JPH1180312A - Perfluoropolyoxyalkyl compound, paint for antireflection film, and low-reflective material using paint for antireflection film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coating material for forming an anti-reflection film having high hardness and excellent abrasion resistance, and to apply the coating material to one or both surfaces of a base material and polymerize and cure the coating material to obtain a high hardness and high resistance. Provided is a low-reflection material having an antireflection film having excellent wear properties. SOLUTION: The compound of the general formula (Chemical Formula 1) and the compound having a polymerizable unsaturated group, which contain at least one perfluoropolyoxyalkyl compound represented by the following General Formula (Chemical Formula 1) as an active ingredient: Or a compound of the general formula (Chemical Formula 1) and a compound having a polymerizable unsaturated group, and a compound of the following general formula
An antireflection film paint comprising a perfluoropolyoxyalkyl diisocyanate represented by the following formula (2) and an antireflection film obtained by polymerizing and curing these paints are directly applied to one or both surfaces of a substrate. Alternatively, a low reflection material formed via an antistatic layer. (Chemical formula 1) (CH ₂ = CRCOOCH ₂ ) ₃ CCH ₂ -Q-CF ₂ (OC ₂ F ₄ ) p (OCF ₂ ) qOCF ₂ -Q′-
CH ₂ C (CH ₂ OCOCR = CH ₂ ) ₃ where Q is OOCNHC ₆ H ₃ (CH ₃ ) NHCO or OCO, and Q ′ is
CONHC ₆ H ₃ (CH ₃ ) NHCOO or COO, R represents H or CH ₃ , and p and q each represent an integer of 1 to 50. (Chemical formula 2) OCNC ₆ H ₃ (CH ₃ ) NHCOCF ₂ (OC ₂ F ₄ ) p (OCF ₂ ) qOCF ₂ CONHC ₆ H ₃ (C
H ₃ ) NCO wherein p and q each represent an integer of 1 to 50.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for reducing the reflection on the surface of a transparent substrate such as glass and plastic.
The present invention relates to a paint for an antireflection film formed on the surface of a base material, and a low-reflection material used as a window material for a display device, a projection television, or the like.

[0002]

2. Description of the Related Art Recently, an antireflection film made of a fluororesin, which has a good productivity and can be easily enlarged, has been studied and put to practical use in a projection television or the like.

As the fluororesin, a transparent solvent-soluble fluoropolymer having a low refractive index and a low refractive index, such as a fluoroaliphatic polymer having a ring structure in the main chain, is used.
(Japanese Unexamined Patent Publication No. Hei 6-115023).

[0004]

However, the conventional antireflection film made of a fluorine-containing polymer has a problem that it has low hardness and poor abrasion resistance because the polymer has a linear structure.

In order to solve such a problem, the present invention provides a paint for forming an antireflection film having a three-dimensional network structure having high hardness and excellent wear resistance, and applying the paint to a substrate. It is an object of the present invention to provide a low-reflection material used as a window material for a display device, a projection television, or the like, which has an antireflection film having high hardness and excellent wear resistance by being polymerized and cured. .

[0006]

According to the present invention, there is provided a coating for an antireflection film comprising at least one perfluoropolyoxyalkyl compound represented by the following general formula (3) as an active ingredient: A compound containing a mixture of a polyoxyalkyl compound and a compound having a polymerizable unsaturated group, or a compound having a perfluoropolyoxyalkyl compound and a compound having a polymerizable unsaturated group and represented by the following general formula (Formula 4) Perfluoropolyoxyalkyl diisocyanate.

[0007]

Embedded image (CH ₂ = CRCOOCH ₂ ) ₃ CCH ₂ -Q-CF ₂ (OC ₂ F ₄ ) p (OCF ₂ ) qO
CF ₂ -Q′-CH ₂ C (CH ₂ OCOCR = CH ₂ ) ₃ where Q is OOCNHC ₆ H ₃ (CH ₃ ) NHCO or OCO, and Q ′ is
CONHC ₆ H ₃ (CH ₃ ) NHCOO or COO, R represents H or CH ₃ , and p and q each represent an integer of 1 to 50.

[0008]

Embedded image OCNC ₆ H ₃ (CH ₃ ) NHCOCF ₂ (OC ₂ F ₄ ) p (OCF ₂ ) qOCF ₂ CONH
C ₆ H ₃ (CH ₃ ) NCO where p and q are integers of 1 to 50.

The low-reflective material of the present invention can be prepared by applying an antireflection coating material directly or through an antistatic layer to one or both surfaces of a substrate and polymerizing and curing the same, thereby obtaining a single- or double-sided substrate. On which an anti-reflection film is formed.

[0010]

Embodiments of the present invention will be described below in detail.

A perfluoropolyoxyalkyl compound represented by the following general formula (Chemical Formula 5) is obtained by combining a perfluoropolyoxyalkyl diisocyanate represented by the following general formula (Chemical Formula 6) with pentaerythritol tri (meth) acrylate. , Dibutyltin dilaurate, triethylamine or the like as a catalyst to perform a normal urethanization reaction, or perfluoropolyoxyalkyldicarboxylic acid [for example, Fomblin Z-DIAC (Average molecular weight: 2,000) manufactured by Audimont Co., Ltd.]
And pentaerythritol tri (meth) acrylate can be easily synthesized by a usual esterification reaction using paratoluenesulfonic acid, sulfuric acid or the like as a catalyst.

[0012]

Embedded image (CH ₂ = CRCOOCH ₂ ) ₃ CCH ₂ -Q-CF ₂ (OC ₂ F ₄ ) p (OCF ₂ ) qO
CF ₂ -Q′-CH ₂ C (CH ₂ OCOCR = CH ₂ ) ₃ where Q is OOCNHC ₆ H ₃ (CH ₃ ) NHCO or OCO, and Q ′ is
CONHC ₆ H ₃ (CH ₃ ) NHCOO or COO, R represents H or CH ₃ , and p and q each represent an integer of 1 to 50.

[0013]

Embedded image OCNC ₆ H ₃ (CH ₃ ) NHCOCF ₂ (OC ₂ F ₄ ) p (OCF ₂ ) qOCF ₂ CONH
C ₆ H ₃ (CH ₃ ) NCO where p and q are integers of 1 to 50.

As the perfluoropolyoxyalkyl diisocyanate represented by the general formula (Chem. 6), for example, those commercially available as Fluorolink B (average molecular weight: 2,000) manufactured by Ausimont Co., Ltd. can be used. This perfluoropolyoxyalkyl diisocyanate reacts with the urethane bonding group in the perfluoropolyoxyalkyl compound or water in the atmosphere during the formation of the antireflection film to form an allophanate bond or a urea bond, and the hardness of the coating film And improve wear resistance.

The molecular weight of the perfluoropolyoxyalkyl group of the general formulas (Chem. 5) and (Chem. 6) is suitably from 800 to 5,000, preferably from 1,000 to 3,000. In this case, the molecular weight is 80
If it is less than 0, the vaporization becomes strong, and these compounds evaporate and decrease by heating or ultraviolet irradiation during polymerization curing,
On the other hand, when the molecular weight exceeds 5,000, the hardness of the antireflection film decreases.

The compound having a polymerizable unsaturated group includes:
Fluorine-containing or fluorine-free (meth) acrylic esters, (meth) acrylic oligoester prepolymers, unsaturated nitriles, unsaturated amides, unsaturated carboxylic acids, unsaturated carboxylic esters, carboxylic acids There are vinyl esters, aromatic vinyl compounds and the like, and a preferable polymerizable compound among these is a polyfunctional (meth) acrylate ester, which improves the hardness and abrasion resistance of the coating film.

Specific examples of the polyfunctional (meth) acrylic acid ester include 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9- Hexadecafluorodecanedi (meth) acrylate, 2,2,3,3,4,
4,5,5,6,6,7,7,8,8,9,9,10,10,11,11-eicosaflorododecane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditri Methylol propane tetra (meth) acrylate, pentaerythritol tetra
(Meth) acrylate, dipentaerythritol hexa
There are (meth) acrylates and the like, and these polyfunctional (meth) acrylates improve the hardness and abrasion resistance of the coating film.

The composition of the active ingredient in the coating for antireflection coating is 50% by weight, the perfluoropolyoxyalkyl compound is 50% to 100%, the perfluoropolyoxyalkyl diisocyanate is 0% to 50%, and the polymerizable unsaturated group is The content of the compound is preferably in the range of 0 to 50%. If the composition of these active ingredients is out of these ranges, the reflectance and the abrasion resistance of the antireflection film decrease. These active ingredients are ketones, carboxylic esters or 1,1,1,2,3,4,4,5,5,5-
It is dissolved in a solvent such as decafluoropentane to a concentration of 1 to 20% by weight to form a coating.

In addition, in the coating for antireflection coating, the polymerization initiator is used in an amount of 1 to 5% by weight based on the total weight of the perfluoropolyoxyalkyl compound and the compound having a polymerizable unsaturated group.
Add so that Examples of the polymerization initiator include azo-based radical polymerization initiators such as azobisisobutyronitrile and azobisvaleronitrile in the case of thermal polymerization, and -1,1,3,3-tetramethyl 2-ethylhexanoate. Organic peroxide radical polymerization initiators such as butyl peroxyester and 2-ethylhexanoic acid-tert-butyl peroxyester, and in the case of ultraviolet polymerization, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl 1-phenylpropane
A radical photopolymerization initiator such as 1-one can be used.

When the perfluoropolyoxyalkyl diisocyanate is contained in the active ingredient of the paint, and the perfluoropolyoxyalkyl diisocyanate and the perfluoropolyoxyalkyl compound are allophanate-bonded, the total weight of the perfluoropolyoxyalkyl diisocyanate is 0.1 to 0.1%. ~ 1% by weight of dibutyltin dilaurate, triethylamine and the like are added as catalyst.

The low reflection material of the present invention is prepared by applying the above-mentioned coating material for an antireflection film to one or both surfaces of a substrate so that the film thickness after drying is 70 to 150 nm, and then heating or irradiating with ultraviolet rays. Then, by polymerizing and curing, an antireflection film is formed on one side or both sides of the substrate to produce the substrate. The application of the paint can be performed by a normal application method such as dip coating, spin coating, flow coating, roll coating, and gravure coating.

Incidentally, the polymerization and curing by heating can be carried out in the range from 60 ° C. to the heat resistant temperature of the substrate for 30 to 120 minutes.

Further, the polymerization and curing by irradiation with ultraviolet light is 120 W
/ Cm high pressure mercury lamp for 10 to 300 seconds.

As the base material of the low reflection material, a transparent base material such as glass or plastic can be used. As the transparent plastic, polymethyl methacrylate, polycarbonate, polyethylene terephthalate, or the like can be used, and the shape may be any of a plate, a sheet, and a film.

A base material having an antistatic layer formed on the surface of plastic can also be used. This antistatic layer is
Alumina sol-based coating agent (for example, Ceramica G1 manufactured by Nippon Laboratories Inc.), siloxane-based coating agent (for example, Colcoat N-103 manufactured by Colcoat Co., Ltd.)
X) and the like, and can be formed by the above-mentioned usual coating method. The thickness is suitably from 10 to 1,000 nm. If the thickness is less than 10 nm, the antistatic effect becomes insufficient, and if it exceeds 1,000 nm, the adhesion to plastic decreases.

[0026]

Next, the present invention will be described in more detail by way of examples.

(Example 1) A synthesis example of a perfluoropolyoxyalkyl compound represented by the general formula (Formula 5) of the present invention will be specifically described.

The compound of this example is represented by the following formula (Formula 7).

[0029]

(CH ₂ = CHCOOCH ₂ ) ₃ CCH ₂ OOCNHC ₆ H ₃ (CH ₃ ) NHCOCF ₂ (O
C ₂ F ₄ ) p (OCF ₂ ) qOCF ₂ CONHC ₆ H _3- (CH ₃ ) NHCOOCH ₂ C (CH ₂ OCOCH =
CH ₂ ) ₃ where p and q are integers of 1 to 50.

59.7 g (0.2 mol) of pentaerythritol triacrylate as a starting material and 0.8 g of dibutyltin dilaurate as a urethanization reaction catalyst (0.3 g based on the total weight of the raw materials)
%), 0.3 g (0.1% based on the total weight of the raw materials) of paramethoxyphenol as a polymerization inhibitor, and 200 ml of 1,4-bistrifluoromethylbenzene, in a 2-liter flask equipped with stirring blades and a dropping funnel. And heated to 90 ° C. with stirring, then 1,4-bistrifluoromethylbenzene 200m
200 g of fluorolink B (average molecular weight: 2,000, manufactured by Audimont Co., Ltd.) represented by the general formula (Chemical Formula 6) as a starting material dissolved in l was dropped in 4 hours. After the completion of the dropwise addition, heating was continued for another 2 hours to complete the reaction.

After completion of the reaction, the solvent was replaced with methanol, and after washing, a trace amount of methanol dissolved in the product was distilled off under reduced pressure to obtain 250 g of a colorless and transparent viscous liquid. This liquid was determined by infrared spectroscopy (IR) and gel permeation chromatography (GPC) to be a perfluoropolyoxyalkyl compound represented by the formula (Formula 7) containing no starting materials and by-products. . IR: there is an absorption peak at 1,725 cm- ¹ of the aliphatic carboxylic acid ester (see FIG. 1). GPC: Starting materials and by-products are not detected.

(Example 2) Another synthesis example of the perfluoropolyoxyalkyl compound represented by the general formula (Formula 5) of the present invention will be specifically described.

The compound of this example is represented by the following formula (Formula 8).

[0034]

Embedded image (CH ₂ = CHCOOCH ₂ ) ₃ CCH ₂ OCOCF ₂ (OC ₂ F ₄ ) p (OCF ₂ ) qOC
F ₂ COOCH ₂ C (CH ₂ OCOCH = CH ₂ ) ₃ where p and q are integers of 1 to 50.

59.7 g (0.2 mol) of pentaerythritol triacrylate as a starting material, 200 g of Fomblin Z-DIAC (perfluoropolyoxyalkyldicarboxylic acid having an average molecular weight of 2,000, manufactured by Audimont Co., Ltd.), and an esterification reaction catalyst 7.8 g of paratoluenesulfonic acid (3% based on the total weight of raw materials) and paramethoxyphenol as a polymerization inhibitor
0.3 g (0.1% based on the total weight of the raw materials) and 800 ml of 1,4-bistrifluoromethylbenzene are collected in a 2 liter flask equipped with a stirring blade and a formed water separator, and then refluxed under reflux. The reaction was continued while stirring for hours. After completion of the reaction, the solvent was replaced with ethyl acetate, and the mixture was washed with water until the pH reached 5 or more.

Next, the ethyl acetate solution was dried over anhydrous sodium sulfate, and the solvent was replaced with methanol, followed by washing. Thereafter, a trace amount of methanol dissolved in the product was distilled off under reduced pressure to obtain 250 g of a colorless and transparent viscous liquid. This liquid was determined by infrared spectroscopy (IR) and gel permeation chromatography (GPC) to be a perfluoropolyoxyalkyl compound represented by the formula (Formula 8) which does not contain starting materials and by-products. . IR: the absorption peak of 1,790cm ~ ¹ absorption peak of 1,725cm ~ ¹ aliphatic carboxylic acid esters and perfluoroalkyl polyoxyethylene alkyl carboxylic acid ester is present (see FIG. 2). GPC: Starting materials and by-products are not detected.

Example 3 An example of the antireflection coating of the present invention will be specifically described.

The perfluoropolyoxyalkyl compound represented by the formula (Formula 7) obtained in Example 1 was used as an active ingredient of the paint, and the content thereof was 10% by weight, and 1-hydroxycyclohexyl phenyl ketone as a photopolymerization initiator was used. Paint 1 was dissolved in 1,1,1,2,3,4,4,5,5,5-decafluoropentane so as to be 0.3% by weight.

Paints 2 to 5 were prepared in the same manner as paint 1 except that the compounds shown in the following (Table 1) were used instead of the perfluoropolyoxyalkyl compound represented by the formula (Formula 7) as the active ingredient of the paint. Was adjusted. However, the paint 5 contains dibutyltin dilaurate as an allophanate reaction catalyst and the total of the perfluoropolyoxyalkyl diisocyanate represented by the general formula (Chemical Formula 6) and the perfluoropolyoxyalkyl compound represented by the chemical formula (Chemical Formula 7). 0.8% by weight was added.

In Table 1, the active ingredient FDMA was used.
Represents 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecafluorodecane dimethacrylate, and the active ingredient PETA is pentaerythritol tetraacrylate Is shown.

[0041]

[Table 1]

(Embodiment 4) An embodiment of the low reflection material of the present invention will be specifically described.

The paints 1 to 5 obtained in Example 3 were applied to both sides of an acrylic plate having a thickness of about 100 nm and a thickness of 2 mm by a dip coating method so that the reflectance after polymerization and curing became the lowest value. Above, the coating film was irradiated with ultraviolet rays by a 120 W / cm high pressure mercury lamp for 180 seconds on each side for 180 seconds to polymerize and cure, thereby producing low reflection materials 1 to 5 having antireflection films formed on both sides of an acrylic plate.

Further, an antireflection film made of paint 5 was formed on both sides of an acrylic plate having a siloxane-based antistatic layer formed thereon.
The low reflection material 6 formed in the same manner as described above was manufactured. This antistatic layer is made of Colcoat N-103 manufactured by Colcoat.
X is applied to a film thickness of 500 nm by a dip coating method, and cured for 1 hour at 80 ° C. and 80% RH.
Formed.

Comparative Example 1 Fluorolink T was used as a starting material.
(Perfluoropolyoxyalkyltetraol having an average molecular weight of 2,000, manufactured by Ausimont Co., Ltd.) and acrylic acid were used in the same manner as in Example 2 to obtain a perfluoropolyoxyalkyltetraol represented by the following formula (Formula 9). Acrylate was synthesized.

[0046]

Embedded image

This was used as an effective component of the paint to prepare a comparative paint in the same manner as in Example 3, and this paint was used to produce a comparative low reflection material 7 in the same manner as in Example 4.

Comparative Example 2 Cytop (manufactured by Asahi Glass Co., Ltd.), which is a conventional fluorine-containing aliphatic polymer having a ring structure in the main chain, was dissolved in perfluorooctane so as to have a concentration of 2% by weight. Adjust paint for paint.

This paint was applied to an acrylic plate having a thickness of about 100 nm and a thickness of about 2 mm by a dip coating method so that the reflectance after drying was the lowest value, and was then dried at 80 ° C. for 30 minutes. Comparative low-reflection material 8 having an anti-reflection film formed on both sides of an acrylic plate was manufactured.

(Example 5) The performance of the low reflection material obtained in Example 4, Comparative Examples 1 and 2 will be specifically described.

The antireflection property of the low-reflection material was measured with an integrating sphere using a spectrophotometer (UV-2500PC manufactured by Shimadzu Corporation).
The light reflectance at 00 nm was measured and evaluated at the lowest value of the reflectance around 600 nm.

The abrasion resistance was obtained by observing the number of sliding operations until the antireflection film peeled off when the surface of the low-reflection material was rubbed with a flannel cloth at a pressure of 500 g / cm ^2. A that is free from peeling after sliding more than 200 times
Grade, 100 to 200 times of delamination after sliding, B class, 10
When the peeling occurred with less than 0 times of sliding, it was evaluated as C class, and the results are shown in the following (Table 2).

[0053]

[Table 2]

From Table 2, it is clear that the low-reflection material produced using the antireflection coating of the present invention has excellent antireflection properties and abrasion resistance.

[0055]

As is apparent from the above description, the antireflection coating of the present invention has a three-dimensional network structure having high hardness and excellent abrasion resistance by ordinary heating or irradiation with ultraviolet rays. Is produced.

The low reflection material of the present invention is used for the antireflection film of the present invention, which is applied directly or through an antistatic layer to one or both sides of a substrate used as a window material of a display device, a projection television or the like. By polymerizing and curing the paint,
This has the effect of forming a three-dimensional network structure antireflection film having high hardness and excellent wear resistance.

[Brief description of the drawings]

FIG. 1 is a diagram showing an infrared spectroscopic analysis result of a colorless and transparent viscous liquid obtained in Example 1.

FIG. 2 is a diagram showing an infrared spectroscopic analysis result of a colorless and transparent viscous liquid obtained in Example 2.

Continued on the front page (51) Int.Cl. ⁶ Identification code FI G02B 1/11 G02B 1/10 A

Claims (6)

[Claims] 1. A perfluoropolyoxyalkyl compound represented by the following general formula (1). Embedded image (CH ₂ = CRCOOCH ₂ ) ₃ CCH ₂ -Q-CF ₂ (OC ₂ F ₄ ) p (OCF ₂ ) qO
CF ₂ -Q′-CH ₂ C (CH ₂ OCOCR = CH ₂ ) ₃ where Q is OOCNHC ₆ H ₃ (CH ₃ ) NHCO or OCO, and Q ′ is
CONHC ₆ H ₃ (CH ₃ ) NHCOO or COO, R represents H or CH ₃ , and p and q each represent an integer of 1 to 50. 2. A paint for an antireflection film, comprising at least the perfluoropolyoxyalkyl compound according to claim 1 as an active ingredient. 3. The perfluoropolyoxyalkyl compound according to claim 1 and a compound having a polymerizable unsaturated group,
3. The antireflection coating according to claim 2, which is contained as an active ingredient. 4. An active ingredient comprising the perfluoropolyoxyalkyl compound according to claim 1, a compound having a polymerizable unsaturated group, and a perfluoropolyoxyalkyl diisocyanate represented by the following general formula (Formula 2). The paint for an antireflection film according to claim 2, which is contained as a component. Embedded image OCNC ₆ H ₃ (CH ₃ ) NHCOCF ₂ (OC ₂ F ₄ ) p (OCF ₂ ) qOCF ₂ CONH
C ₆ H ₃ (CH ₃ ) NCO where p and q are integers of 1 to 50. 5. The reflection according to claim 3, wherein the compound having a polymerizable unsaturated group is a fluorine-containing or fluorine-free polyfunctional (meth) acrylate having two or more polymerizable unsaturated groups. Paint for prevention film. 6. The anti-reflection coating according to claim 2, 3, 4 or 5, applied directly or via an antistatic layer to one or both surfaces of a substrate, and polymerized and cured to obtain the base material. Low-reflection material with antireflection film formed on one or both surfaces of the material.