JP2010085502A - Anti-reflection film, polarizing plate, and image display device - Google Patents

Abstract

[Ｒｆは炭素原子とフッ素原子または炭素原子とフッ素原子と酸素原子のみから構成されるa価の有機基を表し、Ａは単結合または一般式（ＩＩ）で表される２価の連結基を表し、Ｑは重合性基または水素原子を表し、aは３から２０の整数を表し、b、cはそれぞれ独立に０〜１００の整数を表す。但し、a個のＱのうち少なくとも２つは重合性基である。該重合性含フッ素化合物中の重合性基を重合させたとき、各架橋間分子量の計算値の少なくとも一つが３００より大きい。]
（Ｂ）フッ素を含有しない多官能モノマー
（Ｃ）光重合開始剤
を含有する組成物から形成される反射防止フィルム。
【選択図】なしAn antireflection film having a low refractive index layer having a sufficiently low refractive index and excellent scratch resistance is provided.
An antireflection film having a low refractive index layer on a transparent support, the low refractive index layer comprising:
(A) Polymerizable fluorine-containing compound represented by the general formula (I)

[Rf represents a valent organic group composed of only carbon atoms and fluorine atoms or carbon atoms, fluorine atoms and oxygen atoms, and A represents a single bond or a divalent linking group represented by formula (II). Q represents a polymerizable group or a hydrogen atom, a represents an integer of 3 to 20, and b and c each independently represents an integer of 0 to 100. However, at least two of a Q are polymerizable groups. When the polymerizable group in the polymerizable fluorine-containing compound is polymerized, at least one of the calculated values of the molecular weight between crosslinks is larger than 300. ]
(B) An antireflection film formed from a composition containing a polyfunctional monomer not containing fluorine (C) a photopolymerization initiator.
[Selection figure] None

Description

  The present invention relates to an antireflection film, a polarizing plate using the antireflection film, and an image display device using the antireflection film or the polarizing plate on the outermost surface of a display.

  In general, an antireflection film is used for an image display device such as a cathode ray tube display (CRT), a plasma display (PDP), an electroluminescence display (ELD), and a liquid crystal display (LCD). In order to prevent image reflection, it is placed on the top surface of the display to reduce reflectivity using the principle of optical interference.

  Such an antireflection film can be generally produced by forming a low refractive index layer having an appropriate film thickness having a lower refractive index than that of the support on the support. In order to realize a low reflectance, it is desirable to use a material having a refractive index as low as possible for the low refractive index layer.

  Moreover, since an antireflection film is used for the outermost surface of a display, high scratch resistance is required. In order to realize high scratch resistance in a thin film having a thickness of around 100 nm, the strength of the coating itself and the adhesion to the lower layer are required.

  In order to lower the refractive index of the material, it has been known so far to use a fluorine-based compound or a silicon-based compound. However, although the fluorine-based compound has a low refractive index and excellent transparency and chemical resistance, there is a problem that it is difficult to form a coating film excellent in scratch resistance. For this purpose, a means using a fluorine-containing crosslinkable material has been proposed (Patent Document 1).

  On the other hand, silicon-based compounds have a problem of low resistance to chemicals such as acids and alkalis, although they are superior in scratch resistance compared to fluorine-based compounds. From this, it was very difficult to obtain a coating film excellent in scratch resistance, chemical resistance, transparency and the like.

In order to form a film having a low refractive index and excellent scratch resistance, a fluorine-containing polyfunctional monomer having a high fluorine content and a small molecular weight between crosslinkable groups having a plurality of polymerizable groups has been proposed (Patent Document 2).
However, in this case, if the molecular weight between the cross-linking groups is reduced, the hardness of the coating is increased, but the fluorine content is in the direction of decreasing, and the effect of lowering the refractive index is insufficient.

Further, a compound similar to the compound that can be used in the present invention has been proposed as a fluorine-based compound that can be usefully used as a lubricant, a surfactant, and a water / oil repellent material (Patent Document 3).
However, these compounds are not satisfactory in scratch resistance, and improvement has been desired.

JP 2003-222702 A JP 2006-28409 A JP-T-2006-45159

  The present invention provides an antireflection film having a low refractive index layer having a high fluorine content, a sufficiently low refractive index and excellent scratch resistance, and a polarizing plate and an image display device using the same. is there.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the following configuration can solve the problems and achieve the object, and the present invention has been completed.

1. An antireflection film having at least one low refractive index layer on a transparent support, the low refractive index layer comprising:
(A) Polymerizable fluorine-containing compound represented by the following general formula (I)

[In the formula, Rf represents an a-valent organic group substantially composed of carbon atoms and fluorine atoms or only carbon atoms, fluorine atoms and oxygen atoms, and A represents a single bond or a general formula (II). Represents a divalent linking group, Q represents a polymerizable group or a hydrogen atom, a represents an integer of 3 to 20, and b and c each independently represents an integer of 0 to 100. However, at least two of a Q are polymerizable groups. In addition, the compound represented by the general formula (I) is a compound in which at least one of the calculated values of the molecular weight between crosslinks is larger than 300 when the polymerizable group in the polymerizable fluorine-containing compound is polymerized. ]
An antireflection film formed from a coating composition containing (B) a polyfunctional monomer containing no fluorine and (C) a photopolymerization initiator.
2. In the general formula (I), Q is —COC (R ₀ ) ═CH ₂ , an allyl group, an epoxyalkylene group, — (CH ₂ ) _x Si (W) ₃ , — (CH ₂ ) _y NCO or — (CH ₂ ) _z CN (wherein R ₀ represents a hydrogen atom, a halogen atom or an alkyl group which may have a substituent. W represents an alkoxy group or a hydroxyl group. X, y and z each represents one or more. 2. The antireflection film as described in 1 above, wherein the three Ws may be different from each other.
3. In the above general formula (I), Q is —COC (R) ═CH ₂ (wherein R represents a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group). Antireflection film.
4. The antireflection film as described in any one of 1 to 3, wherein a is an integer of 3 to 6.
5. The antireflection film as described in any one of 1 to 3 above, wherein b and c are 0.
6. In the general formula (I), Q is —COC (R) ═CH ₂ (wherein R represents a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group), and a is an integer of 3 to 6 3. The antireflection film as described in 1 or 2 above, wherein b and c are 0.
7. The antireflection film according to any one of 1 to 6, wherein the polyfunctional monomer (B) containing no fluorine is a polyfunctional (meth) acrylate having three or more functional groups.
8. The antireflection film as described in any one of 1 to 7, wherein the coating composition further contains (D) inorganic fine particles.
9. The average particle diameter of the (D) inorganic fine particles is 20 nm or more and 100 nm or less, and the proportion of the (D) inorganic oxide fine particles is 10 to 70 mass% with respect to the total solid content in the coating composition. 9. The antireflection film as described in 8 above.
10. The antireflection film as described in 8 or 9 above, wherein the inorganic fine particles (D) are surface-treated with a hydrolyzate of an organosilane compound and / or a partial condensate thereof.
11. The antireflection film as described in any one of 8 to 10 above, wherein at least one of the (D) inorganic fine particles is a particle having pores therein.
12. The polymerizable fluorine-containing compound has 3 or more carbon atoms substituted with at least one of an oxygen atom, a carbon atom, and a silicon atom in the molecule (however, all are substituted with a single bond) ) The antireflection film as described in any one of 1 to 11 above.
13. The antireflection film according to any one of 1 to 12, wherein the polyfunctional monomer (B) containing no fluorine contains an organosilane compound having an unsaturated double bond.
14. The antireflection film as described in any one of 1 to 13 above, wherein the fluorine content of the polymerizable fluorine-containing compound (A) is 40.0% by mass or more of the molecular weight of the polymerizable fluorine-containing compound.
15. When the total amount of the (A) polymerizable fluorine-containing compound and (B) the polyfunctional monomer not containing fluorine is 100 parts by mass, the content of the (A) polymerizable fluorine-containing compound is 30 to 80 parts by mass. The antireflection film according to any one of 1 to 14 above.
16. The polarizing plate in which the antireflection film according to any one of 1 to 15 is used for at least one of the two protective films of the polarizing film in the polarizing plate.
17. An image display device in which the antireflection film according to any one of 1 to 15 or the polarizing plate according to 16 is used on the outermost surface of a display.

  According to the present invention, an antireflection film having a low refractive index layer having a high fluorine content, a sufficiently low refractive index, and excellent scratch resistance, a polarizing plate and an image display device using the same Provided.

The present invention will be described in detail below.
The polymerizable fluorine-containing compound represented by the general formula (I) of the present invention will be described.

Rf represents an a-valent organic group consisting essentially of carbon atoms and fluorine atoms or carbon atoms, fluorine atoms and oxygen atoms, and A represents a single bond or a divalent linkage represented by the general formula (II). Q represents a polymerizable group or a hydrogen atom, a represents an integer of 3 to 20, and b and c each independently represents an integer of 0 to 100. However, at least two of a Q are polymerizable groups.
The term “substantially composed only of carbon atoms and fluorine atoms or carbon atoms, fluorine atoms and oxygen atoms” means that the proportion of subcomponents containing hydrogen atoms is 10 mol% or less, preferably 5 mol% or less. Preferably, it means 1 mol% or less.
In addition, the compound represented by the general formula (I) is a compound in which at least one of the calculated values of the molecular weight between crosslinks is larger than 300 when the polymerizable group in the polymerizable fluorine-containing compound is polymerized. Here, the calculated value of the molecular weight between crosslinks is a polymer in which all the polymerizable groups of the polymerizable fluorine-containing compound (hereinafter also referred to as fluorine-containing polyfunctional monomer) are polymerized, and in total 3 or more carbon atoms and / or When (a) represents a carbon atom substituted with a silicon atom, and (b) represents a silicon atom substituted with three or more carbon atoms and / or oxygen atoms, (a), (a), (b) and (B) or the total atomic weight of the atomic group sandwiched between (a) and (b).

  For example, F-1 will be described as an example among the fluorine-containing polyfunctional monomers described later. Assuming that all the polymerizable groups of F-1 are polymerized, it is expressed as in formula (A).

In this case, the partial structure that is the target of calculation of the molecular weight between crosslinks defined above is a portion surrounded by a broken line in formula (A), and the calculated value of the molecular weight between crosslinks is C ₁₅ H ₆ F ₁₇ O _9. = 653.0, which is greater than 300.
Rf has preferably 1 to 100 carbon atoms, more preferably 3 to 50 carbon atoms, and still more preferably 6 to 30 carbon atoms. a preferably represents an integer of 3 to 6, b and c preferably represent an integer of 0 to 10, more preferably 0 or 1, and particularly preferably 0.

The polymerizable group represented by Q is preferably a radical, a cation, or a condensation polymerizable group, and —COC (R ₀ ) ═CH ₂ , an allyl group, an epoxyalkylene group (preferably an epoxymethylene group), More preferably, it is — (CH ₂ ) _X Si (W) ₃ , — (CH ₂ ) _y NCO or — (CH ₂ ) _z CN. Here, R ₀ represents a hydrogen atom, a halogen atom or an alkyl group which may have a substituent, W represents an alkoxy group or a hydroxyl group, x, y and z each represents an integer of 1 or more, W may be different from each other. Each of x, y, and z is preferably 1 to 5, and more preferably 1 to 3. The substituent for the alkyl group in R ₀ may be any substituent, but is preferably a halogen atom. R ₀ is preferably a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group. The a Qs may be the same or different, but are preferably the same. Moreover, it is preferable that 3 or more of a Q is a polymerizable group.

  More preferred embodiments of the polymerizable fluorine-containing compound represented by the general formula (I) are those represented by the following general formulas (I-1), (I-2) and (I-3).

In the formula, Rf ₁ represents an oxygen atom, or a d-valent organic group substantially composed of only a carbon atom and a fluorine atom or a carbon atom, a fluorine atom and an oxygen atom, and Rf ₂ represents an oxygen atom or a substantial substance. Represents an e-valent organic group composed of only carbon atoms and fluorine atoms or carbon atoms, fluorine atoms and oxygen atoms, and Lf represents CF ₂ CF ₂ CH ₂ O or CF ₂ CH ₂ O (both are on the carbon atom side). And A and Q are as defined above, d and e each independently represent an integer of 2 or more, and f represents an integer of 1 or more. Rf ₁ and Rf ₂ preferably have 0 to 30 carbon atoms, and more preferably 0 to 10 carbon atoms.

  Further preferred embodiments of the compounds represented by the above general formulas (I-1), (I-2) and (I-3) include the following general formulas (I-1 ′), (I-2 ′) and ( I-3 ′).

In the formula, Rf ₁ ′ represents an oxygen atom, or a d′-valent organic group substantially composed of only a carbon atom and a fluorine atom or a carbon atom, a fluorine atom and an oxygen atom, and Rf ₂ ′ represents an oxygen atom, Or, it represents an e′-valent organic group substantially composed of only carbon atoms and fluorine atoms or carbon atoms, fluorine atoms and oxygen atoms, R represents the same meaning as described above, and d ′ and e ′ each independently The integer of 2 or 3 is represented, f 'represents the integer of 1-4. Rf ₁ ′ and Rf ₂ ′ preferably have 0 to 30 carbon atoms, and more preferably 0 to 10 carbon atoms.

  Specific examples of the polymerizable fluorine-containing compound represented by the general formula (I) of the present invention are shown below, but the present invention is not limited thereto.

Although the manufacturing method of the polymeric fluorine-containing compound represented by general formula (I) of this invention is not specifically limited, For example, it can manufacture by the combination of the following well-known methods. In the following description, the above-mentioned symbols have the same meaning as described above unless otherwise specified.
Step 1: A liquid represented by Rh (CO ₂ R ₁ ) a or Rh (CH ₂ OCOR ₂ ) a described in US Pat. No. 5,093,432 and International Publication No. 00/56694 A step of obtaining methyl ester Rf (CO ₂ CH ₃ ) a by phase fluorination reaction and subsequent reaction with methanol. (Wherein R ₁ represents a lower alkyl group such as a methyl group or an ethyl group, R ₂ represents an alkyl group, preferably a fluorinated alkyl group, more preferably a perfluoroalkyl group, and Rh represents a liquid phase fluorination reaction. Represents a group that can be Rf.)

Step 2: A step of reducing the compound represented by Rf (CO ₂ CH ₃ ) a with a reducing agent such as lithium aluminum hydride or sodium borohydride to obtain alcohol Rf (CH ₂ OH) a.
Step 3: One or more kinds selected from ethylene carbonate or ethylene oxide and glycidyl alcohol are added to the compound represented by Rf (CH ₂ OH) a in a block or random manner to add the alcohol to Rf (CH ₂ O-A -H) a obtaining step. If b = c = 0, this step is not necessary.

Step 4: A polymerizable group is introduced into a compound represented by Rf (CH ₂ O—A—H) a to obtain a compound Rf (CH ₂ O—AQ) a represented by the general formula (I). Process. Here, when Q is _{-COC (R 0) = CH 2} , as the polymerizable group introduction reaction, the alcohol _{Rf (CH 2 O-A-} H) a and acid halide _{XCOC (R 0) = CH 2} (X Represents a halogen atom, and preferably represents a chlorine atom), and dehydration condensation with carboxylic acid HOCOC (R ₀ ) ═CH ₂ can be used. When Q is other polymerizable group, a nucleophilic substitution reaction between the alcohol Rf (CH ₂ O—A—H) a and the corresponding halide compound can be used.

Next, a specific method for synthesizing the polymerizable fluorine-containing compound represented by the general formula (I) of the present invention will be described.
The compound represented by Compound Example F-1 was synthesized by the following route.

(Synthesis of Compound 3)
A known 1 (36.6 g, 145.6 mmol) / methanol (4 ml) solution of literature [eg, Journal of American Chemical Society 70, 214 (1948)] was added dropwise to concentrated hydrochloric acid (110 ml) at 50 ° C. over 1 hour. The reaction mixture was stirred at 65 ° C. for 6 hours, cooled to 35 ° C., methanol (80 ml) was added, and the mixture was further stirred at that temperature for 5 hours. The reaction solution was extracted with toluene (150 ml) / 10 wt% brine (100 ml), and the organic layer was concentrated under reduced pressure. Methanol (40 ml) and concentrated hydrochloric acid (1 ml) were added to the concentrated residue, and the mixture was stirred at room temperature for 4 hours. The reaction solution was extracted with toluene (150 ml) /7.5 wt% sodium bicarbonate water (150 ml), and the organic layer was washed with 25 wt% brine (150 ml) and dried over sodium sulfate. After the solvent was distilled off under reduced pressure, the residue was purified by column chromatography (developing solvent: ethyl acetate / hexane = 1/3) to obtain Compound 3 (40.8 g, 116.5 mmol, 80%).

(Synthesis of Compound 4)
A 1L Teflon (registered trademark) container equipped with a raw material supply port, a fluorine supply port, a helium gas supply port, and an exhaust port connected to a fluorine trap via a reflux device cooled with dry ice is charged with a chlorofluorocarbon solvent ( 750 ml) and helium gas was blown in at an internal temperature of 30 ° C. for 30 minutes at a flow rate of 100 ml / min. Subsequently, 20% F ₂ / N ₂ gas was blown at 100 ml / min for 30 minutes, the fluorine flow rate was changed to 200 ml / min, and a mixed solution of compound 3 (15 g, 42.8 mmol) and hexafluorobenzene (4.0 ml) was added. Added at 1 ml / h. The fluorine flow rate was lowered to 100 ml / min, hexafluorobenzene (1.2 ml) was added at 0.6 ml / h, and 20% F ₂ / N ₂ gas was further allowed to flow at 100 ml / min for 15 minutes. After replacing the reactor with helium gas, methanol (100 ml) was added and stirred for 1 hour, and then the solvent was distilled off under reduced pressure. The concentrated residue was washed with an ether / aqueous sodium bicarbonate solution, and the ether layer was dried over magnesium sulfate. After the ether was distilled off, the residue was purified by distillation at 2 mmHg to obtain Compound 4 (17.4 g, 26.5 mmol, 62%).

(Synthesis of Compound 5)
Lithium aluminum hydride (3.5 g) was dispersed in diethyl ether (300 ml), and a solution of compound 4 (10 g, 15.2 mmol) in diethyl ether (100 ml) was added dropwise at a temperature of 10 ° C. or lower. The reaction solution was stirred at room temperature for 6 hours, and ethyl acetate (100 ml) was slowly added dropwise. This solution was slowly poured into dilute hydrochloric acid / ice / ethyl acetate, and insolubles were filtered off. The organic layer was washed with water and brine, dried over magnesium sulfate and concentrated under reduced pressure. The residue was purified by column chromatography (developing solvent: ethyl acetate / hexane = 1/1) to obtain Compound 5 (8.0 g, 14.0 mmol, 92%) as a viscous oil.

(Synthesis of Compound F-1)
Acrylic acid chloride (2.7 ml) was added dropwise to a solution of compound 5 (5.7 g, 10 mmol) and potassium carbonate (9.0 g) in acetonitrile (120 ml) at a temperature of 10 ° C. or lower. The reaction mixture was stirred at room temperature for 5 hours, potassium carbonate (8 g) and acrylic acid chloride (2.5 ml) were added, and the mixture was further stirred for 20 hours. The reaction solution was poured into ethyl acetate (500 ml) / dilute aqueous hydrochloric acid (500 ml) and separated. The organic layer was washed with aqueous sodium hydrogen carbonate solution and brine, and purified by column chromatography (developing solvent: ethyl acetate / hexane = 1/3) to give compound F-1 (5.4 g, 74%).

  Other compound examples can be synthesized by the same method.

  The polymerizable fluorine-containing compound of the present invention is a fluorine-containing compound in which all calculated values of the molecular weight between crosslinks are larger than 300 when all the polymerizable groups of the fluorine-containing polyfunctional monomer are polymerized from the viewpoint of the crosslinking density and fluorine content. It is preferable to have a core portion Rf.

The calculated value of the molecular weight between crosslinks is preferably greater than 300 and not greater than 2000, more preferably greater than 300 and not greater than 1000, and even more preferably greater than 300 and not greater than 800. When the molecular weight between crosslinks is less than 300 when all the polymerizable groups of the polymerizable fluorine-containing compound are polymerized, the hardness of the coating film tends to increase, but the fluorine content decreases and the refractive index increases. . On the other hand, when the molecular weight between crosslinks is larger than 300, the hardness of the coating film tends to decrease, but the refractive index tends to decrease. Therefore, even if the molecular weight between crosslinks is more than 300, it is possible to achieve both high hardness and low refractive index by using a polyfunctional monomer not containing fluorine, preferably inorganic fine particles, in combination. When the molecular weight between cross-links exceeds 2000, the polyfunctional monomer that does not contain fluorine, preferably even when used in combination with inorganic fine particles, the hardness when it is made into a coating film is remarkably lowered, and further, the antifouling property and scratch resistance are deteriorated. To do.
Further, the polymerizable fluorine-containing compound preferably has 3 or more oxygen atoms and / or carbon atoms and / or carbon atoms substituted with silicon atoms in the molecule (excluding the carbonyl oxygen atom). It is more preferable that these are all substituted with a single bond. By containing the above carbon atoms, even when the molecular weight between crosslinks is larger than 300, a dense crosslink network structure can be constructed during curing, and the hardness of the coating film tends to increase.

  In the present invention, the fluorine content of the polymerizable fluorine-containing compound (A) is preferably 40.0% by mass or more of the molecular weight of the polymerizable fluorine-containing compound. More preferably, it is 45.0-70.0 mass%, Most preferably, it is 50.0-70.0 mass%. If it is this range, in the composition of this invention, the effect that low refractive index and the hardness of a coating film can be made compatible will be show | played, and it is preferable.

(B) Polyfunctional monomer not containing fluorine In the present invention, a polyfunctional monomer not containing fluorine is used as a curing agent in combination with the polymerizable fluorine-containing compound.

  The polyfunctional monomer containing no fluorine used in the present invention will be described. Examples of the monomer include compounds having a polymerizable functional group such as a (meth) acryloyl group, a vinyl group, a styryl group, and an allyl group, and among them, a (meth) acryloyl group is preferable. Particularly preferably, a compound containing two or more (meth) acryloyl groups in one molecule described below can be used. These compounds are particularly preferred because they have a large combined effect for improving scratch resistance or scratch resistance after chemical treatment, particularly when a compound having a polymerizable unsaturated group is used in the polymer body.

Specific examples of the component (B) include (meth) acrylic acid diesters of alkylene glycol such as neopentyl glycol acrylate, 1,6-hexanediol (meth) acrylate, and propylene glycol di (meth) acrylate;
(Meth) acrylic acid diesters of polyoxyalkylene glycols such as triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate;
(Meth) acrylic acid diesters of polyhydric alcohols such as pentaerythritol di (meth) acrylate;
(Meth) acrylic acid diesters of ethylene oxide or propylene oxide adducts such as 2,2-bis {4- (acryloxy · diethoxy) phenyl} propane and 2-bis {4- (acryloxy · polypropoxy) phenyl} propane ;
Etc.

  Furthermore, epoxy (meth) acrylates, urethane (meth) acrylates, and polyester (meth) acrylates are also preferably used as the photopolymerizable polyfunctional monomer.

  Among these, esters of polyhydric alcohol and (meth) acrylic acid are preferable. More preferably, a polyfunctional monomer having 3 or more (meth) acryloyl groups in one molecule is preferable, and one having 4 or more (meth) acryloyl groups in one molecule is most preferable. For example, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate, PO-modified trimethylolpropane tri (meth) acrylate, EO Modified tri (meth) acrylate phosphate, trimethylolethane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa ( (Meth) acrylate, pentaerythritol hexa (meth) acrylate, 1,2,3-chlorohexane tetramethacrylate, polyurethane polyacrylate Over DOO, polyester polyacrylate and caprolactone-modified tris (acryloyloxyethyl) isocyanurate.

  Specific compounds of polyfunctional acrylate compounds having a (meth) acryloyl group include KAYARAD DPHA, DPHA-2C, PET-30, TMPTA, TPA-320, and TPA- manufactured by Nippon Kayaku Co., Ltd. 330, RP-1040, T-1420, D-310, DPCA-20, DPCA-30, DPCA-60, GPO-303, Osaka Organic Chemical Industry Co., Ltd. V # 3PA, V Examples include esterified products of polyols such as # 400, V # 36095D, V # 1000, V # 1080, and (meth) acrylic acid. Also, purple light UV-1400B, UV-1700B, UV-6300B, UV-7550B, UV-7600B, UV-7605B, UV-7610B, UV-7620EA, UV-7630B, UV-7630B, UV-7640B. UV-6630B, UV-7000B, UV-7510B, UV-7461TE, UV-3000B, UV-3200B, UV-3210EA, UV-3210EA, UV-3310EA, UV-3310B, UV-3500BA , UV-3520TL, UV-3700B, UV-6100B, UV-6640B, UV-2000B, UV-2010B, UV-2250EA, UV-2750B (manufactured by Nippon Synthetic Chemical Co., Ltd.), UL-503LN (manufactured by Kyoeisha Chemical Co., Ltd.), Unidic 17-80 17-813, V-4030, V-4000BA (Dainippon Ink Chemical Co., Ltd.), EB-1290K, EB-220, EB-5129, EB-1830, EB-4858 (Daicel UCB ( Ltd.), High Corp AU-2010, AU-2020 (manufactured by Tokushi Co., Ltd.), Aronix M-1960 (manufactured by Toagosei Co., Ltd.), Art Resin UN-3320HA, UN-3320HC, UN-3320HS, UN -904, a trifunctional or higher urethane acrylate compound such as HDP-4T, 3 such as Aronix M-8100, M-8030, M-9050 (manufactured by Toagosei Co., Ltd., KRM-8307 (manufactured by Daicel Cytec Co., Ltd.)) A functional or higher polyester compound can also be suitably used.

  Furthermore, resins having three or more (meth) acryloyl groups, such as relatively low molecular weight polyester resins, polyether resins, acrylic resins, epoxy resins, urethane resins, alkyd resins, spiroacetal resins, polybutadiene resins, polythiol polyene resins And oligomers or prepolymers such as polyfunctional compounds such as polyhydric alcohols.

  As the monomer binder, for example, dendrimers described in JP-A-2005-76005 and JP-A-2005-36105, and norbornene ring-containing monomers as described in JP-A-2005-60425 can be used.

  Two or more polyfunctional monomers may be used in combination. Polymerization of the monomer having an ethylenically unsaturated group can be performed by irradiation with ionizing radiation or heating in the presence of a photo radical initiator or a thermal radical initiator.

  It is preferable to use a photopolymerization initiator for the polymerization reaction of the photopolymerizable polyfunctional monomer. As the photopolymerization initiator, a photoradical polymerization initiator and a photocationic polymerization initiator are preferable, and a photoradical polymerization initiator is particularly preferable.

(Polymerization initiator)
The polymerization initiator effective for curing the low refractive index layer of the present invention will be described. When the constituent component of the low refractive index layer is a radical polymerizable compound, the polymerization of these compounds can be carried out by irradiation with ionizing radiation or heating in the presence of a photo radical initiator or a thermal radical initiator.

(Photo radical initiator)
As radical photopolymerization initiators, acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides, 2,3-dialkyldione compounds, disulfide compounds , Fluoroamine compounds, aromatic sulfoniums, lophine dimers, onium salts, borate salts, active esters, active halogens, inorganic complexes, coumarins and the like.

  Examples of acetophenones include 2,2-dimethoxyacetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, 1-hydroxy-dimethylphenylketone, 1-hydroxy-dimethyl-p-isopropylphenylketone, 1-hydroxy Cyclohexyl phenyl ketone, 2-methyl-4-methylthio-2-morpholinopropiophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, 4-phenoxydichloroacetophenone, 4-t-butyl -Dichloroacetophenone and the like are included.

  Examples of benzoins include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyl dimethyl ketal, benzoin benzene sulfonate, benzoin toluene sulfonate, benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether. included.

Examples of benzophenones include benzophenone, hydroxybenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 2,4-dichlorobenzophenone, 4,4-
Examples include dichlorobenzophenone and p-chlorobenzophenone, 4,4′-dimethylaminobenzophenone (Michler ketone), 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, and the like.

Examples of phosphine oxides include 2,4,6-trimethylbenzoyl diphenylphosphine oxide. Examples of active esters include 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], sulfonate esters,
Examples include cyclic active ester compounds. Specifically, compounds described in Examples in JP-A No. 2000-80068 are particularly preferable.

  Examples of the onium salts include aromatic diazonium salts, aromatic iodonium salts, and aromatic sulfonium salts. Examples of borate salts include ion complexes with cationic dyes.

  Specific examples of the active halogens include Wakabayashi et al., “Bull Chem. Soc Japan”, 42, 2924 (1969), US Pat. No. 3,905,815, JP-A-5-27830, M.M. P. Examples include compounds described in Hutt “Journal of Heterocyclic Chemistry”, Vol. 1 (No. 3), (1970), and in particular, oxazole compounds substituted with a trihalomethyl group: s-triazine compounds. More preferred are s-triazine derivatives in which at least one mono-, di- or trihalogen-substituted methyl group is bonded to the s-triazine ring. Specific examples include S-triazine and oxathiazole compounds, such as 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl). -4,6-bis (trichloromethyl) -s-triazine, 2- (p-styrylphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (3-Br-4-di (ethyl) Acetate) amino) phenyl) -4,6-bis (trichloromethyl) -s-triazine, 2-trihalomethyl-5- (p-methoxyphenyl) -1,3,4-oxadiazole. Specifically, Nos. In p14 to p30 in JP-A-58-15503, p6-p10 in JP-A-55-77742, and p287 in JP-B-60-27673. 1-No. 8, No. pp. 443 to p444 of JP-A-60-239736. 1-No. 17, No. 4,701,399. Compounds such as 1-19 are particularly preferred.

  Specific examples of the active halogens are as follows.

Examples of inorganic complexes include bis (η ⁵ -2,4-cyclopentadien-1-yl) -bis [2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl] titanium. . Examples of coumarins include 3-ketocoumarin.
These initiators may be used alone or in combination.

In the present invention, an oligomer type polymerization initiator is preferred as the compound having a high molecular weight and hardly volatilizing from the coating film. The oligomer type radiation polymerization initiator is not particularly limited as long as it has a site that generates a photo radical upon irradiation. In order to prevent volatilization by heat treatment, the molecular weight of the polymerization initiator is preferably 280 or more and 10,000 or less, more preferably 300 or more and 10,000 or less. More preferably, the mass average molecular weight is 400 to 10,000. A mass average molecular weight of 400 or more is preferable because of low volatility, and 10,000 or less is preferable because hardness of the resulting cured coating film is sufficient. Specific examples of the oligomer type radiation polymerization initiator include oligo [2-hydroxy-2-methyl-1- {4- (1-methylvinyl) phenyl} propanone] represented by the following general formula (5). .
General formula (5)

In the general formula (5), R ⁵¹ represents a monovalent group, preferably a monovalent organic group, and q represents an integer of 2 to 45.

  As a commercially available product of the oligo [2-hydroxy-2-methyl-1- {4- (1-methylvinyl) phenyl} propanone] represented by the general formula (5), trade name “Ezacure KIP150” manufactured by Fratelli Lamberti (CAS-No. 163702-01-0, q = 4-6), “Ezacure KIP65LT” (a mixture of “Ezacure KIP150” and tripropylene glycol diacrylate), “Ezacure KIP100F” (“Ezacure KIP150” and 2- Hydroxy-2-methyl-1-phenylpropan-1-one mixture), “Ezacure KT37”, “Ezacure KT55” (above, “Ezacure KIP150” and a mixture of methylbenzophenone derivatives), “Ezacure KTO46” (“Ezacure KIP150”) ”Methylbenzofu Non-derivative and a mixture of 2,4,6-trimethylbenzoyldiphenylphosphine oxide), “Ezacure KIP75 / B” (a mixture of “Ezacure KIP150” and 2,2-dimethoxy-1,2-diphenylethane-1-one), etc. Can be mentioned.

  “Latest UV Curing Technology” {Technical Information Association, Inc.} (1991), p. 159 and “UV Curing System” written by Kiyotsugu Kato (published by the General Technology Center in 1989), pages 65-148, are also useful in the present invention.

  Commercially available photocleavable photoradical polymerization initiators include “Irgacure 651”, “Irgacure 184”, “Irgacure 819”, “Irgacure 907”, “Irgacure 1870” (CGI) manufactured by Ciba Specialty Chemicals Co., Ltd. -403 / Irg184 = 7/3 mixing initiator), "Irgacure 500", "Irgacure 369", "Irgacure 1173", "Irgacure 2959", "Irgacure 4265", "Irgacure 4263", "Irgacure 127", "OXE01 “Kaya Cure DETX-S”, “Kaya Cure BP-100”, “Kaya Cure BDK”, “Kaya Cure CTX”, “Kaya Cure BMS”, “Kaya Cure 2-EAQ”, “Kaya Cure ABQ” manufactured by Nippon Kayaku Co., Ltd. ”,“ Kayaki "ACPTX", "Kayacure EPD", "Kayacure ITX", "Kayacure QTX", "Kayacure BTC", "Kayacure MCA", etc .; , KIP150, TZT) ", etc., and combinations thereof are preferred examples.

  In addition to the photopolymerization initiator, a photosensitizer may be used. Specific examples of the photosensitizer include n-butylamine, triethylamine, tri-n-butylphosphine, Michler's ketone and thioxanthone. Further, one or more auxiliary agents such as an azide compound, a thiourea compound, and a mercapto compound may be used in combination.

  Examples of commercially available photosensitizers include “Kaya Cure (DMBI, EPA)” manufactured by Nippon Kayaku Co., Ltd.

(D) Inorganic fine particles The inorganic fine particles that can be used in the low refractive index layer of the present invention will be described. In the present invention, it is preferable to use inorganic fine particles in the low refractive index layer from the viewpoint of lowering the refractive index and improving the scratch resistance. The inorganic fine particles preferably have an average particle size of 20 to 100 nm, but inorganic low refractive index particles are preferable from the viewpoint of lowering the refractive index.

  Examples of the inorganic fine particles include magnesium fluoride and silica fine particles because of their low refractive index. In particular, silica fine particles are preferable in terms of refractive index, dispersion stability, and cost. The size (primary particle size) of these inorganic particles is preferably 20 to 100 nm, more preferably 30 to 80 nm, and most preferably 40 to 70 nm.

  If the particle size of the inorganic fine particles is too small, the effect of improving the scratch resistance is reduced. If the particle size is too large, fine irregularities are formed on the surface of the low refractive index layer, and the appearance such as black tightening and the integrated reflectance are deteriorated. The inorganic fine particles may be either crystalline or amorphous, and may be monodispersed particles or aggregated particles as long as a predetermined particle size is satisfied. The shape is most preferably a spherical diameter, but there is no problem even if the shape is indefinite.

The coating amount of the inorganic fine particles is ^{preferably 1mg / m 2 ~100mg / m 2} , more preferably ^{5mg / m 2 ~80mg / m 2} , more preferably from ^{10mg / m 2 ~60mg / m 2} . If the amount is too small, the effect of improving the scratch resistance is reduced. If the amount is too large, fine irregularities are formed on the surface of the low refractive index layer, and the appearance such as black tightening and the integrated reflectance are deteriorated.

(Porous or hollow fine particles)
In order to reduce the refractive index, it is particularly preferable to use fine particles having a porous structure or a hollow structure having pores therein. The porosity of these particles is preferably 10 to 80%, more preferably 20 to 60%, and most preferably 30 to 60%. It is preferable that the void ratio of the hollow fine particles be in the above range from the viewpoint of lowering the refractive index and maintaining the durability of the particles.

  When the porous or hollow particles are silica, the refractive index of the fine particles is preferably 1.10 to 1.40, more preferably 1.15 to 1.35, and most preferably 1.15 to 1.30. is there. The refractive index here represents the refractive index of the entire particle, and does not represent the refractive index of only the outer shell silica forming the silica particles.

  A method for producing porous or hollow silica is described in, for example, Japanese Patent Application Laid-Open Nos. 2001-233611 and 2002-79616. In particular, particles having cavities inside the shell and having fine pores in the shell are particularly preferred. The refractive index of these hollow silica particles can be calculated by the method described in JP-A No. 2002-79616.

The coating amount of the porous or hollow silica is ^preferably from ^{1mg / m 2 ~100mg / m 2} , more preferably ^{5mg / m 2 ~80mg / m 2} , more preferably is 10mg ^{/ m 2} ~60mg ^/ m 2 . If the amount is too small, the effect of reducing the refractive index and the effect of improving the scratch resistance are reduced. If the amount is too large, fine irregularities are formed on the surface of the low refractive index layer, and the appearance such as black tightening and the integrated reflectance are deteriorated.

  The average particle size of the porous or hollow silica is preferably 30% or more and 150% or less, more preferably 35% or more and 80% or less, and still more preferably 40% or more and 60% or less of the thickness of the low refractive index layer. That is, if the thickness of the low refractive index layer is 100 nm, the particle size of the hollow silica is preferably 30 nm to 150 nm, more preferably 35 nm to 100 nm, and still more preferably 40 nm to 65 nm. In the present invention, the pore-containing fine particles may have a size distribution, and the coefficient of variation thereof is preferably 60% to 5%, more preferably 50% to 10%. In addition, two or more kinds of particles having different average particle sizes can be mixed and used.

  If the particle size of the silica particles is too small, the proportion of cavities will decrease and a decrease in refractive index cannot be expected. Getting worse. The silica fine particles may be either crystalline or amorphous, and monodisperse particles are preferred. The shape is most preferably a spherical diameter, but there is no problem even if the shape is indefinite.

  Further, two or more kinds of hollow silica having different particle average particle sizes can be used in combination. Here, the average particle diameter of the hollow silica can be determined from an electron micrograph.

The specific surface area of the hollow silica in the present invention is preferably from 20 to 300 m ² / g, more preferably 30~120m ² / g, most preferably 40~90m ² / g. The surface area can be obtained by the BET method using nitrogen.

  In the present invention, silica particles having no voids can be used in combination with hollow silica. The preferred particle size of silica without voids is 30 nm to 150 nm, more preferably 35 nm to 100 nm, and most preferably 40 nm to 80 nm.

[Preparation method of porous or hollow fine particles]
A preferred method for producing hollow fine particles is described below. The first step is the formation of core particles that can be removed by post-treatment, the second step is the formation of a shell layer, the third step is the dissolution of core particles, and the fourth step is the formation of an additional shell phase if necessary. Specifically, the hollow particles can be produced according to the method for producing hollow silica fine particles described in, for example, JP-A-2001-233611.

  A preferred method for producing porous particles is to produce porous core particles by controlling the degree of hydrolysis and condensation of alkoxide and the type and amount of coexisting substances as the first step, and a shell layer on the surface as the second step. It is a method of forming. Specifically, the production of porous particles can be performed by the methods described in JP-A Nos. 2003-327424, 2003-335515, 2003-226516, 2003-238140, and the like. it can.

  In the present invention, it is preferable to reduce the amount of adsorbed water of inorganic fine particles, which will be described later, and it can be controlled by changing the particle size, changing the shell thickness, hydrothermal treatment conditions, and the like. Also, the amount of adsorbed water can be reduced by firing the particles.

(Coated particles)
Increasing the shell thickness is preferable because the adsorption sites on the particle surface can be reduced and the amount of adsorbed water can be reduced. Furthermore, it is preferable to form a shell with a conductive component since conductivity can be imparted. Particularly preferred is a combination using silica-based porous or hollow particles as the core particles and ZnO ₂ , Y ₂ O ₃ , Sb ₂ O ₅ , ATO, ITO, SnO ₂ as the shell. Hereinafter, particularly preferred antimony oxide-coated silica-based fine particles will be described.

  In the antimony oxide-coated silica-based fine particles according to the present invention, porous silica-based fine particles or silica-based fine particles having cavities therein are coated with an antimony oxide coating layer. The porous silica-based fine particles include porous silica fine particles and composite oxide fine particles containing silica as a main component, and the surface of the porous inorganic oxide fine particles disclosed in JP-A-7-133105 is used. Low refractive index nanometer-sized composite oxide fine particles coated with silica or the like can be suitably used.

  The silica-based fine particles having cavities therein are composed of inorganic oxides other than silica and silica, disclosed in JP-A-2001-233611, and low-refractive-index nanometer-sized silica-based particles having cavities inside. Fine particles can also be suitably used.

  Such porous silica-based fine particles or silica-based fine particles having cavities therein preferably have an average particle size in the range of 4 to 100 nm, more preferably 10 to 90 nm. If the average particle diameter is 4 nm or more, silica-based fine particles can be obtained without problems during production, and the obtained particles are also sufficiently stable, and can occur when small-sized particles are used. The problem that dispersed antimony oxide-coated silica-based fine particles cannot be obtained does not occur. If the average particle size is 100 nm or less, the average particle size of the obtained antimony oxide-coated silica-based fine particles can be suppressed to 120 nm or less, and when a transparent coating is formed using large-sized antimony oxide-coated silica-based fine particles. It is preferable because it can suppress a possible decrease in transparency and an increase in haze.

  The refractive index of the porous silica-based fine particles or the silica-based fine particles having cavities therein is preferably 1.45 or less, more preferably 1.40 or less, which is the refractive index of silica. In addition, although nonporous silica fine particles having a refractive index of 1.45 to 1.46 can be used alone, it is preferable to use silica-based fine particles that are porous or have cavities inside from the viewpoint of antireflection performance. preferable.

  The silica-based fine particles are preferably coated with antimony oxide having an average coating layer thickness of 0.5 to 30 nm, preferably 1 to 10 nm. If the average thickness of the coating layer is 0.5 nm or more, it is preferable because the silica-based fine particles can be completely coated, and the resulting antimony oxide-coated silica-based fine particles have sufficient conductivity. If the thickness of the coating layer is 30 nm or less, the effect of improving the conductivity can be sufficiently obtained, and the shortage of the refractive index when the average particle diameter of the antimony oxide-coated silica-based fine particles is small can be suppressed.

  The antimony oxide-coated silica-based fine particles according to the present invention preferably have an average particle size in the range of 5 to 120 nm, more preferably 10 to 100 nm. When the average particle diameter of the antimony oxide-coated silica-based fine particles is 5 nm or more, the fine particles can be obtained without problems during production, and aggregated particles in the obtained particles can be suppressed, which is preferable. In addition, it can occur with small particles, and when used for forming a transparent film due to insufficient dispersibility, transparency, haze, film strength, adhesion to a substrate, etc. do not become insufficient. ,preferable. If the average particle diameter of the antimony oxide-coated silica-based fine particles is 120 nm or less, the formed transparent film is preferable because the transparency is sufficient and the haze is kept low. Further, the adhesion with the base material does not become insufficient.

  The refractive index of the antimony oxide-coated silica-based fine particles is preferably in the range of 1.25 to 1.60, more preferably 1.30 to 1.50. A refractive index of 1.25 or more is preferred because the particles can be obtained without problems during production. Moreover, there is no shortage in the strength of the obtained particles. On the other hand, if the refractive index is 1.60 or less, the antireflection performance of the transparent coating is also sufficient, which is preferable.

The volume resistance value of the antimony oxide-coated silica-based fine particles is preferably in the range of 10 to 5000 Ω / cm, more preferably 10 to 2000 Ω / cm. If the volume resistance value is 10 Ω / cm or more, the particles can be obtained without problems during production, which is preferable. Moreover, the refractive index of the obtained particle | grain becomes 1.6 or less, and the anti-reflective performance of a transparent film is sufficient, and it is preferable. On the other hand, if the volume resistance value is 5000 Ω / cm or less, the antistatic performance of the obtained transparent film is sufficient, which is preferable. The antimony oxide-coated silica-based fine particles of the present invention can be used after surface treatment with a silane coupling agent according to a conventional method, if necessary.

[Inorganic fine particle surface treatment method]
The method for treating the surface of the inorganic fine particles will be described by taking porous or hollow inorganic fine particles as an example. In order to improve the dispersibility in the binder for forming the low refractive index layer, the surface of the inorganic fine particles is treated with a hydrolyzate of organosilane represented by the following general formula (1) and / or a partial condensate thereof. It is preferable that either an acid catalyst or a metal chelate compound or both be used in the treatment.

(Organosilane compound)
The organosilane compound used in the present invention will be described in detail.
General formula (1):
_{^{(R 10) a1 -Si (X}} 11) 4-a1

In the general formula (1), R ¹⁰ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. Examples of the alkyl group include methyl group, ethyl group, propyl group, i-propyl group, hexyl group, t-butyl group, s-butyl group, hexyl group, decyl group, hexadecyl group and the like. The alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 6 carbon atoms. Examples of the aryl group include a phenyl group and a naphthyl group, and a phenyl group is preferable.

X ¹¹ represents a hydroxyl group or a hydrolyzable group. Examples of the hydrolyzable group include an alkoxy group (preferably an alkoxy group having 1 to 5 carbon atoms, such as a methoxy group and an ethoxy group), a halogen atom (for example, Cl, Br, I and the like), and R ^12. A group represented by COO (R ¹² is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, such as CH ₃ COO, C ₂ H ₅ COO, etc.), preferably an alkoxy group, Particularly preferred is a methoxy group or an ethoxy group.
a1 represents an integer of 1 to 3. 1 or 2 is preferable, and 1 is particularly preferable. When R ¹⁰ or the X ¹¹ there are a plurality, a plurality of R ¹⁰ or X ¹¹ may be different, respectively.

The substituent contained in R ¹⁰ is not particularly limited, but is a halogen atom (fluorine atom, chlorine atom, bromine atom, etc.), hydroxyl group, mercapto group, carboxyl group, epoxy group, alkyl group (methyl group, ethyl group, i -Propyl group, propyl group, t-butyl group etc.), aryl group (phenyl group, naphthyl group etc.), aromatic heterocyclic group (furyl group, pyrazolyl group, pyridyl group etc.), alkoxy group (methoxy group, ethoxy group) I-propoxy group, hexyloxy group, etc.), aryloxy group (phenoxy group etc.), alkylthio group (methylthio group, ethylthio group etc.), arylthio group (phenylthio group etc.), alkenyl group (vinyl group, 1-propenyl group) Etc.), acyloxy group (acetoxy group, acryloyloxy group, methacryloyloxy group, etc.), alkoxycarbonyl group Methoxycarbonyl group, ethoxycarbonyl group, etc.), aryloxycarbonyl group (phenoxycarbonyl group, etc.), carbamoyl group (carbamoyl group, N-methylcarbamoyl group, N, N-dimethylcarbamoyl group, N-methyl-N-octylcarbamoyl group) Etc.), acylamino groups (acetylamino group, benzoylamino group, acrylamino group, methacrylamino group, etc.) and the like, and these substituents may be further substituted. In the present specification, even if a hydrogen atom is replaced by a single atom, it is treated as a substituent for convenience.

When there are a plurality of R ^{10 s} , at least one of them is preferably a substituted alkyl group or a substituted aryl group. Among these, the substituted alkyl group or substituted aryl group preferably further has a vinyl polymerizable group, and the compound represented by the general formula (1) is a vinyl polymerizable substituent represented by the following general formula (1-2). It can be expressed as an organosilane compound having a group.
General formula (1-2):

In General Formula (1-2), R ¹¹ represents a hydrogen atom, a methyl group, a methoxy group, an alkoxycarbonyl group, a cyano group, a fluorine atom, or a chlorine atom. Examples of the alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group. R ¹¹ is preferably a hydrogen atom, a methyl group, a methoxy group, a methoxycarbonyl group, a cyano group, a fluorine atom or a chlorine atom, more preferably a hydrogen atom, a methyl group, a methoxycarbonyl group, a fluorine atom or a chlorine atom, And a methyl group are particularly preferred.

Y ¹¹ represents a single bond, an ester group, an amide group, an ether group or a urea group. Single bonds, ester groups and amide groups are preferred, single bonds and ester groups are more preferred, and ester groups are particularly preferred.

L ¹¹ is a divalent linking chain, specifically, a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, and a linking group (for example, an ether group, an ester group, an amide group) inside. A substituted or unsubstituted alkylene group, or a substituted or unsubstituted arylene group having a linking group therein, among which a substituted or unsubstituted alkylene group having 2 to 10 carbon atoms, a substituted or unsubstituted carbon number of 6 An alkylene group having 3 to 10 carbon atoms having a linking group therein and an unsubstituted alkylene group, an unsubstituted arylene group, and an alkylene group having an ether linking group or an ester linking group therein. An unsubstituted alkylene group and an alkylene group having an ether linking group or an ester linking group therein are particularly preferred. Examples of the substituent include a halogen, a hydroxyl group, a mercapto group, a carboxyl group, an epoxy group, an alkyl group, and an aryl group, and these substituents may be further substituted.

a2 represents 0 or 1. When X ¹¹ there are a plurality, it may be different even multiple X ¹¹ is the same, respectively. a2 is preferably 0.

R ¹⁰ has the same meaning as R ^{10 in} formula (1), preferably a substituted or unsubstituted alkyl group or an unsubstituted aryl group, and more preferably an unsubstituted alkyl group or an unsubstituted aryl group. X ^{11 is} also synonymous with X ^{11 in the} general formula (1), preferably a halogen, a hydroxyl group or an unsubstituted alkoxy group, more preferably a chlorine, a hydroxyl group or an unsubstituted alkoxy group having 1 to 6 carbon atoms, a hydroxyl group or a carbon atom. A C 1-3 alkoxy group is more preferable, and a methoxy group is particularly preferable.

As the organosilane compound used in the present invention, those represented by the following general formula (2) are also preferred.
Formula ^{_{(2) :( R f -L 21}} ) b1 -Si (X 21) 4- b1

In the general formula (2), R _f represents a linear, branched or cyclic fluorinated alkyl group having 1 to 20 carbon atoms or a fluorinated aromatic group having 6 to 14 carbon atoms. R _f is preferably a linear, branched, or cyclic fluoroalkyl group having 3 to 10 carbon atoms, and more preferably a linear fluoroalkyl group having 4 to 8 carbon atoms. L ²¹ represents a divalent linking group having 10 or less carbon atoms, preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 5 carbon atoms. The alkylene group is a linear or branched, substituted or unsubstituted alkylene group that may have a linking group (for example, ether, ester, amide) inside. The alkylene group may have a substituent, and preferable substituents in that case include a halogen atom, a hydroxyl group, a mercapto group, a carboxyl group, an epoxy group, an alkyl group, and an aryl group. X ²¹ has the same meaning as X ^{11 in} formula (1), preferably a halogen, a hydroxyl group, or an unsubstituted alkoxy group, more preferably a chlorine, a hydroxyl group, or an unsubstituted alkoxy group having 1 to 6 carbon atoms, a hydroxyl group, An alkoxy group having 1 to 3 carbon atoms is more preferable, and a methoxy group is particularly preferable.
b1 is synonymous with a1 of the said General formula (1), and represents the integer of 1-3. 1 or 2 is preferable, and 1 is particularly preferable.

Next, among the fluorine-containing silane coupling agents represented by the general formula (2), a fluorine-containing silane coupling agent represented by the following general formula (2-1) is preferable.
Formula _{(2-1): C n F 2n} + 1 - (CH 2) m -Si (X 22) 3
In the general formula (2-1), n represents an integer of 1 to 10, and m represents an integer of 1 to 5. n is preferably 4 to 10, m is preferably 1 to 3, and X ²² represents a methoxy group, an ethoxy group, and a chlorine atom.

  Two or more compounds represented by general formula (1), general formula (1-2), general formula (2), and general formula (2-1) may be used in combination.

  Specific examples of the compounds represented by general formula (1), general formula (1-2), general formula (2), and general formula (2-1) are shown below, but the present invention is limited to these. It is not a thing.

Disiloxane compounds can also be used as surface treating agents, such as hexamethyldisiloxane, 1,3-dibutyltetramethyldisiloxane, 1,3-diphenyltetramethyldisiloxane, 1,3-divinyltetra. Examples thereof include methyldisiloxane, hexaethyldisiloxane, and 3-glycidoxypropylpentamethyldisiloxane.
Among these specific examples, (M-1), (M-2), (M-30), (M-35), (M-49), (M-51), (M-56), (M-57) and the like are particularly preferable. Further, the compounds of A, B and C described in Reference Examples of Japanese Patent No. 3474330 are also preferable because of excellent dispersion stability.

  The amount of the organosilane compound represented by the general formula (1), general formula (1-2), general formula (2), and general formula (2-1) is not particularly limited, but is 1 per inorganic fine particle. -300 mass% is preferable, More preferably, it is 3-100 mass%, Most preferably, it is 5-50 mass%. It is preferably 1 to 300 mol%, more preferably 5 to 300 mol%, most preferably 10 to 200 mol% per hydroxyl group on the surface of the inorganic fine particles. When the amount of the organosilane compound used is in the above range, a sufficient stabilizing effect of the dispersion can be obtained, and the film strength is also increased during coating film formation. In the present invention, it is also preferable to use a plurality of types of organosilane compounds in combination, and a plurality of types of compounds can be added simultaneously, or the addition time can be shifted for reaction. Also, it is preferable to add a plurality of types of compounds after making them into partial condensates in advance because the reaction control is easy.

[Improved dispersibility of inorganic fine particles]
The dispersibility of the inorganic fine particles can be improved by allowing the hydrolyzate and / or partial condensate thereof of the organosilane compound described above to act on the surface of the inorganic fine particles. The hydrolysis / condensation reaction of the organosilane compound is 0.3 to 2.0 mol, preferably 0.5 to 1.0 mol, relative to 1 mol of the hydrolyzable group (X ¹¹ , X ²¹ and X ²² ). It is preferable to carry out by stirring at 15-100 degreeC in the presence of the acid catalyst used for this invention, or the metal chelate compound.

[Catalyst for Dispersibility Improvement Treatment]
The treatment for improving the dispersibility by the hydrolyzate and / or condensation reaction product of the organosilane is preferably performed in the presence of a catalyst. Catalysts include inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid; organic acids such as oxalic acid, acetic acid, formic acid, methanesulfonic acid and toluenesulfonic acid; inorganic bases such as sodium hydroxide, potassium hydroxide and ammonia; triethylamine, Examples include organic bases such as pyridine; metal alkoxides such as triisopropoxyaluminum and tetrabutoxyzirconium. From the viewpoint of production stability and storage stability of the inorganic oxide fine particle liquid, an acid catalyst is used in the present invention. (Inorganic acids, organic acids) and / or metal chelate compounds are used. Among inorganic acids, hydrochloric acid, sulfuric acid, and organic acids preferably have an acid dissociation constant in water (pKa value (25 ° C.)) of 4.5 or less, and an acid dissociation constant in hydrochloric acid, sulfuric acid, or water of 3.0 or less. More preferred is an organic acid, hydrochloric acid, sulfuric acid, an organic acid having an acid dissociation constant of 2.5 or less in water is more preferred, an organic acid having an acid dissociation constant in water of 2.5 or less is more preferred, and methanesulfonic acid Further, oxalic acid, phthalic acid, and malonic acid are more preferable, and oxalic acid is particularly preferable.

  When the hydrolyzable group of the organosilane is an alkoxy group and the acid catalyst is an organic acid, the amount of water added can be reduced because the carboxyl group or sulfo group of the organic acid supplies protons. The amount of water added to 1 mol of the alkoxide group of the organosilane is 0 to 2 mol, preferably 0 to 1.5 mol, more preferably 0 to 1 mol, and particularly preferably 0 to 0.5 mol. Moreover, when alcohol is used for the solvent, an embodiment in which water is not substantially added is also suitable.

(Metal chelate compound)
The metal chelate compound used for the improvement treatment of dispersibility by hydrolyzate and / or condensation reaction product of organosilane is represented by the alcohol represented by the following general formula (3-1) and the following general formula (3-2). At least one metal chelate compound having a metal selected from Zr, Ti, or Al as a central metal and having a compound as a ligand is preferred. As long as the metal chelate compound has a metal selected from Zr, Ti or Al as the central metal, it can be suitably used without any particular limitation. Within this category, two or more metal chelate compounds may be used in combination.
Formula (3-1): R ³¹ OH
Formula (3-2): R ³² COCH ₂ COR ³³
(In the formula, R ³¹ and R ³² may be the same or different and each represents an alkyl group having 1 to 10 carbon atoms, and R ³³ represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms. Show.)

  Specific examples of the metal chelate compound suitably used in the present invention include tri-n-butoxyethyl acetoacetate zirconium, di-n-butoxybis (ethyl acetoacetate) zirconium, n-butoxy tris (ethyl acetoacetate) zirconium, tetrakis Zirconium chelate compounds such as (n-propylacetoacetate) zirconium, tetrakis (acetylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium; diisopropoxy bis (ethylacetoacetate) titanium, diisopropoxy bis (acetylacetate) ) Titanium chelate compounds such as titanium, diisopropoxy bis (acetylacetone) titanium; diisopropoxyethyl acetoacetate aluminum , Diisopropoxyacetylacetonate aluminum, isopropoxybis (ethylacetoacetate) aluminum, isopropoxybis (acetylacetonate) aluminum, tris (ethylacetoacetate) aluminum, tris (acetylacetonate) aluminum, monoacetylacetonate -Aluminum chelate compounds, such as bis (ethyl acetoacetate) aluminum, etc. are mentioned.

  Among these metal chelate compounds, tri-n-butoxyethyl acetoacetate zirconium, diisopropoxy bis (acetylacetonate) titanium, diisopropoxyethyl acetoacetate aluminum, and tris (ethyl acetoacetate) aluminum are preferable. . These metal chelate compounds can be used individually by 1 type or in mixture of 2 or more types. Moreover, the partial hydrolyzate of these metal chelate compounds can also be used. The amount of these metal chelate compounds is preferably 0.1 to 10.0% by mass, more preferably 0.5 to 5.0% by mass, and most preferably 1.0 to 3.0% with respect to the organosilane compound. % By mass.

(Organosilane compound having an unsaturated double bond)
In the low refractive index layer, as the component (B), an organosilane compound having an unsaturated double bond, a hydrolyzate of the organosilane compound having an unsaturated double bond, and / or a partial condensate thereof, etc. It is preferable from the viewpoint of scratch resistance that the obtained reaction solution is also referred to as “sol component”.
These compounds function as a binder by applying the curable composition and then condensing in a drying and heating process to form a cured product. Moreover, when it has a polyfunctional acrylate polymer / or a monomer, the binder which has a three-dimensional structure is formed by irradiation of actinic light.
When used in combination with a polymerizable fluorine-containing compound in the present invention, these organosilane compounds tend to segregate in the lower part. On the contrary, since the polymerizable fluorine-containing compound tends to segregate on the upper part of the coating film, the adhesiveness with the lower layer can be improved by using it together, and the scratch resistance can be greatly improved.

  As specific compound examples, the above-described inorganic fine particle organosilane compounds (M-1) to (M-88) can be used. Of these, (M-1), (M-2), (M-30) and (M-35) are preferred.

The amount of the organosilane compound or its hydrolyzate and / or its partial condensate is preferably from 0.1 to 50% by mass, more preferably from 0.5 to 30% by mass, based on the total solid content of the low refractive index layer. Preferably, 1-20 mass% is the most preferable.
The organosilane compound may be added directly to the coating composition, but the organosilane compound is treated in advance in the presence of a catalyst to prepare a hydrolyzate and / or partial condensate of the organosilane compound. It is preferable to prepare the coating composition by using the reaction solution (sol solution) obtained. In the present invention, first, a composition containing a hydrolyzate and / or partial condensate of the organosilane compound and a metal chelate compound. It is preferable to prepare a coating composition containing a liquid obtained by adding a β-diketone compound and / or a β-ketoester compound to the coating composition.

(Fluorine-containing copolymer)
A fluorine-containing copolymer compound can be preferably used for the low refractive index layer in the present invention. In the present specification, “(meth) acrylate”, “(meth) acrylic acid”, and “(meth) acryloyl” represent “acrylate or methacrylate”, “acrylic acid or methacrylic acid”, and “acryloyl or methacryloyl”, respectively. .
The fluorine-containing copolymer is preferably 0 to 50% by mass, more preferably 5 to 30% by mass in the solid content of the coating composition.

  Examples of the fluorine-containing vinyl monomer include fluoroolefins (for example, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, etc.), (meth) acrylic acid moieties or fully fluorinated alkyl ester derivatives (for example, biscoat 6FM (trade name) , Osaka Organic Chemical Co., Ltd.) and R-2020 (trade name, manufactured by Daikin Co., Ltd.), fully or partially fluorinated vinyl ethers, and the like. Preferred are perfluoroolefins, refractive index, solubility, and transparency. From the viewpoint of availability, hexafluoropropylene is particularly preferable. Increasing the composition ratio of these fluorinated vinyl monomers can lower the refractive index but lowers the film strength. In the present invention, the fluorine-containing vinyl monomer is preferably introduced so that the fluorine content of the copolymer is 20 to 60% by mass, more preferably 25 to 55% by mass, and particularly preferably 30 to 50%. This is a case of mass%.

  For the purpose of imparting crosslinking reactivity with the above-mentioned fluorine-containing vinyl monomer, a copolymer with a unit represented by the following (A), (B), (C) can be preferably used.

(A): a structural unit obtained by polymerization of a monomer having a self-crosslinkable functional group in the molecule in advance such as glycidyl (meth) acrylate or glycidyl vinyl ether,
(B): Monomer having a carboxyl group, hydroxy group, amino group, sulfo group, etc. (for example, (meth) acrylic acid, methylol (meth) acrylate, hydroxyalkyl (meth) acrylate, allyl acrylate, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether) , Maleic acid, crotonic acid, etc.)
(C): A group having a crosslinkable functional group separately from a group that reacts with the functional groups (A) and (B) in the molecule and a structural unit of the above (A) and (B). Examples of the structural unit to be obtained (for example, a structural unit that can be synthesized by a technique such as allowing acrylic acid chloride to act on a hydroxyl group).

  In the structural unit (C), the crosslinkable functional group is preferably a photopolymerizable group. Examples of the photopolymerizable group include (meth) acryloyl group, alkenyl group, cinnamoyl group, cinnamylideneacetyl group, benzalacetophenone group, styrylpyridine group, α-phenylmaleimide group, phenylazide group, sulfonylazide. Group, carbonyl azide group, diazo group, o-quinonediazide group, furylacryloyl group, coumarin group, pyrone group, anthracene group, benzophenone group, stilbene group, dithiocarbamate group, xanthate group, 1,2,3-thiadiazole group, cyclo A propene group, an azadioxabicyclo group, etc. can be mentioned, These may be not only 1 type but 2 or more types. Of these, a (meth) acryloyl group and a cinnamoyl group are preferable, and a (meth) acryloyl group is particularly preferable.

Specific methods for preparing the photopolymerizable group-containing copolymer include, but are not limited to, the following methods.
a. A method of esterifying by reacting a (meth) acrylic acid chloride with a crosslinkable functional group-containing copolymer containing a hydroxyl group,
b. A method of urethanization by reacting a (meth) acrylic acid ester containing an isocyanate group with a crosslinkable functional group-containing copolymer containing a hydroxyl group,
c. A method of reacting (meth) acrylic acid with a crosslinkable functional group-containing copolymer containing an epoxy group,
d. A method in which a crosslinkable functional group-containing copolymer containing a carboxyl group is reacted with a containing (meth) acrylic acid ester containing an epoxy group for esterification.

  The amount of the photopolymerizable group introduced can be arbitrarily adjusted, and a certain amount of carboxyl groups, hydroxyl groups, etc., from the viewpoints of surface stability of the coating film, reduction of surface failure when coexisting with inorganic particles, and improvement of film strength. It is also preferable to leave.

  In the copolymer useful for the present invention, in addition to the repeating unit derived from the above-mentioned fluorine-containing vinyl monomer and the repeating unit having a (meth) acryloyl group in the side chain, it contributes to adhesion to the substrate and Tg of the polymer (film hardness). And other vinyl monomers can be copolymerized as appropriate from various viewpoints such as solubility in a solvent, transparency, slipperiness, dust resistance and antifouling properties. A plurality of these vinyl monomers may be combined depending on the purpose, and are preferably introduced in the range of 0 to 65 mol% in the copolymer in total, and in the range of 0 to 40 mol%. More preferably, it is particularly preferably in the range of 0 to 30 mol%.

  The vinyl monomer unit that can be used in combination is not particularly limited. For example, olefins (ethylene, propylene, isoprene, vinyl chloride, vinylidene chloride, etc.), acrylic esters (methyl acrylate, methyl acrylate, ethyl acrylate, acrylic acid) 2-ethylhexyl, 2-hydroxyethyl acrylate), methacrylic acid esters (methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-hydroxyethyl methacrylate, etc.), styrene derivatives (styrene, p-hydroxymethylstyrene, p -Methoxystyrene, etc.), vinyl ethers (methyl vinyl ether, ethyl vinyl ether, cyclohexyl vinyl ether, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, etc.), vinyl esters (vinyl acetate) Vinyl propionate, vinyl cinnamate, etc.), unsaturated carboxylic acids (acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, etc.), acrylamides (N, N-dimethylacrylamide, N-tert-butylacrylamide, N -Cyclohexyl acrylamide, etc.), methacrylamides (N, N-dimethylmethacrylamide), acrylonitrile and the like.

  The fluorine-containing polymer particularly useful in the present invention is a random copolymer of perfluoroolefin and vinyl ethers or vinyl esters. In particular, it preferably has a group capable of undergoing a crosslinking reaction alone (a radical reactive group such as a (meth) acryloyl group, a ring-opening polymerizable group such as an epoxy group or an oxetanyl group). These crosslinkable group-containing polymerized units preferably occupy 5 to 70 mol% of the total polymerized units of the polymer, particularly preferably 30 to 60 mol%. Regarding preferred polymers, JP-A-2002-243907, JP-A-2002-372601, JP-A-2003-26732, JP-A-2003-222702, JP-A-2003-294911, JP-A-2003-329804, JP-A-2004. -4444 and JP, 2004-45462, A can be mentioned.

  For the purpose of imparting antifouling properties, it is preferable that a polysiloxane structure is introduced into the fluoropolymer of the present invention. There is no limitation on the method of introducing the polysiloxane structure, but for example, as described in JP-A-6-93100, JP-A-11-189621, JP-A-11-228631 and JP-A-2000-313709, the initiation of silicone macroazo A method of introducing a polysiloxane block copolymer component using an agent, and a method of introducing a polysiloxane graft copolymer component using a silicone macromer as described in JP-A-2-251555 and JP-A-2-308806. preferable. Particularly preferred compounds include the polymers of Examples 1, 2, and 3 of JP-A-11-189621, and the copolymers A-2 and A-3 of JP-A-2-251555. These polysiloxane components are preferably 0.5 to 10% by mass in the polymer, and particularly preferably 1 to 5% by mass.

  The preferred molecular weight of the polymer that can be preferably used in the present invention is a mass average molecular weight of 5,000 or more, preferably 10,000 to 500,000, most preferably 15,000 to 200,000. By using polymers having different average molecular weights in combination, it is possible to improve the surface state of the coating film and the scratch resistance.

(Polysiloxane compounds)
Next, the polysiloxane compound will be described. In the present invention, it is preferable to use a compound having a polysiloxane structure for the purpose of improving scratch resistance by imparting slipperiness and imparting antifouling property. There is no restriction | limiting in particular in the structure of a compound, What has a substituent in the terminal and / or side chain of a compound chain | strand which contains multiple dimethylsilyloxy units as a repeating unit is mentioned. The compound chain containing dimethylsilyloxy as a repeating unit may contain a structural unit other than dimethylsilyloxy.

  When these compounds are added, it is preferably added in the range of 0.01 to 20% by mass of the total solid content of the low refractive index layer, more preferably in the range of 0.05 to 10% by mass. Particularly preferably 0.1 to 5% by mass.

  Although there is no restriction | limiting in particular in the molecular weight of the compound which has a polysiloxane structure, It is preferable that it is 100,000 or less, It is especially preferable that it is 50,000 or less, It is most preferable that it is 3000-30000.

  From the viewpoint of preventing transfer, it is preferable to contain a (meth) acryloyl group or a functional group that reacts with the (meth) acryloyl group to form a bond. This bond formation reaction preferably proceeds rapidly in the presence of a polymerization initiator. Although the following are mentioned as an example of a preferable compound, It is not limited to these.

  Preferable examples include those having a substituent at the terminal and / or side chain of a compound chain containing a plurality of dimethylsilyloxy units as repeating units. The compound chain containing dimethylsilyloxy as a repeating unit may contain a structural unit other than dimethylsilyloxy. The substituents may be the same or different, and a plurality of substituents are preferable. Examples of preferred substituents include groups containing acryloyl group, methacryloyl group, vinyl group, aryl group, cinnamoyl group, oxetanyl group, fluoroalkyl group, polyoxyalkylene group, carboxyl group, amino group and the like. In particular, it preferably contains a (meth) acryloyl group. Although there is no restriction | limiting in particular in molecular weight, It is preferable that it is 100,000 or less, It is more preferable that it is 50,000 or less, It is especially preferable that it is 3000-30000, It is most preferable that it is 10,000-20000. Although there is no restriction | limiting in particular in silicone atom content of a silicone type compound, it is preferable that it is 18.0 mass% or more, it is especially preferable that it is 25.0-37.0 mass%, and 30.0-37.0. Most preferably, it is mass%. Examples of preferred silicone compounds include X-22-174DX, X-22-2426, X-22-164B, X22-164C, X-22-1821 (above trade names) and Chisso (manufactured by Shin-Etsu Chemical Co., Ltd.). Co., Ltd., FM-0725, FM-7725, FM6621, FM-1121 and Gelest DMS-U22, RMS-033, RMS-083, UMS-182, DMS-H21, DMS-H31, HMS-301, FMS121, Examples thereof include, but are not limited to, FMS123, FMS131, FMS141, and FMS221 (hereinafter, trade names).

  For the purpose of imparting properties such as dust resistance and antistatic properties, a known cationic surfactant or a dustproof agent such as a polyoxyalkylene compound, an antistatic agent, or the like can be appropriately added. These dustproofing agent and antistatic agent may contain the structural unit as a part of the function in the above-mentioned silicone compound. When these are added as additives, it is preferably added in the range of 0.01 to 20% by mass of the total solid content of the low refractive index layer, more preferably in the range of 0.05 to 10% by mass. Particularly preferred is 0.1 to 5% by mass. Examples of preferred compounds include SH-3748 (trade name) manufactured by Toray Dow Corning Co., Ltd., but are not limited thereto.

(Layer structure of antireflection film)
The antireflection film of the present invention has at least one antireflection layer on a transparent support (hereinafter sometimes referred to as a support) in consideration of the refractive index, film thickness, number of layers, layer order, and the like. Are stacked.

  In general, the antireflection film of the present invention has a simplest configuration in which only a low refractive index layer is coated on a substrate. In order to further reduce the reflectance, the antireflection layer is preferably constituted by combining a high refractive index layer having a higher refractive index than that of the base material and a low refractive index layer having a lower refractive index than that of the base material. Examples of configurations include two layers of a high refractive index layer / low refractive index layer from the base material side, and three layers having different refractive indices, a medium refractive index layer (having a higher refractive index than the base material or the hard coat layer). , A layer having a refractive index lower than that of a high refractive index layer) / a layer having a high refractive index / a layer having a low refractive index, and the like. Especially, it is preferable to apply | coat in order of a middle refractive index layer / high refractive index layer / low refractive index layer on the base material which has a hard-coat layer from durability, an optical characteristic, cost, productivity, etc.

  The example of the preferable layer structure of the antireflection film of this invention is shown below. In the following configuration, what is described as (antistatic layer) is a configuration in which a layer having other functions also has the function of an antistatic layer. Since the number of layers to be formed can be reduced by providing the antistatic layer with a function other than antistatic, this structure is preferable because productivity is improved.

・ Support / Antistatic layer / Low refractive index layer,
-Support / low refractive index layer (antistatic layer),
Support / antiglare layer (antistatic layer) / low refractive index layer,
Support / antiglare layer / antistatic layer / low refractive index layer,
Support / hard coat layer / antiglare layer (antistatic layer) / low refractive index layer,
Support / hard coat layer / antiglare layer / antistatic layer / low refractive index layer,
Support / hard coat layer / antistatic layer / antiglare layer / low refractive index layer,
Support / hard coat layer (antistatic layer) / antiglare layer / low refractive index layer,
Support / hard coat layer / high refractive index layer / antistatic layer / low refractive index layer,
Support / hard coat layer / high refractive index layer (antistatic layer) / low refractive index layer,
Support / hard coat layer / antistatic layer / high refractive index layer / low refractive index layer,
Support / hard coat layer / medium refractive index layer / high refractive index layer (antistatic layer) / low refractive index layer,
Support / hard coat layer / medium refractive index layer (antistatic layer) / high refractive index layer / low refractive index layer,
Support / hard coat layer (antistatic layer) / medium refractive index layer / high refractive index layer / low refractive index layer,
Support / antiglare layer / high refractive index layer (antistatic layer) / low refractive index layer,
Support / antiglare layer / medium refractive index layer (antistatic layer) / high refractive index layer / low refractive index layer,
Support / antistatic layer / hard coat layer / medium refractive index layer / high refractive index layer / low refractive index layer,
Antistatic layer / support / hard coat layer / medium refractive index layer / high refractive index layer / low refractive index layer,
Support / antistatic layer / antiglare layer / medium refractive index layer / high refractive index layer / low refractive index layer,
Antistatic layer / support / antiglare layer / medium refractive index layer / high refractive index layer / low refractive index layer,
Antistatic layer / support / antiglare layer / high refractive index layer / low refractive index layer / high refractive index layer / low refractive index layer.

  As long as the reflectance can be reduced by optical interference, it is not limited to these layer configurations.

(Transparent support)
The support for the film of the present invention is not particularly limited, such as a transparent resin film, a transparent resin plate, a transparent resin sheet, or transparent glass. Transparent resin films include cellulose acylate films (for example, cellulose triacetate film (refractive index 1.48), cellulose diacetate film, cellulose acetate butyrate film, cellulose acetate propionate film), polyethylene terephthalate film, polyethersulfone. Films, polyacrylic resin films, polyurethane resin films, polyester films, polycarbonate films, polysulfone films, polyether films, polymethylpentene films, polyetherketone films, (meth) acrylonitrile films, and the like can be used.

(Cellulose acylate film)
Among them, a cellulose acylate film having high transparency, optically low birefringence, easy production, and generally used as a protective film for a polarizing plate is preferable, and a cellulose triacetate film is particularly preferable. The thickness of the transparent support is usually about 25 μm to 1000 μm.

  In the present invention, it is preferable to use cellulose acetate having an acetylation degree of 59.0 to 61.5% for the cellulose acylate film. The degree of acetylation means the amount of bound acetic acid per unit mass of cellulose. The degree of acetylation follows the measurement and calculation of the degree of acetylation in ASTM: D-817-91 (test method for cellulose acetate and the like). The viscosity average degree of polymerization (DP) of cellulose acylate is preferably 250 or more, and more preferably 290 or more.

  The cellulose acylate used in the present invention has a Mw / Mn (Mw is a mass average molecular weight, Mn is a number average molecular weight) value by gel permeation chromatography close to 1.0, in other words, a molecular weight distribution. Narrow is preferred. The specific value of Mw / Mn is preferably 1.0 to 1.7, more preferably 1.3 to 1.65, and most preferably 1.4 to 1.6. preferable.

In general, the hydroxyl groups at 2, 3, and 6 positions of cellulose acylate are not evenly distributed by 1/3 of the total substitution degree, and the substitution degree of the 6-position hydroxyl group tends to be small. In the present invention, it is preferable that the substitution degree of the 6-position hydroxyl group of cellulose acylate is larger than that of the 2- and 3-positions.
The hydroxyl group at the 6-position with respect to the total substitution degree is preferably substituted with 32% or more of an acyl group, more preferably 33% or more, and particularly preferably 34% or more. Furthermore, the substitution degree of the 6-position acyl group of cellulose acylate is preferably 0.88 or more. The 6-position hydroxyl group may be substituted with a propionyl group, butyroyl group, valeroyl group, benzoyl group, acryloyl group or the like, which is an acyl group having 3 or more carbon atoms, in addition to the acetyl group. The degree of substitution at each position can be determined by NMR.

  In the present invention, the cellulose acylate is described in paragraph Nos. 0043 to 0044, Examples, Synthesis Example 1, Paragraph Nos. 0048 to 0049, Synthesis Examples 2, Paragraph Nos. 0051 to 0052, and Synthesis Example 3 of JP-A No. 11-5851. The cellulose acetate obtained by the method can be used.

(Polyethylene terephthalate film)
In the present invention, a polyethylene terephthalate film is also preferably used because it is excellent in transparency, mechanical strength, flatness, chemical resistance and moisture resistance, and is inexpensive.
In order to further improve the adhesion strength between the transparent plastic film and the hard coat layer provided thereon, the transparent plastic film is more preferably subjected to an easy adhesion treatment. Examples of commercially available PET films with an easily adhesive layer for optics include Cosmo Shine A4100 and A4300 manufactured by Toyobo Co., Ltd.

[Coating composition]
The coating composition of the present invention comprises (A) a polymerizable fluorine-containing compound, (B) a polyfunctional monomer not containing fluorine, (C) a photopolymerization initiator, (D) inorganic fine particles as necessary, and the above-mentioned other Contains ingredients. Although content of solid content of a coating composition is not specifically limited, When the total amount of (A) and (B) is 100 mass parts, it is preferable that content of (A) is 30-80 mass parts. . More preferably, it is 40-80 mass parts, and it is most preferable that it is 50-80 mass parts. When the content of (A) exceeds 80 parts by mass, the scratch resistance is deteriorated. When the content is less than 30 parts by mass, the refractive index is not sufficiently lowered and the antireflection effect is reduced.

  Regarding (C), 1 to 10% by mass is preferable, and 1 to 5% by mass is more preferable, based on the solid content. Regarding (D), it is preferable to contain 10-70 mass% with respect to solid content, it is more preferable to contain 20-60 mass%, and it is most preferable to contain 30-60 mass%.

  A solvent can be further used for the coating composition. When a solvent is used, it is preferable to use the solvent so that the solid content in the coating composition is in the range of 0.1 to 90% by mass.

〔solvent〕
The solvent for dissolving the compound semiconductor is not particularly limited, but alcohol solvents and ketone solvents are preferably used. Specifically, acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone, 2-hexane, 2-heptanone, 4-heptanone, methyl isopropyl ketone, ethyl isopropyl ketone, diisopropyl ketone, methyl isobutyl ketone, methyl-t-butyl ketone, Examples thereof include diacetyl, acetylacetone, acetonylacetone, diacetone alcohol, mesityl oxide, chloroacetone, cyclopentanone, cyclohexanone, acetophenone, and the like. Among these, methyl ethyl ketone and methyl isobutyl ketone are preferable. These solvents may be used alone or in a mixture at an arbitrary mixing ratio.

  As the auxiliary solvent, an ester solvent such as propylene glycol monomethyl ether acetate or a fluorinated solvent (such as a fluorinated alcohol) can be used as appropriate. These solvents may be used alone or in a mixture at an arbitrary mixing ratio.

(Application method)
The antireflection film of the present invention can be formed by the following method, but is not limited to this method. First, a coating composition containing components for forming each layer is prepared. Next, the coating composition is applied on a transparent support by dip coating, air knife coating, curtain coating, roller coating, wire bar coating, gravure coating or die coating, and heated and dried. A micro gravure coating method, a wire bar coating method, and a die coating method (see US Pat. No. 2,681,294 and JP-A-2006-122889) are more preferable, and a die coating method is particularly preferable.

  After coating, the layer formed from the coating composition is cured by light irradiation or heating. Thereby, a low refractive index layer is formed. If necessary, an optical layer (a layer constituting a film described below, for example, a hard coat layer, an antiglare layer, a medium refractive index layer, a high refractive index layer, etc.) is coated on the transparent support in advance. A low refractive index layer can be formed thereon. In this way, the antireflection film of the present invention is obtained.

(Hard coat layer)
The film of the present invention can be provided with a hard coat layer in order to impart the physical strength of the film.
Preferably, a low refractive index layer is provided thereon, and more preferably, an intermediate refractive index layer and a high refractive index layer are provided between the hard coat layer and the low refractive index layer to constitute an antireflection film.
The hard coat layer may be composed of two or more layers.

  The refractive index of the hard coat layer in the present invention is preferably in the range of 1.48 to 2.00, more preferably 1.52 to 1, from the optical design for obtaining an antireflection film. .90, more preferably 1.55 to 1.80. In the present invention, since there is at least one low refractive index layer on the hard coat layer, if the refractive index is too small, the antireflection property is lowered, and if it is too large, the color of the reflected light tends to be strong. is there.

From the viewpoint of imparting sufficient durability and impact resistance to the film, the thickness of the hard coat layer is usually about 0.5 μm to 50 μm, preferably 1 μm to 20 μm, more preferably 5 μm. ˜20 μm.
Further, the strength of the hard coat layer is preferably H or more, more preferably 2H or more, and most preferably 3H or more in a pencil hardness test. Furthermore, in the Taber test according to JIS K5400, the smaller the wear amount of the test piece before and after the test, the better.

The hard coat layer is preferably formed by a crosslinking reaction or a polymerization reaction of an ionizing radiation curable compound. For example, it may be formed by applying a coating composition containing an ionizing radiation-curable polyfunctional monomer or polyfunctional oligomer on a transparent support and subjecting the polyfunctional monomer or polyfunctional oligomer to a crosslinking reaction or a polymerization reaction. it can.
The functional group of the ionizing radiation-curable polyfunctional monomer or polyfunctional oligomer is preferably a light, electron beam, or radiation polymerizable group, and among them, a photopolymerizable functional group is preferable.
Examples of the photopolymerizable functional group include unsaturated polymerizable functional groups such as a (meth) acryloyl group, a vinyl group, a styryl group, and an allyl group. Among them, a (meth) acryloyl group is preferable. Specifically, the compounds mentioned in (Polyfunctional monomer containing no fluorine) can be preferably used.

  The hard coat layer contains matte particles having an average particle diameter of 1.0 to 10.0 μm, preferably 1.5 to 7.0 μm, such as inorganic compound particles or resin particles, for the purpose of imparting internal scattering properties. May be.

  For the purpose of controlling the refractive index of the hard coat layer, a high refractive index monomer, inorganic particles, or both can be added to the binder of the hard coat layer. In addition to the effect of controlling the refractive index, the inorganic particles also have the effect of suppressing cure shrinkage due to the crosslinking reaction. In the present invention, a polymer formed by polymerizing the polyfunctional monomer and / or the high refractive index monomer after the hard coat layer is formed, and the inorganic particles dispersed therein are referred to as a binder.

  In order to maintain the sharpness of the image, it is preferable to adjust the clarity of the transmitted image in addition to adjusting the uneven shape of the surface. The clearness of the transmitted image of the clear antireflection film is preferably 60% or more. The transmitted image clarity is generally an index indicating the degree of blurring of an image reflected through a film, and the larger this value, the clearer and better the image viewed through the film. The transmitted image definition is preferably 70% or more, and more preferably 80% or more.

(Anti-glare layer)
The antiglare layer is formed for the purpose of contributing to the film an antiglare property due to surface scattering and preferably a hard coat property for improving the hardness and scratch resistance of the film.

  As a method of forming the antiglare property, a method of laminating and forming a mat-shaped shaping film having fine irregularities on the surface as described in JP-A-6-16851, as described in JP-A-2000-206317 A method of forming by curing shrinkage of an ionizing radiation curable resin due to a difference in the amount of ionizing radiation applied, and by reducing the mass ratio of a good solvent to a light transmitting resin by drying as described in JP-A No. 2000-338310. A method of solidifying the light-sensitive fine particles and the translucent resin while gelling to form unevenness on the coating film surface, a method of imparting surface unevenness by external pressure as described in JP-A-2000-275404, etc. These known methods can be used.

The antiglare layer that can be used in the present invention preferably contains a binder capable of imparting hard coat properties, translucent particles for imparting antiglare properties, and a solvent as essential components. It is preferable that irregularities on the surface be formed by the protrusions of the protrusions themselves or protrusions formed by an aggregate of a plurality of particles.
The antiglare layer formed by dispersing the matte particles is composed of a binder and translucent particles dispersed in the binder. The antiglare layer having antiglare properties preferably has both antiglare properties and hard coat properties.

(High refractive index layer, medium refractive index layer)
The film of the present invention can be provided with a high refractive index layer and a medium refractive index layer to enhance antireflection properties. In the following specification, the high refractive index layer and the medium refractive index layer may be collectively referred to as a high refractive index layer. In the present invention, “high”, “medium”, and “low” in the high refractive index layer, medium refractive index layer, and low refractive index layer represent the relative refractive index relationship between the layers. In terms of the relationship with the transparent support, the refractive index preferably satisfies the relationship of transparent support> low refractive index layer, high refractive index layer> transparent support. In the present specification, the high refractive index layer, the middle refractive index layer, and the low refractive index layer may be collectively referred to as an antireflection layer.

  In order to construct an antireflection film by constructing a low refractive index layer on a high refractive index layer, the refractive index of the high refractive index layer is preferably 1.55 to 2.40, more preferably It is 1.60 to 2.20, more preferably 1.65 to 2.10, and most preferably 1.80 to 2.00.

  When an antireflective film is prepared by coating a medium refractive index layer, a high refractive index layer, and a low refractive index layer in order from the support, the refractive index of the high refractive index layer is 1.65 to 2.40. Preferably, it is 1.70 to 2.20. The refractive index of the middle refractive index layer is adjusted to be a value between the refractive index of the low refractive index layer and the refractive index of the high refractive index layer. The refractive index of the middle refractive index layer is preferably 1.55 to 1.80.

The inorganic particles mainly composed of TiO ₂ used for the high refractive index layer and the medium refractive index layer are used for forming the high refractive index layer and the medium refractive index layer in the state of dispersion.
In the dispersion of the inorganic particles, the inorganic particles are dispersed in the dispersion medium in the presence of a dispersant.

  The high refractive index layer and the medium refractive index layer used in the present invention are preferably used in a dispersion liquid in which inorganic particles are dispersed in a dispersion medium, preferably a binder precursor necessary for matrix formation (for example, an ionizing radiation curable composition described later). Polyfunctional monomer, polyfunctional oligomer, etc.), photopolymerization initiator, etc. are added to form a coating composition for forming a high refractive index layer and a medium refractive index layer, and a high refractive index layer and a medium refractive index layer are formed on a transparent support. It is preferable that the coating composition is applied and cured by a crosslinking reaction or a polymerization reaction of an ionizing radiation curable compound (for example, a polyfunctional monomer or a polyfunctional oligomer).

Furthermore, it is preferable to cause the binder of the high refractive index layer and the medium refractive index layer to undergo a crosslinking reaction or a polymerization reaction with the dispersant simultaneously with or after the coating of the layer.
The binder of the high refractive index layer and the medium refractive index layer produced in this way is, for example, the above-mentioned preferred dispersant and ionizing radiation curable polyfunctional monomer or polyfunctional oligomer are crosslinked or polymerized to form a binder. The anionic group of the dispersant is incorporated. Furthermore, the binder of the high refractive index layer and the medium refractive index layer has a function in which the anionic group maintains the dispersion state of the inorganic particles, and the crosslinked or polymerized structure imparts a film forming ability to the binder and contains inorganic particles. To improve the physical strength, chemical resistance and weather resistance of the high refractive index layer and medium refractive index layer.

  The binder of the high refractive index layer is added in an amount of 5 to 80% by mass based on the solid content of the coating composition of the layer.

The content of the inorganic particles in the high refractive index layer is preferably 10 to 90% by mass, more preferably 15 to 80% by mass, and particularly preferably 15 to 75% by mass with respect to the mass of the high refractive index layer. . Two or more kinds of inorganic particles may be used in combination in the high refractive index layer.
When the low refractive index layer is provided on the high refractive index layer, the refractive index of the high refractive index layer is preferably higher than the refractive index of the transparent support.
The high refractive index layer contains an ionizing radiation curable compound containing an aromatic ring, an ionizing radiation curable compound containing a halogenated element other than fluorine (for example, Br, I, Cl, etc.), and atoms such as S, N, P, etc. A binder obtained by a crosslinking or polymerization reaction such as an ionizing radiation curable compound can also be preferably used.

  The film thickness of the high refractive index layer can be appropriately designed depending on the application. When using a high refractive index layer as an optical interference layer described later, the thickness is preferably 30 to 200 nm, more preferably 50 to 170 nm, and particularly preferably 60 to 150 nm.

The haze of the high refractive index layer is preferably as low as possible when it does not contain particles that impart an antiglare function. It is preferably 5% or less, more preferably 3% or less, and particularly preferably 1% or less.
The high refractive index layer is preferably constructed directly on the transparent support or via another layer.

(Low refractive index layer)
In order to reduce the reflectance of the film of the present invention, a low refractive index layer is used. The refractive index of the low refractive index layer is preferably 1.20 to 1.46, more preferably 1.25 to 1.40, and particularly preferably 1.30 to 1.37.

  The thickness of the low refractive index layer is preferably 30 to 500 nm, and more preferably 70 to 500 nm.

  The haze of the low refractive index layer is preferably 3% or less, more preferably 2% or less, and most preferably 1% or less.

  The strength of the low refractive index layer is preferably H or more, more preferably 2H or more, and most preferably 3H or more in a pencil hardness test with a load of 500 g.

  In order to improve the antifouling performance of the antireflection film, the contact angle of the surface of the antireflection film with respect to water is preferably 90 degrees or more. More preferably, it is 95 degrees or more, and particularly preferably 100 degrees or more.

(Polarizer)
The polarizing plate is mainly composed of a polarizing film and two protective films for protecting both the front side and the back side. The antireflection film of the present invention is preferably used for at least one of the two protective films sandwiching the polarizing film from both sides. Since the antireflection film of the present invention also serves as a protective film, the production cost of the polarizing plate can be reduced. Further, by using the antireflection film of the present invention as the outermost layer, reflection of external light and the like can be prevented, and a polarizing plate having excellent scratch resistance, antifouling property and the like can be obtained.

  The surface hydrophilized by the saponification treatment is particularly effective for improving the adhesion with a polarizing film containing polyvinyl alcohol as a main component. In addition, the hydrophilic surface makes it difficult for dust in the air to adhere to it, so that it is difficult for dust to enter between the polarizing film and the antireflection film when adhered to the polarizing film, and to prevent point defects due to dust. It is valid.

  The saponification treatment is preferably carried out so that the contact angle of water on the surface of the transparent support opposite to the side having the outermost layer is 40 ° or less. More preferably, it is 30 ° or less, particularly preferably 20 ° or less.

(Image display device)
The antireflection film or polarizing plate of the present invention is an image such as a liquid crystal display (LCD), a plasma display panel (PDP), an electroluminescence display (ELD), a cathode ray tube display (CRT), or a surface electric field display (SED). It can be applied to a display device. It is particularly preferably used for a liquid crystal display (LCD).

  In order to describe the present invention in detail, examples will be described below, but the present invention is not limited to these examples. Unless otherwise specified, “part” and “%” are based on mass.

(Various evaluation of antireflection film)
(Steel wool (SW) scratch resistance evaluation)
By using a rubbing tester and carrying out a rubbing test under the following conditions, it can be used as an index of scratch resistance.
Evaluation environmental conditions: 25 ° C., 60% RH
Rubbing material: Steel wool (Nippon Steel Wool Co., Ltd., gelled No. 0000)
Wrap around the tip (1cm x 1cm) of the scraper of the tester that comes into contact with the sample, and fix the band.
Travel distance (one way): 13cm
Rubbing speed: 13 cm / second,
Load: 500 g / cm ²
Tip contact area: 1 cm × 1 cm, rubbing frequency: 10 reciprocations.
Oily black ink is applied to the back side of the rubbed sample, and the scratches on the rubbed portion are visually observed with reflected light, or evaluated based on the difference in the amount of reflected light other than the rubbed portion.

(Specular reflectance)
The specular reflectivity is measured by attaching an adapter “ARV-474” to a spectrophotometer “V-550” [manufactured by JASCO Corporation], and an emission angle at an incident angle of 5 ° in a wavelength region of 380 to 780 nm. The antireflection property can be evaluated by measuring a specular reflectance of −5 °, calculating an average reflectance of 450 to 650 nm.

(Anti-fouling test)
<Magic wiping durability>
The film is fixed on the glass surface with an adhesive, and a circle with a diameter of 5 mm is written three times with a pen tip (thin) of black magic “Mckey extra fine (product name: made by ZEBRA)” at 25 ° C. and 60 RH%. After 5 seconds, wipe it back and forth 20 times with a load that dents the bundle of Bencot (Brand name, Asahi Kasei Co., Ltd.) folded into 10 sheets. The writing and wiping are repeated under the above conditions until after the magic does not disappear by wiping, and the antifouling property can be evaluated by the number of times of wiping.
The number of times until it no longer disappears is preferably 5 times or more, and more preferably 10 times or more.

(Preparation of coating liquid for hard coat layer (HCL-1))
With respect to 90 parts by mass of MEK, 10 parts by mass of cyclohexanone, 95 parts by mass of partially caprolactone-modified polyfunctional acrylate (DPCA-20, Nippon Kayaku Co., Ltd.), photopolymerization initiator (Irgacure 184, Ciba Specialty Chemicals ( 5 parts by mass) were added and stirred. It filtered with the polypropylene filter with the hole diameter of 0.4 micrometer, and prepared the coating liquid (HCL-1) for hard-coat layers.

(Preparation of antireflection film sample 1)
An 80 μm-thick triacetyl cellulose film “TAC-TD80U” (manufactured by FUJIFILM Corporation) is unwound in the form of a roll, and the hard coat layer coating solution (HCL-1) is directly applied to the 180-wire film. Using a micro gravure roll with a diameter of 50 mm and a doctor blade having a gravure pattern with a depth of 40 μm and a doctor blade, it was applied at a gravure roll rotational speed of 30 rpm and a conveying speed of 30 m / min, and dried at 60 ° C. for 150 seconds. Furthermore, using an “air-cooled metal halide lamp” {manufactured by Eye Graphics Co., Ltd.) with an oxygen concentration of 0.1% by volume under a nitrogen purge, ultraviolet rays having an irradiance of 400 mW / cm ² and an irradiation amount of 70 mJ / cm ² are emitted. The coating layer was cured by irradiation to form a 10.0 μm thick layer and wound up. In this way, a hard coat layer (HC-1) was obtained.

(Preparation of hollow silica particle dispersion)
Hollow silica particle fine particle sol (isopropyl alcohol silica sol, CS60-IPA manufactured by Catalyst Chemical Industry Co., Ltd., average particle diameter 60 nm, shell thickness 10 nm, silica concentration 20%, silica particle refractive index 1.31) in 500 parts, acryloyloxy After 20 parts of propyltrimethoxysilane and 1.5 parts of diisopropoxyaluminum ethyl acetate were added and mixed, 9 parts of ion-exchanged water was added. After reacting at 60 ° C. for 8 hours, the mixture was cooled to room temperature, and 1.8 parts of acetylacetone was added to obtain dispersion A. Then, while adding cyclohexanone so that the silica content was substantially constant, the solvent was replaced by distillation under reduced pressure at a pressure of 30 Torr. Finally, a dispersion having a solid content concentration of 18.2% was obtained by adjusting the concentration. When the amount of IPA remaining in the obtained dispersion was analyzed by gas chromatography, it was 0.5% or less.

(Synthesis of polymerizable fluorine-containing compounds)
The (F-8) compound, the (F-10) compound, and the (F-13) compound were synthesized in the same manner as the synthesis of the (F-1) compound described above.

(Preparation of coating solution for low refractive index layer)
Each component was mixed as shown in Table 1 (parts by mass) and dissolved in MEK to prepare a coating solution for a low refractive index layer having a solid content of 5%.

  In addition, the symbol in the said table | surface is as follows.

“P-1”: fluorine-containing copolymer P-3 described in JP-A-2004-45462 (mass average molecular weight: about 50,000)
DPHA: a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd., Irg. 127: Irgacure 127, polymerization initiator (manufactured by Ciba Geigy Japan)
F-1, F-8, F-10, F-13: The above-described exemplary compounds (polymerizable fluorine-containing compounds)
A-1: Fluorine-containing acrylate M-1 exemplified in JP-A-2006-28280
RMS-033: Methacryloxy-modified silicone (manufactured by Gelest Co., Ltd.)

(Preparation of coating liquid A for medium refractive index layer)
Hard coating agent containing ZrO ₂ fine particles (Desolite Z7404 [refractive index 1.72, solid content concentration: 60% by mass, zirconium oxide fine particle content: 70% by mass (solid content), average particle size of zirconium oxide fine particles: about 20 nm, Solvent composition: MIBK / MEK = 9/1, manufactured by JSR Corporation]) 10.0 parts by mass, mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA) 3.0 parts by mass, photopolymerization started 0.1 parts by weight of an agent (Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.), methyl isobutyl ketone 86.9. A part by mass was added and stirred. After sufficiently stirring, the solution was filtered through a polypropylene filter having a pore diameter of 0.4 μm to prepare a coating solution A for medium refractive index layer.

(Preparation of coating liquid A for high refractive index layer)
Hard coating agent containing ZrO ₂ fine particles (Desolite Z7404 [refractive index 1.72, solid content concentration: 60% by mass, zirconium oxide fine particle content: 70% by mass (solid content), average particle size of zirconium oxide fine particles: about 20 nm, Solvent composition: MIBK / MEK = 9/1, manufactured by JSR Corporation]) 15.0 parts by mass was added with 85.0 parts by mass of methyl isobutyl ketone and stirred. Filtration through a polypropylene filter having a pore diameter of 0.4 μm prepared a coating solution A for a high refractive index layer.

(Coating of sample Nos. 1-8)
On the hard coat layer (HC-1), by using the coating liquids Ln-1 to 8 for the low refractive index layer, the thickness of the low refractive index layer is adjusted to 95 nm, and the microgravure coating method is used. Antireflection film samples 1 to 8 were prepared.

The low refractive index layer was dried at 60 ° C. for 60 seconds, and the ultraviolet curing condition was 240 W / cm air-cooled metal halide lamp (eye graphics) while purging with nitrogen so that the atmosphere had an oxygen concentration of 0.1% by volume or less. ), And the irradiation amount was 600 mW / cm ² and the irradiation amount was 600 mJ / cm ² .

(Coating of sample No. 9)
On the hard coat layer (HC-1), the medium refractive index layer is formed by the microgravure coating method by adjusting the film thickness of the medium refractive index layer to 60 nm using the coating liquid A for medium refractive index layer. After coating, the high refractive index layer is adjusted to 110 nm using the coating solution A for high refractive index layer, and the high refractive index layer is applied by the microgravure coating method. An antireflective film sample 9 was prepared by providing a low refractive index layer using a coating solution Ln-5 for low refractive index layer so that the film thickness of the low refractive index layer was 90 nm. The coating conditions of the low refractive index layer were the same as those of the antireflection film samples 1 to 8.

The medium refractive index layer was dried at 90 ° C. for 30 seconds, and the ultraviolet curing condition was 180 W / cm air-cooled metal halide lamp (eye graphics) while purging with nitrogen so that the atmosphere had an oxygen concentration of 1.0% by volume or less. ), And an irradiation dose of 400 mW / cm ² and an irradiation dose of 240 mJ / cm ² was used.

The drying condition of the high refractive index layer is 90 ° C. for 30 seconds, and the ultraviolet curing condition is a 240 W / cm air-cooled metal halide lamp (eye graphics) while purging with nitrogen so that the atmosphere has an oxygen concentration of 1.0% by volume or less. ), And an irradiation dose of 400 mW / cm ² and an irradiation dose of 240 mJ / cm ² was used.

(Evaluation of antireflection film)
The following evaluation was performed using said antireflection film.

(Evaluation 1) Steel Wool Scratch Resistance Evaluation Oil-based black ink was applied to the back side of the sample that had been rubbed and tested by the method described above, and visually observed with reflected light, and scratches on the rubbed portion were evaluated according to the following criteria. . The load was 500 g / cm ² and the number of times was 10 reciprocations.
A: Even if you look very carefully, no scratches are visible.
B: Slightly weak scratches can be seen when viewed very carefully.
C: A weak wound is visible.
D: A moderate crack is visible.
E: There is a scratch that can be seen at first glance.

(Evaluation 2) Antifouling Durability Tested by the method described above, the number of times until the magic did not disappear was determined. The number of times until it no longer disappears is preferably 5 times or more, and more preferably 10 times or more.

(Evaluation 3) Evaluation of specular reflectivity The specular reflectivity at an exit angle of -5 ° at an incident angle of 5 ° was measured by the method described above.

  The evaluation results are shown in Table 2.

  From the above results, it can be seen that, in the present invention, the antireflection film of the present invention has a low refractive index and excellent scratch resistance and antifouling durability.

Claims (17)

An antireflection film having at least one low refractive index layer on a transparent support, the low refractive index layer comprising:
(A) Polymerizable fluorine-containing compound represented by the following general formula (I)

[In the formula, Rf represents an a-valent organic group substantially composed of carbon atoms and fluorine atoms or only carbon atoms, fluorine atoms and oxygen atoms, and A represents a single bond or a general formula (II). Represents a divalent linking group, Q represents a polymerizable group or a hydrogen atom, a represents an integer of 3 to 20, and b and c each independently represents an integer of 0 to 100. However, at least two of a Q are polymerizable groups. In addition, the compound represented by the general formula (I) is a compound in which at least one of the calculated values of the molecular weight between crosslinks is larger than 300 when the polymerizable group in the polymerizable fluorine-containing compound is polymerized. ]
An antireflection film formed from a coating composition containing (B) a polyfunctional monomer containing no fluorine and (C) a photopolymerization initiator. In the general formula (I), Q is —COC (R ₀ ) ═CH ₂ , an allyl group, an epoxyalkylene group, — (CH ₂ ) _x Si (W) ₃ , — (CH ₂ ) _y NCO or — (CH ₂ ) _z CN (wherein R ₀ represents a hydrogen atom, a halogen atom or an alkyl group which may have a substituent. W represents an alkoxy group or a hydroxyl group. X, y and z each represents an integer of 1 or more. 3. The antireflection film according to claim 1, wherein three Ws may be different from each other. _2. The reflection according to claim 1, wherein in the general formula (I), Q is —COC (R) ═CH ₂ (wherein R represents a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group). Prevention film.   The antireflection film according to any one of claims 1 to 3, wherein the a is an integer of 3 to 6.   Said b and c are 0, The antireflection film in any one of Claims 1-3. In the general formula (I), Q is —COC (R) ═CH ₂ (wherein R represents a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group), a is an integer of 3 to 6, b The antireflection film according to claim 1, wherein c and c are 0.   The antireflection film according to claim 1, wherein the polyfunctional monomer (B) containing no fluorine is a polyfunctional (meth) acrylate having three or more functional groups.   The antireflection film according to any one of claims 1 to 7, wherein the coating composition further contains (D) inorganic fine particles.   The average particle diameter of the (D) inorganic fine particles is 20 nm or more and 100 nm or less, and the ratio of the (D) inorganic oxide fine particles is 10 to 70% by mass with respect to the total solid content in the coating composition. The antireflection film according to claim 8.   The antireflection film according to claim 8 or 9, wherein the (D) inorganic fine particles are surface-treated with at least one of a hydrolyzate of an organosilane compound and a partial condensate thereof.   The antireflection film according to claim 8, wherein at least one of the (D) inorganic fine particles is a particle having pores therein.   The polymerizable fluorine-containing compound has 3 or more carbon atoms substituted with at least one of oxygen atom, carbon atom and silicon atom in the molecule (however, all are substituted with a single bond) Item 12. The antireflection film according to any one of Items 1 to 11.   The antireflection film according to any one of claims 1 to 12, wherein the polyfunctional monomer (B) containing no fluorine contains an organosilane compound having an unsaturated double bond.   The antireflection film according to claim 1, wherein the fluorine content of the polymerizable fluorine-containing compound (A) is 40.0% by mass or more of the molecular weight of the polymerizable fluorine-containing compound.   When the total amount of the (A) polymerizable fluorine-containing compound and (B) the polyfunctional monomer not containing fluorine is 100 parts by mass, the content of the (A) polymerizable fluorine-containing compound is 30 to 80 parts by mass. Item 15. The antireflection film according to any one of Items 1 to 14.   The polarizing plate in which the antireflection film in any one of Claims 1-15 is used for at least one of the two protective films of the polarizing film in a polarizing plate.   An image display device in which the antireflection film according to claim 1 or the polarizing plate according to claim 16 is used on an outermost surface of a display.