JP2012126804A - Ultraviolet-curable resin composition, and glaring-proof hardcoat film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a film prevented from flaws which may be developed by pressing with a touch-pen, good in writing touch/smoothness, and suppressed from external light mirroring.SOLUTION: An ultraviolet-curable resin composition comprising a polyfunctional (meth)acrylate and an organic and/inorganic filler(s) is provided, which contains no leveling agent and uses at least one selected from the group consisting of toluene, butyl acetate and 1-butanol as a dilutive solvent. A plastic film is coated with the ultraviolet-curable resin composition and irradiated with ultraviolet rays.

Description

  The present invention relates to a film suitable for a transparent touch panel or the like, and more particularly to an antiglare hard coat film that prevents glare, has good writing with a touch pen, and has high hardness and flexibility.

  In recent years, liquid crystal display devices have attracted attention as image display elements, and are used in portable electronic notebooks, information terminals, car navigation systems, personal computers, and the like. As these input devices, those having a transparent touch panel on a liquid crystal display element are known, and when the touch-side panel surface is pressed with a finger or a pen, necessary information is input as an electrical signal. The result is displayed on the screen. Further, in a system equipped with a touch panel, a more intuitive operation is possible by directly inputting characters and figures using a touch pen or the like.

  However, the pressing operation with the pen causes scratches on the screen, resulting in poor visibility. A film with a hard coat treatment is used to suppress scratches on the screen, but general hard coat agents have a leveling function that lowers the surface tension to improve the surface appearance during coating. Since the agent was used, the film surface was slippery and difficult to write compared to writing on paper.

  In addition, the display device described above is often used outdoors, and there are many cases in which reflection of external light becomes a problem, and external light is diffusely reflected by providing irregularities on the surface, for example, by kneading a filler into a coating agent. Anti-glare treatment may be performed.

However, when unevenness is formed on the film surface by coating, fillers such as inorganic fine particles such as silica and titanium oxide, and organic fine particles such as acrylic beads and styrene beads are often kneaded, and the filler settles during coating storage or coating. It was difficult to stabilize the coating appearance.
JP 2010-70602 A

  The present invention relates to a film suitable for a transparent touch panel and the like, and prevents the occurrence of glare, the antiglare hard coat film for a touch panel having a good writing feeling with a touch pen, and the film having a good coating appearance with less filler settling It is related with the coating agent for an object.

The present invention has been studied in view of such a situation, and an object thereof is to provide a film that prevents scratches caused by pressing with a touch pen by an operator, has good writing quality, and suppresses reflection of external light. To do.
The present invention is an ultraviolet curable resin composition containing a polyfunctional (meth) acrylate and an organic and / or inorganic filler, does not contain a leveling agent, and consists of toluene, butyl acetate and 1-butanol as a diluent solvent. It is an ultraviolet curable resin composition characterized by using at least one selected from the group.
In the present specification, “(meth) acrylate” means “acrylate or methacrylate”.

  The ultraviolet curable resin composition of the present invention can be coated with good appearance without streaking by selecting a diluting solvent without containing a leveling agent.

  Further, since the filler does not settle into a hard cake over time and the filler does not settle easily during coating, it is suitable for stable production of a film.

  Moreover, the fine unevenness | corrugation formed with the compound containing the (meth) acrylate containing a filler turns into a layer which disperse | distributes reflected light, and can prevent reflection of external light.

  Furthermore, in the film coated with the ultraviolet curable resin composition of the present invention, since the surface tension of the coating liquid is reduced and the so-called leveling agent that exhibits the wetting and spreading effect is not used, the slipperiness is not adversely affected. It can be applied to touch panels with good writing quality.

  Examples of the polyfunctional (meth) acrylate used in the present invention include dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, and trimethylolpropane triacrylate.

  Examples of the fine particles used for forming the fine unevenness used in the present invention include inorganic fine particles such as silica and organic fine particles such as styrene, urethane, and acrylic.

  Examples of the initiator used for polymerization by ionizing radiation of ultraviolet rays and electron beams include 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, Carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 4,4′-dimethoxybenzophenone, 4,4′-diaminobenzophenone, Michler's ketone, benzoin propyl ether, benzoin ethyl ether, benzyldimethyl ketal, 1- (4-isopropylphenyl) 2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, thioxanthone, diethylthioxanthone, 2-i Propylthioxanthone, 2-chlorothioxanthone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis- (2 , 6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide and the like, and as commercially available products Irgacure 127, 184, 369, 651, 500, 891, 907, Darocur 1173, TPO (manufactured by BASF Japan Ltd.) , Product name).

  In addition, you may mix | blend what is called a rheology control agent which has the effect of constructing a needle-like crystal and raising a viscosity.

  As a means for applying the ultraviolet curable resin composition to the film, it may be applied by a generally known method such as reverse roll coater, gravure coater, knife coater, or screen printing and cured.

  In the present invention, when at least one selected from the group consisting of toluene, butyl acetate and 1-butanol is used as a diluent solvent, sedimentation of fillers, particularly silica fine particles, can be prevented, resulting in coating unevenness and streaks. The appearance is good.

  The film used in the present invention is not particularly limited as long as it is a transparent plastic film. Among them, a polyester film that has been biaxially stretched from the viewpoint of weather resistance, processability, dimensional stability, etc. is preferably used. The thickness of the film may be approximately 25 μm to 250 μm.

For the purpose of improving the adhesion to the ultraviolet curable resin composition, the film is subjected to surface roughening treatment such as primer treatment, sandblasting method, solvent treatment method, corona discharge treatment, chromic acid treatment, ozone Surface treatment such as surface oxidation treatment such as ultraviolet irradiation treatment can be performed.
EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example and a comparative example, a specific example is shown and it does not specifically limit to these.

Dipentaerythritol hexaacrylate (trade name: KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd., solid content: 100%) 900.00 parts by weight and silica (trade name: Nipsil E-220A, manufactured by Tosoh Silica Co., Ltd.) 100.00 3 parts by weight, a dispersant (trade name: DISPERBYK184, manufactured by Big Chemie Japan Co., Ltd.) 3.00 parts by weight, and a rheology control agent (trade name: BYK410, manufactured by Big Chemie Japan Co., Ltd.) 2.00 parts by weight are mixed. Dispersion was performed using the present roll to obtain a dispersion (A). In 411.81 parts by weight of the above dispersion (A), 14.23 parts by weight of polyfunctional (meth) acrylate (trade name: CN2303, manufactured by Sartomer Japan Co., Ltd., solid content 100%), photoinitiator (trade name) : IRGACURE184, manufactured by BASF Japan Ltd., trade name) 23.60 parts by weight, HALS (polymer light stabilizer) as TINUVIN152, manufactured by BASF Japan Ltd., trade name) 2.31 parts by weight, toluene 500.00 After mixing the weight parts, foreign matter was removed with a # 200 stainless mesh to obtain a coating liquid (B).
The coating solution (B) was applied to a 188 μm PET (polyethylene terephthalate) film (trade name: Lumirror U46, manufactured by Toray Industries, Inc.) with a # 5 bar coater, dried for 2 minutes in an 80 ° C. hot air dryer, and then 300 mJ The film was cured by irradiating with / cm ² of ultraviolet rays to obtain an antiglare film.

  In Example 1, it implemented similarly except having changed 500.00 weight part of toluene into butyl acetate.

  In Example 1, it implemented similarly except having changed 500.00 weight part of toluene into 1-butanol.

  The same procedure as in Example 1 was carried out except that 500.00 parts by weight of toluene were changed to 166.66 parts by weight of toluene, 166.66 parts by weight of 1-butanol, and 166.67 parts by weight of butyl acetate.

  In Example 1, it implemented similarly except having changed 500.00 weight part of toluene into 250.00 weight part of toluene, and 250.00 weight part of butyl acetate.

  In Example 1, it implemented similarly except having changed 500.00 weight part of toluene into 250.00 weight part of 1-butanol and 250.00 weight part of butyl acetate.

To 474.09 parts by weight of the dispersion (A) of Example 1, 23.60 parts by weight of a photoinitiator (IRGACURE184, manufactured by BASF Japan Ltd., trade name), TINUVIN152 as HALS (polymer light stabilizer), BASF Japan Co., Ltd., trade name) 2.31 parts by weight, toluene 166.66 parts by weight, 1-butanol 166.66 parts by weight, butyl acetate 166.67 parts by weight and then mixed with a # 200 stainless mesh A coating liquid (C) was obtained.
The coating solution (C) was applied to a # 5 bar coater on a 188 μm PET (polyethylene terephthalate) film (trade name: Lumirror U46, manufactured by Toray Industries, Inc.), dried for 2 minutes in an 80 ° C. hot air dryer, and then 300 mJ / The film was cured by irradiating cm ² ultraviolet rays to obtain an antiglare film.

  In Example 7, it implemented similarly except having excluded 166.66 weight part of toluene 500.00 weight part, 1-butanol, and butyl acetate.

  In Example 8, it carried out similarly except having made 500.00 weight part of toluene into 500.00 weight part of butyl acetate.

  In Example 8, it carried out similarly except having made 500.00 weight part of toluene into 500.00 weight part of 1-butanol.

Comparative Example 1
In Example 1, 500.00 parts by weight of toluene was changed to 150.00 parts by weight of toluene and 350.00 parts by weight of isobutyl alcohol, and 0.5 part by weight of BYK310 (manufactured by Big Chemie Japan Co., Ltd.) as a silicone-based leveling agent. It carried out similarly except having added.

Comparative Example 2
In the comparative example 1, it carried out similarly except having changed BYK310, 0.5 weight part into 1 weight part of BYK325 (Bic Chemie Japan KK make, silicone type leveling agent).

Comparative Example 3
In the comparative example 1, it carried out similarly except having changed BYK310 and 0.5 weight part to BYK333 (Bic-Chemie Japan Co., Ltd. make, silicone type leveling agent) 0.5 weight part.

Comparative Example 4
In Example 1, it implemented similarly except having changed 500.00 weight part of toluene into 500.00 weight part of methyl ethyl ketone.

Comparative Example 5
In Example 1, it implemented similarly except having changed 500.00 weight part of toluene into 500.00 weight part of isobutyl alcohol.

Comparative Example 6
In Example 1, it implemented similarly except having changed 500.00 weight part of toluene into 500.00 weight part of propylene glycol monomethyl ether acetate.

Comparative Example 7
In Example 1, it implemented similarly except having changed 500.00 weight part of toluene into 500.00 weight part of methanol.

Comparative Example 8
In Example 1, it implemented similarly except having changed 500.00 weight part of toluene into 500.00 weight part of ethanol.

Comparative Example 9
In Example 1, it implemented similarly except having changed 500.00 weight part of toluene into 500.00 weight part of isopropyl alcohol.

Comparative Example 10
In Example 1, it implemented similarly except having changed 500.00 weight part of toluene into 500.00 weight part of n-pentanol.

Comparative Example 10
In Example 1, it implemented similarly except having changed 500.00 weight part of toluene into 500.00 weight part of ethyl acetate.

Pencil hardness: Based on JIS K5600-5-4, evaluation was performed with a load of 750 g. When the test was conducted 5 times and there were no scratches 4 times, it was indicated as “4/5”. Also, 3/5 or more is “◯”, and less than 2/5 is “×”.

  Appearance: The presence or absence of bar coater streaks and coating unevenness was visually confirmed, and those having no streaks or coating unevenness were evaluated as “◯”, and those having streaks or coating unevenness were evaluated as “x”.

  Written: Place the film on a glass plate, scratch the coated surface with a touch pen made of polyacetal, evaluate it as “○” if it feels similar to writing on a paper with a pencil, and “×” if it feels slippery did.

  Sedimentation stability: Put the coating solution in a glass sample bottle to a height of 3 cm, and evaluate that there is no transparent part of the supernatant after 2 hours as “◯” and that with a transparent part as “x” did. Moreover, the case where the transparent part after 24 hours was less than 1.0 mm was evaluated as “◯”, 1.0 mm or more and less than 2.0 mm as “Δ”, and 2.0 mm or more as “×”.

  Hard cake: The sample used in the sedimentation stability test was allowed to stand at room temperature for 1 month. The case where the settled fine particles were redispersed was evaluated as “◯”, and the case where the particles were not redispersed was evaluated as “x”.

Haze: Based on JIS K7136, evaluation was performed by “Haze Guard II” manufactured by Gardner.

Claims (2)

In the ultraviolet curable resin composition containing a polyfunctional (meth) acrylate and an organic and / or inorganic filler, it does not contain a leveling agent and is selected from the group consisting of toluene, butyl acetate and 1-butanol as a diluent solvent. An ultraviolet curable resin composition comprising at least one kind. An antiglare hard coat film obtained by applying the ultraviolet curable resin composition according to claim 1 to a plastic film and irradiating with ultraviolet rays.