JP2009161609A - Hard coat film and printed matter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hard coat film having a hard coat layer having scratch preventing capability and printing suitability and to provide printed matter obtained by printing on the film. <P>SOLUTION: The hard coat film consists of (i) a substrate and (ii) a hard coat layer formed by coating a coating composition on the substrate surface and curing it by UV irradiation. The coating composition contains a photoinitiator, a (meth)acrylate monomer and a (meth)acrylic monomer having an alkylamide group and/or a phosphate (meth)acrylate. The ratio by mass of the formulation amount of the (meth)acrylate monomer and that of the (meth)acrylic monomer having an alkylamide group and/or phosphate (meth)acrylate is 100:5-100:50. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a hard-coded film and a printed body obtained by printing on the film.

  In order to prevent scratches on the surface of a plastic or plastic film, a hard coat film obtained by applying a hard coat to a film is generally used. Moreover, the graphic film which printed on the surface of the film is used.

A hard coat film having a hard coat layer coated with a curable composition containing a photocurable substance and an oligomer type photopolymerization initiator on the surface of a substrate and cured by light irradiation is disclosed (for example, Patent Document 1). The hard coat film can be used as a protective film for a liquid crystal display device, a CRT display device, a plasma display device, an electronic display device, a light emitting diode display device, an EL display device, or a display device component such as a touch panel. It can be used as a functional film. Furthermore, it is excellent in the adhesiveness after heat processing between a hard-coat layer and a base material, and can suppress the gas emitted at the time of heat processing.
However, detailed studies have not yet been made on printing on the surface of the hard coat layer or ink jet printing with an ultraviolet curable ink on the surface of the hard coat layer.
Under such a background, there is a demand for a hard coat film that has an ability to prevent scratches and is suitable for printing, in particular, a hard coat film with good ink adhesion by ink jet printing using an ultraviolet curable ink or the like.

Japanese Patent Laid-Open No. 2002-256092

  An object of the present invention is to provide a hard coat film having a hard coat layer having scratch-preventing performance and printability, and a printed body obtained by printing the film.

That is, the present invention comprises (i) a base material, and (ii) a hard coat layer obtained by applying a coating composition to the surface of the base material and curing it by ultraviolet irradiation.
The coating composition contains a photopolymerization initiator, a (meth) acrylate monomer, and a (meth) acryl monomer having an alkylamide group and / or a phosphate (meth) acrylate,
The mass ratio of the blending amount of the (meth) acrylate monomer and the blending amount of the (meth) acrylic monomer and / or phosphate (meth) acrylate having the alkylamide group is 100: 5 to 100: 50. A hard coat film is provided.

  Furthermore, this invention provides the printed body which printed on the surface of the hard-coat layer of the said hard-coat film.

  The hard coat film of the present invention is a film in which a hard coat layer is laminated on a substrate.

  Although the said base material is not specifically limited, For example, films, such as a polyester resin, a polyethylene resin, a polypropylene resin, a polystyrene resin, or a polycarbonate resin, can be mentioned.

  The thickness of the substrate is not particularly limited, and can be, for example, about 10 μm to about 350 μm, about 25 μm to about 300 μm, or about 50 μm to about 250 μm. The base material can be subjected to a commonly performed surface treatment such as a primer treatment.

  The hard coat layer of the present invention first comprises a coating composition containing a photopolymerization initiator, a (meth) acrylate monomer, and a (meth) acryl monomer having an alkylamide group and / or a phosphate (meth) acrylate. It is a layer applied on the surface of a substrate and subsequently cured by ultraviolet irradiation. Only one of the (meth) acrylic monomer having an alkylamide group and the phosphate (meth) acrylate may be contained, or both of them may be contained.

  A conventionally well-known thing can be used as said photoinitiator, and it is not specifically limited. For example, acetophenones, benzophenone, Michler's ketone, benzoin, benzylmethyl ketal, benzoylbenzoate, α-acyloxime ester, 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, or thioxanthone Can do. These may be used alone or in combination of two or more.

  The blending amount of the photopolymerization initiator is not particularly limited, and a commonly used amount can be adopted. For example, when the entire coating composition is 100 parts by mass, it can be about 0.5 parts by mass to about 5.0 parts by mass.

  The (meth) acrylate monomer is not particularly limited as long as it is a monomer curable by ultraviolet irradiation. In the present specification, “(meth) acrylate” means acrylate or methacrylate.

Examples of the (meth) acrylate monomer include urethane acrylate, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, hexanediol di ( (Meth) acrylate, trimethylolethane di (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate,
Examples thereof include pentaerythritol tetra (meth) acrylate, pentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glyceryl tri (meth) acrylate, and bisphenol A ethylene oxide-modified di (meth) acrylate.

  The blending amount of the (meth) acrylate monomer is not particularly limited, and a commonly used amount can be adopted. For example, when the entire coating composition is 100 parts by mass, it can be about 60 parts by mass to about 95 parts by mass.

  The (meth) acrylic monomer having an alkylamide group of the present invention means a (meth) acrylic monomer having an acrylamide group. For example, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, ethylmethyl (meth) acrylamide, dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylamide, or isopropyl (meth) Examples include acrylamide.

  Examples of the phosphate (meth) acrylate of the present invention include phosphoric acid (meth) acrylate, phosphoric acid di (meth) acrylate, ethylene oxide-modified phosphoric acid di (meth) acrylate, and the like.

  In the present invention, the blending amount of the (meth) acrylate monomer and the blending amount of the (meth) acrylic monomer having an alkylamide group and / or the phosphate (meth) acrylate is about 100: about 5 by mass ratio. To about 100: 50. By setting it as this mass ratio, the hard coat film which has a hard-coat layer suitable for the printing by an ultraviolet curable type jet can be obtained.

  The hard coat layer of the present invention may further contain a (meth) acrylate oligomer in the coating composition. The (meth) acrylate oligomer can have the monomer exemplified as the (meth) acrylate monomer as a constituent component.

When the hard coat layer of the present invention further contains a (meth) acrylate oligomer, (i) the total amount of the (meth) acrylate monomer and the (meth) acrylate oligomer and the alkylamide group (meta) ) The mass ratio of the acrylic monomer is about 100: about 5 to about 100: about 50,
(Ii) The mass ratio between the total amount of the (meth) acrylate monomer and the (meth) acrylate oligomer and the amount of the phosphate (meth) acrylate is about 100: about 5 to about 100: about 50, and
(Iii) The sum of the blending amounts of the (meth) acrylate monomer and the (meth) acrylate oligomer, and the sum of the blending amounts of the (meth) acrylic monomer having the alkylamide group and the phosphate (meth) acrylate The mass ratio can be about 100: about 5 to about 100: about 50.
By setting it as this mass ratio, the hard coat film which has a hard-coat layer suitable for the printing by an ultraviolet curable type jet can be obtained.

  The thickness of the hard coat layer of the present invention is not particularly limited, and can be, for example, about 0.1 μm to about 10 μm, about 0.5 μm to about 5 μm, or about 1 μm to about 3 μm.

  The printed body of the present invention is obtained by printing on the outer surface of the hard coat layer of the hard coat film of the present invention.

  The printing can be performed using a conventionally known method and is not particularly limited. For example, ink jet printing using various conventionally known ultraviolet curable inks can be used.

  The hard coat film of the present invention can be obtained as follows. First, the components of the hard coat layer are mixed with or without using a solvent to produce a coating composition. Subsequently, the composition obtained is applied to the surface of the base material by a conventionally known method, then cured by irradiation with ultraviolet rays, and further dried when a solvent is used.

  As a method for applying the coating composition, a conventionally known coating method using a wire bar, a knife, a bar coater or the like can be used.

  The ultraviolet irradiation can be performed using an ultraviolet irradiation device such as a UV oven. At this time, ultraviolet irradiation may be performed while filling with nitrogen as necessary.

  The printed body of the present invention can be obtained by printing on the outer surface of the hard coat layer of the hard coat film obtained as described above by inkjet printing using a conventionally known ink.

  The hard coat film of the present invention can be used as a protective film or functional film for mud, doors, walls, vehicles, or floors. Furthermore, the hard coat film of the present invention can be used as a protective film or a functional film for various display devices such as a liquid crystal display device, a CRT display device, an LED display device, or an EL display device. Alternatively, the hard coat film of the present invention can be formed into a graphics film by printing on the film surface by inkjet or the like. In this case, the graphics film can be applied to a mud, a door, a wall, a vehicle, a floor, or the above various display devices.

  The printed body of the present invention can also be applied to various displays such as a mad, door, wall, vehicle, or floor, or a liquid crystal display, a CRT display, or an EL display.

  The hard coat film or printed body of the present invention can be provided with an adhesive layer on the surface of the substrate opposite to the hard coat layer. As the pressure-sensitive adhesive layer, a conventionally known pressure-sensitive adhesive such as an acrylic pressure-sensitive adhesive, a silicon pressure-sensitive adhesive, or a rubber pressure-sensitive adhesive can be used. Known additives can be blended as necessary.

  A release paper (liner) can be provided on the outer surface of the pressure-sensitive adhesive layer, that is, the surface opposite to the surface in contact with the substrate. Such release paper may be one generally used in the field of adhesive tape and the like, and is not limited to a specific member. Suitable release papers include, for example, plastic materials such as paper, polyethylene, polypropylene, polyester, or cellulose acetate, or paper or other materials coated or laminated with such plastic materials. . These release papers have irregularities on the surface, and the irregularities on the surface of the pressure-sensitive adhesive layer can be provided by the irregularities. These release papers may be used as they are, but can be used after being treated with a silicone treatment or other methods to improve the release characteristics.

Example 1
A mixture of urethane acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, and a photopolymerization initiator (1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide) (KAYANOVA FOP4000 manufactured by Nippon Kayaku Co., Ltd.) ) Was mixed with 100 parts by weight of solid content and 7 parts by weight of N, N-dimethylacrylamide (manufactured by Kojin Co., Ltd. DMAA) to prepare a coating composition. The obtained coating composition was applied to the easy-adhesive surface of a 100 μm thick polyester film (registered trademark Cosmo Shine A4100 manufactured by Toyobo Co., Ltd.) whose one side was easy-adhesive treated with a wire bar, and UV oven (Fusion UV A hard coat film was prepared by curing with a system VPS6 and Hbulb). Curing was performed under nitrogen filling with an irradiation amount of 0.7 W / cm ² (measured with a registered trademark UVICURE Plus manufactured by EIT). The thickness of the hard coat layer after curing was 2 μm. In this way, a hard coat film having a printable hard coat layer was obtained.

Example 2
A hard coat film was prepared in the same manner as in Example 1 except that 7 parts by mass of ethylene oxide-modified phosphoric acid acrylate (KAYAMER PM-21 manufactured by Nippon Kayaku Co., Ltd.) was used instead of N, N-dimethylacrylamide. The thickness of the hard coat layer after curing was 2 μm. In this way, a hard coat film having a printable hard coat layer was obtained.

Examples 3-6
KAYANOVA FOP4000 (manufactured by Nippon Kayaku Co., Ltd.) was mixed with 100 parts by mass of solid content, DMAA (manufactured by Kojin Co., Ltd.), and KAYAMER PM-21 (manufactured by Nippon Kayaku Co., Ltd.) to prepare a hard coat composition. . The content of each component is as shown in Table 1. The obtained hard coat composition was applied to a substrate and cured in the same manner as in Example 1 to obtain a hard coat film. The thickness of the hard coat layer after curing was 2 μm. In this way, a hard coat film having a printable hard coat layer was obtained.

Examples 7-8
Mixture of pentaerythritol diacrylate, hexanediol diacrylate, and photoinitiator (UVHC8558 manufactured by Momentive Performance Materials Japan), DMAA (manufactured by Kojin Co., Ltd.), and KAYAMER PM-21 (Nippon Kayaku Co., Ltd.) To produce a hard coat composition. The content of each component is as shown in Table 1. Subsequently, as in Example 1, it was applied to a substrate and cured to prepare a hard coat film. The thickness of the hard coat layer after curing was 2 μm. In this way, a hard coat film having a printable hard coat layer was obtained.

Comparative Example 1
A 100 μm-thick polyester film (registered trademark Cosmo Shine A4100 manufactured by Toyobo Co., Ltd.) whose one surface was easily adhered was evaluated.

Comparative Examples 2-6
UVHC8558 (made by Momentive Performance Materials Japan), DMAA (made by Kojin Co., Ltd.), and KAYAMER PM-21 (made by Nippon Kayaku Co., Ltd.) are mixed as shown in Table 1 to create a hard coat composition. A hard coat film was prepared in the same manner as in Example 1. The thickness of the hard coat layer after curing was 2 μm. In this way, a hard coat film having a hard coat layer was obtained.

Comparative Example 7
UVHC8558 (made by Momentive Performance Materials Japan) was applied to the easy-adhesive surface of a 100 μm thick polyester film (registered trademark Cosmo Shine A4100 manufactured by Toyobo Co., Ltd.) with one side easy-adhesive treated with a wire bar. A hard coat film was obtained by curing under the same conditions as in Example 1. The thickness of the hard coat layer after curing was 2 μm. In this way, a hard coat film having a hard coat layer was obtained.

Steel Wool Test Steel wool # 00000 loaded with a 1000 g weight was placed on each film obtained in Examples 1-8 and Comparative Examples 1-7. Subsequently, the weighted steel wool was reciprocated 10 times on the surface of the film. The results are shown in Table 2. The results are shown in Table 2 when the scratches were seen visually, and when the scratches were not seen visually.

UV Ink Adhesion Test UV curable ink (PressVu200 UVC white ink, manufactured by Vutek) was cured on the films obtained in Examples 1 to 8 and Comparative Examples 1 to 7. The size of the obtained film was 210 mm × 300 mm, and the thickness of the cured ink was 10 μm. The obtained film was cut into a size of 150 mm × 70 mm, an adhesive was applied, and it was attached to a 150 mm × 70 mm aluminum plate with a squeegee. Subsequently, each was cured for 5 days under three conditions: 1) 20 ° C., 2) 65 ° C., 3) 65 ° C., and relative humidity (RH) 95%. After curing, 6 incisions with a length of about 10 mm are put into the film (test piece) at intervals of 1 mm, and then further, 6 incisions with a length of about 10 mm are intersected at right angles with the 6 incisions. I put it in. Then, Sumitomo 3M Co., Ltd. mending tape # 810 was affixed to these test pieces, crimped with a squeegee, and peeled off by hand. The ratio of the area where the ink layer remained was visually confirmed, and the results are shown in Table 2. In all three conditions, the case of 70% or more was accepted, and even if one of the three conditions was less than 70%, the case was rejected.

Claims (5)

(I) a base material, and (ii) a hard coat layer obtained by applying the coating composition to the surface of the base material and curing it by ultraviolet irradiation,
The coating composition contains a photopolymerization initiator, a (meth) acrylate monomer, and a (meth) acryl monomer having an alkylamide group and / or a phosphate (meth) acrylate,
The mass ratio of the blending amount of the (meth) acrylate monomer and the blending amount of the (meth) acrylic monomer and / or phosphate (meth) acrylate having the alkylamide group is 100: 5 to 100: 50. Hard coat film.   The hard coat film according to claim 1, wherein the hard coat layer further contains a (meth) acrylate oligomer. The total amount of the (meth) acrylate monomer and the (meth) acrylate oligomer;
The hard coat film according to claim 2 whose mass ratio with the compounding quantity of the (meth) acryl monomer which has said alkylamide group, and / or said phosphate (meth) acrylate is 100: 5-100: 50.   The printed body which printed on the surface of the hard-coat layer of the hard-coat film as described in any one of Claims 1-3.   The printed body according to claim 4, wherein the printing is printing obtained by inkjet printing using an ultraviolet curable ink.