorine-containing silane (B)-(1), 18.6 g (0.04 mol) of the following fluorine-containing silane (B)-(3) and fluorine-containing silane (B)-(2) An antireflection coating solution (IV) was obtained in the same manner using 46.1 g (0.06 mol) of the mixture.
Content ratio of ((B)-(2) + (B)-(3)) = 57 mass%
F / Si = 8.9 (molar ratio)
Perfluoroalkyl group bonded to Si / all monovalent organic substituents bonded to Si = 100 mol%
_{(CH 3 O) 3 Si-} C 2 H 4 -C 12 F 25 (B) - (2)
_{(CH 3 O) 3 Si-} C 2 H 4 -C 4 F 9 (B) - (3)

[Synthesis Example 5]
In Synthesis Example 1, in addition to various silane compounds, 1 g of a compound containing an end-capped diorganopolysiloxane chain (Si polymerization degree = 15) shown below was added, and the same was applied to the antireflection coating solution. (V) was obtained.
_{[(CH 3) 3 Si (} -O- (CH 3) 2 Si-) 9 -CH 2 CH 2 -] 0.07 Si (OCH 3) 0.78 O 1.58

[Synthesis Example 6] (Comparative Example)
In Synthesis Example 1, in addition to the various silane compounds, 4.2 g (0.02 mol) of tetraethoxysilane was further added, and the coating agent solution (VI) was prepared in the same manner.

[Synthesis Example 7] (Comparative Example)
In Synthesis Example 1, the bissilane compound (A)-(1) was changed to 79.7 g (0.16 mol) and the fluorine-containing silane (B)-(1) was changed to 22.7 g (0.04 mol). Thus, a coating solution (VII) was prepared.
Content ratio of (B)-(1) = 22% by mass
F / Si = 5.4 (molar ratio)
Perfluoroalkyl group bonded to Si / all monovalent organic substituents bonded to Si = 100 mol%

[Synthesis Example 8] (Comparative Example)
In Synthesis Example 1, the bissilane compound (A)-(1) was changed to 19.9 g (0.04 mol) and the fluorine-containing silane (B)-(1) was changed to 90.9 g (0.16 mol). Thus, a coating solution (VIII) was prepared.
Content ratio of (B)-(1) = 82 mass%
F / Si = 12.7 (molar ratio)
Perfluoroalkyl group bonded to Si / all monovalent organic substituents bonded to Si = 100 mol%

[Synthesis Example 9]
In a 2 liter flask equipped with a stirrer, a condenser and a thermometer, 236.3 g (1.00 mol) of γ-glycidoxypropyltrimethoxysilane and 74.5 g (0.30) of γ-glycidoxypropyldiethoxysilane were added. Mol) 700 g of methanol-dispersed sol having a primary particle diameter of 20 nm and a mass composition ratio of TiO ₂ / ZrO ₂ / SiO ₂ = 85/3/12 with an active ingredient amount of 30% is being stirred at room temperature. 70 g of 0.1N acetic acid was added dropwise over 1 hour. Further, the mixture was stirred at room temperature for 5 hours to complete the hydrolysis. Thereto was added 150 g of diacetone alcohol, 2 g of aluminum acetylacetonate as a condensation catalyst, and 2 g of polyether-modified silicone as a leveling agent, and the mixture was further stirred for 30 minutes to prepare a silicone solution containing a high refractive index sol. To 100 g of this solution, 600 g of ethanol was added to prepare a thermosetting high refractive index layer forming coating agent (K).

[Synthesis Example 10]
In a 1-liter flask equipped with a stirrer, a condenser and a thermometer, 82.0 g (0.35 mol) of γ-acryloxypropyltrimethoxysilane and 32.7 g (0.15 mol) of γ-acryloxypropylmethyldimethoxysilane. Then, 104.2 g (0.50 mol) of tetraethoxysilane and 50 g of isobutanol were charged, and 65 g of 0.1N aqueous acetic acid was added dropwise over 1 hour while stirring at 10 ° C. Further, the mixture was stirred at room temperature for 5 hours to complete the hydrolysis. Thereto was added 150 g of diacetone alcohol, 1 g of aluminum acetylacetonate as a condensation catalyst, and 1 g of polyether-modified silicone as a leveling agent, and the mixture was further stirred for 30 minutes to prepare a silicone solution (L) containing an acrylic functional group.
100 g of the silicone solution thus obtained was mixed with 50 g of trimethylolpropane triacrylate as a polyfunctional acrylic component, 50 g of propylene glycol monomethyl ether, and 1 g of 2-hydroxy-2-methyl-1-phenylpropan-1-one as a photoinitiator. Added and stirred. Thereby, a UV curable protective coating solution (M) was obtained.

[Synthesis Example 11]
Methanol-dispersed sol having a primary particle size of 20 nm and a mass composition ratio of TiO ₂ / ZrO ₂ / SiO ₂ = 85/3/12 and an active ingredient amount of 30% in 100 g of an acrylic functional group-containing silicone solution (L) 80 g, 10 g of trimethylolpropane triacrylate, 1 g of aluminum acetylacetonate as a condensation catalyst, 1 g of polyether-modified silicone as a leveling agent, and 2-hydroxy-2-methyl-1-phenylpropane-1-one as a photoinitiator 1 g was added and stirred at room temperature. To 100 g of the solution thus obtained, 500 g of ethanol was added for dilution to prepare a UV curable high refractive index layer forming coating agent (N).

[Synthesis Example 12]
A 1 liter flask equipped with a stirrer, a condenser and a thermometer was charged with 24.8 g (0.10 mol) of γ-methacryloxypropyltrimethoxysilane and 450 g of isopropanol, and water-dispersed colloidal silica (active ingredient = 20%). 300 g was added dropwise. 0.1g of tetramethylammonium hydroxide was added here, and it heat-stirred at 50 degreeC for 3 hours. By this method, a silica sol surface-treated with a methacryl functional silane was obtained.
To 100 g of this surface-treated silica sol, 40 g of a silicone solution (L) containing an acrylic functional group, 40 g of trimethylolpropane triacrylate, 20 g of hexamethylenediol diacrylate, 2-hydroxy-2-methyl-1-phenylpropane-1- 1 g of ON was added and stirred. Thus, a UV curable protective coating solution (P) was prepared.

[Synthesis Example 13]
A 1 liter flask equipped with a stirrer, a condenser and a thermometer was charged with 330 g of a 2: 1 mixed solvent of diacetone alcohol and methyl isobutyl ketone, and the temperature was raised to 80 ° C. In the above-mentioned solvent heated and stirred under a nitrogen atmosphere, 24.8 g (0.10 mol) of γ-methacryloxypropyltrimethoxysilane, 180 g (1.80 mol) of methyl methacrylate, 14.2 g (0.2 mol of glycidyl methacrylate). 10 mol) and 2 g of azobisisobutyronitrile were added dropwise over 30 minutes. Further, the mixture was heated and stirred at 80 ° C. for 5 hours. An acrylic polymer solution containing a hydrolyzable silyl group containing an acrylic polymer having a number average molecular weight of 125,000 was obtained.
Separately, 60 g of 0.1N aqueous acetic acid was added dropwise at room temperature over 30 minutes to a solution in which 136 g (1.00 mol) of methyltrimethoxysilane and 72 g of isopropanol were mixed. After completion of dropping, 200 g of the above acrylic polymer solution, 0.1 g of sodium formate as a condensation catalyst, 10 g of acetic acid, and 1 g of polyether-modified silicone as a leveling agent are added to this solution, and mixed with stirring. A curable protective coating solution (Q) was prepared.

[Synthesis Example 14]
In the same manner as in Synthesis Example 13, 24.8 g (0.10 mol) of γ-methacryloxypropyltrimethoxysilane, 160 g (1.60 mol) of methyl methacrylate, 2- (2′-hydroxy) with respect to 370 g of the mixed solvent. -5'-methacryloxyethylphenyl) -2H-benzotriazole 64.6 g (0.20 mol) and 2 g of azobisisobutyronitrile are added dropwise to contain an acrylic polymer having a number average molecular weight of 103,000. A solution was obtained.
100 g of this solution was subjected to a ring-opening reaction of 1.00 mol of γ-aminoethyl-aminopropyltrimethoxysilane and 2.00 mol of γ-glycidoxypropyldimethoxysilane in the presence of 3.00 mol of hexamethyldisilazane, Further, 10 g of MIBK (methyl isobutyl ketone) solution containing 20% of an adhesion improver reacted with 2.00 mol of acetic anhydride was added to prepare a moisture curing type protective coating solution (R).

[Synthesis Example 15]
Add 3 g of 2,4-dihydroxybenzophenone and 150 g of diacetone alcohol to 100 g of a propylene glycol monomethyl ether acetate solution containing 30% of a polymethyl methacrylate resin having a number average molecular weight of 200,000, and stir until dissolved. A protective coating solution (S) was prepared.

Hereinafter, the present invention will be described in more detail with reference to examples. In addition, various physical properties in the examples were measured and evaluated by the following methods.
Scratch resistance test:
(Method-1)
Steel wool # 0000 was attached to a reciprocating scratch tester (manufactured by KT Corporation), and the number of scratches after 10 reciprocations was measured under a load of 100 g / cm ² .
<Level of evaluation>
◎: 0 ◯: 1 to 2 △: 3 to 5 ×: 6 or more (Method-2)
In Method-1, flannel cloth was attached instead of steel wool, and the number of scratches after reciprocating 1,000 times under the condition of 1 kg load was measured.
○: No scratch △: Cloudy ×: Peeling

Hardened film adhesion:
In accordance with JIS K5400, make a sample with 100 razors by cutting 11 samples at 1 mm intervals vertically and horizontally with a razor blade, and after making close contact with commercially available cello tape (registered trademark), suddenly 90 degrees forward When the film was peeled off, the number of squares (X) remaining without peeling off the film was indicated by X / 100.
Refractive index:
The refractive index of the film was measured with a prism coupler (manufactured by Seki Technotron Co., Ltd.).
Anti-reflective properties:
The antireflection property was confirmed by visual observation. Good ones are indicated by “◯”.
chemical resistance:
One drop of the following drug was dropped on the film, left for 30 minutes, the drug was removed, and the surface condition was visually observed.
<Level of evaluation>
○: No change △: Trace remains *: Film dissolution

The alkali resistance was confirmed using two levels of a 0.1N (0.4%) aqueous NaOH solution and a 1% aqueous NaOH solution.
Painting method:
The transparent resin plate has a thickness of 0.5 mm, a size of 10 cm × 10 cm, a PC (polycarbonate) resin and an acrylic resin,
As the film, a PET film having a thickness of 50 μm and a size of 10 cm × 10 cm was used.
Painting method:
It applied to the transparent resin board or film which cleaned the surface using a bar coater so that it may become a predetermined film thickness, or it apply | coated by the immersion method.
(1) In the case of single coating The cured film was coated so that the film thickness was 2 to 3 μm.
(2) When laminated in multiple layers Protective layer → 3 to 5 μm thick cured film High refractive index layer → 0.1 to 0.3 μm thick cured film Low refractive index layer → 0.1 to 0.3 μm thick Cured film curing conditions:
(1) When heat-curing After applying the solution, the solvent was volatilized by air-drying, and kept in a hot-air circulating oven at 80 to 120 ° C. for 5 to 30 minutes for curing.
(2) In case of UV curing 200 mJ / cm ² was repeatedly irradiated 3 times using a high pressure mercury lamp to be cured. When laminating each layer, the upper layer was applied and cured after the underlying layer was cured.

[ Reference Examples 1-3]
(N) or (Q) was coated and cured on the acrylic plate and the PC plate as a protective layer coating solution. On this cured film, the antireflection coating solutions (I), (II), and (III) were applied and cured. The characteristics of the coating film thus obtained were examined.

  As shown in the following table, the film obtained from the antireflection film according to the present invention had good scratch resistance and chemical resistance, and the refractive index of the film was 1.400 or less.

* Household detergent, manufactured by Kao Corporation ** Skin protectant, manufactured by Kao Corporation *** Household detergent, manufactured by Johnson Corporation

[Example 1, Reference Examples 4-7 , Comparative Examples 1-3]
On the PET film, a protective layer coating solution, a high refractive index coating agent, and an antireflection coating solution were sequentially applied and cured to prepare a laminate, and the coating properties of this laminate were confirmed.

  As shown in the following table, the film obtained by the antireflection coating agent according to the present invention had good scratch resistance and chemical resistance, and also excellent antireflection properties.

Claims (10)

(1) a bissilane compound (A) and / or its (partial) hydrolyzate and / or its condensate;
_{X m R 3-m Si-} C 2 H 4 (CF 2) n C 2 H 4 -SiR 3-m X m (A)
(Wherein R is the same or different monovalent hydrocarbon group selected from an alkyl group having 1 to 6 carbon atoms and a phenyl group, X is an OH group, a halogen atom, an alkoxy group having 1 to 4 carbon atoms, acyloxy A group, an alkenoxy group, a ketoxime group, an alkoxyalkoxy group or an —NCO group, m is 2 or 3, and n is 4 or 6.)
(2) Organosilicon compound (B) containing a perfluoroalkyl group and / or its (partial) hydrolyzate and / or its condensate F (CF ₂ ) _a C ₂ H ₄ —SiR _3-b X _b ( B)
(In the formula, R and X have the same meanings as described above, a is 4, 6, 8, 10 or 12, and b is 2 or 3.)
Or a mixture of components (1) and (2) that is co- (partially) hydrolyzed / condensed as a main component, with respect to the total mass of components (1) and (2), content of 42-70% by mass of 2) is, further, (3) an organosilicon compound represented by the following average composition formula (C)
[R ₃ Si— (O—R ₂ Si—) _c —Y—] _p R _q SiX _r O _{(4-pqr) / 2} (C)
(In the formula, R and X have the same meanings as described above, Y is —O— or an alkylene group having 2 to 10 carbon atoms, and 0.01 ≦ p <1, 0 ≦ q <1, 0.5. ≦ r <3, 1 <p + q + r <4, c is 1 to 100)
An antireflection film-forming coating agent composition having excellent alkali resistance, characterized by comprising Further, the silicon-based or fluorine-based surfactant characterized in that the addition of claim 1 for forming an antireflective film coating composition. Alkyl silicates, epoxy functional silanes, (meth) acryl functional silanes, mercapto functional silanes, amino functional silanes and their (partial) hydrolysates, mixtures of organosilicon compounds of components (1) and (2) The coating composition for forming an antireflective film according to claim 1 or 2 , wherein the composition is not contained in 1% by mass or more in or in a co- (partial) hydrolysis / condensate thereof. The coating agent composition for forming an antireflection film excellent in alkali resistance according to any one of claims 1 to 3 , wherein the solvent is contained in an amount of 50 to 99% by mass in the coating agent composition. The coated optical article which formed in the outermost layer of the synthetic resin transparent base material the cured film of the coating agent composition for antireflection film formation of any one of Claims 1 thru | or 4 as an antireflection film. 6. The coated optical article according to claim 5, wherein a coating film and / or a scratch-resistant protective layer having a higher refractive index than the base material is provided between the synthetic resin transparent base material and the antireflection film. 7. The coated optical article according to claim 6, wherein the high refractive index film contains a metal oxide sol containing atoms selected from at least Ti, Sn, Ce, Al, Zr, In, and Fe. Synthetic resin, polycarbonate resin, polyalkylene terephthalate resin, either an acrylic resin, triacetyl cellulose resin, polystyrene resin, according to claim 5 to 7, characterized in that those selected from the polyolefin resin The coated optical article according to claim 1. The coated optical article according to any one of claims 5 to 8 , wherein the transparent substrate is in the form of a film or a plate. A multilayer laminate comprising a coated optical article according to any one of claims 5 to 9 further provided with a pressure-sensitive adhesive or adhesive layer on the transparent substrate side, and a release film further laminated thereon.