JPS6280041A - Mar-proof composite film and manufacture thereof - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a scratch-resistant composite film and its production -1
To J, A. [Background Art] In recent years, synthetic resin films have been widely used as base materials for decorative materials such as interior materials and light-shielding films for automobile window glasses.

Conventionally, decorative materials based on synthetic resin films include:
After simply printing on the synthetic resin film.

A transparent synthetic resin film with an adhesive layer on the back side, and a transparent synthetic resin film with an adhesive layer containing a colorant on the back side were used, but 1. Because the synthetic resin film is easily damaged, 1. Decorative materials that only have an adhesive layer on them have the disadvantage that they cannot maintain a beautiful appearance for a long period of time. For this reason, instead of mere synthetic resin films, composite films, which have a surface protective layer such as thermoplastic resin on the surface of a synthetic resin film, have come to be used as base materials for applications such as cosmetics. There is.

[Problem that the invention seeks to solve]

However, conventional composite films with a surface protective layer such as thermoplastic resin do not necessarily have sufficient surface hardness, and cannot reliably prevent scratches on the synthetic resin film. When used as a base material for a car, the surface protective layer becomes soft and easily scratched due to the rise in temperature inside a car, especially in the summer.

The present invention has been made in view of the above points, and is a scratch-resistant composite material having a surface protective layer with excellent heat resistance and a surface hardness of 9, which can be used as a base material for interior materials, light-shielding films, or other decorative materials. The purpose of the present invention is to provide a film and a method for producing the same.

[Means for solving problems]

As a result of intensive research by the present inventors to solve the above problems,
A composite film in which a three-dimensional crosslinked cured film formed by curing an i1c radiation-curable resin is provided as a surface protective layer. It has been found that it has excellent heat resistance and scratch resistance. In addition, when applying and curing an ionizing radiation-curable resin to a synthetic resin film base material, the base material is heated together with the ionizing radiation-curable resin coating layer, and ionizing radiation is irradiated to cure the coating layer to form a surface protective layer. The present inventors have discovered that by forming a ionizing radiation-curable resin, distortion caused by curing shrinkage can be prevented, and an excellent scratch-resistant composite film with excellent adhesion and surface protection can be obtained, and the present invention has been completed. .

One of the gist of the present invention is a synthetic resin film base material.

The present invention provides an abrasion-resistant composite film comprising a surface protective layer comprising a three-dimensional crosslinked cured film of an ionizing radiation-curable resin provided on one or both sides of the base material. Another gist of the present invention is to form an ionizing radiation-curable resin coating layer on one or both sides of a synthetic resin film base material, and then irradiate the base material with ionizing radiation while heating the coating layer to form an ionizing radiation-curable resin coating layer. A method for producing a scratch-resistant composite film, which comprises curing a resin to form a surface protective layer.

〔Example〕

An embodiment of the present invention will be described below with reference to the drawings.

As shown in FIG. 1, a composite film 1 of the present invention is shown.

It consists of a synthetic resin film base material 2 and a surface protection layer 3 made of a three-dimensional crosslinked cured film provided on one side of the base material 2.

As the film base material 2, polyester film, polyethylene film, polypropylene film, polyvinyl chloride film, polyvinylidene chloride film, polycarbonate film, nylon film, polystyrene film, ethylene-vinyl acetate copolymer film, etc. are used. Film, polycarbonate film, and polyvinyl chloride film are preferred.

The surface protection layer 3 is formed by curing an ionizing radiation curable resin. The ionizing radiation used for curing is Kotscroft Walton type and Bump Graffon.

Emitted from various electron beam accelerators such as co-transformer type, insulated core transformer type, linear type, dynamidron type, and high frequency type,
50-1000 Key, preferably 100-30
Examples include electron beams having an energy of 0 KeV, and ultraviolet rays emitted from light sources such as ultra-high pressure mercury lamps, high-pressure mercury lamps, low-pressure mercury lamps, carbon arcs, xenon arcs, and metal halide lamps.

These ionizing radiation-curable resins that are cured by electron beams and ultraviolet rays include unsaturated polyester, polyether acrylate, and epoxy acrylate.

Urethane acrylate, spiroacetal acrylate, polybutadiene resin, polythiol polyene resin, etc. can be used, and the curing speed can be improved.

To improve hardness, trimethylolprobant IJ R diacrylate, tripropylene glycol diacrylate, dieterenoglycol diacrylate, l, 6-
Difunctional monomers such as hexaneshiolne acrylate; and other polyfunctional monomers such as dipentaerythritol hexaacrylate can be used in combination. In addition, when ultraviolet rays are used as ionizing radiation, acetophenones, benzophenone, Michler's keto/, benzoin, benzyl methyl ketal are used as photopolymerization initiators.

Benzoyl benzoate, α-amyloki/muester,
Tetramethylthiuram monosulfide.

Thioxannones and photosensitizers such as n-butylamine, triethylamine, and tri-n-butylphosphine can be used in combination.

In the above embodiments, the case where the surface protective layer 3 was provided on one side of the base material 2 was explained, but the surface protective layer 3 can also be provided on both sides of the base material 2.

Next, a method for producing the scratch-resistant composite film of the present invention will be explained.

First, an ionizing radiation-curable resin is applied to one or both sides of the synthetic resin film base material 2. However, if the coating thickness is too thin, sufficient scratch resistance may not be obtained, and if it is too thick, the curing speed may decrease or Since distortion such as curling is likely to occur in the base material 2, 1
It is preferred to coat to a thickness of ~50μ, especially 1.5 to 10μ. The application method is blade coating method,
Gravure coating method, rod coating method, knife coating method, reverse roll coating method.

Kiss coating method, spray coach ink method.

Although offset gravure coating method etc. are adopted,
Preferred are the gravure coating method, the reverse roll coating method, and the offset gravure coating method, which depend on the degree of coating thickness and the smoothness of the coating surface.

Next, the ionizing radiation curable resin coated on the base material 2 is irradiated with ionizing radiation to cure the ionizing radiation curable resin.9 In the present invention, the ionizing radiation curable resin is heated while the base material 2 is heated together with the ionizing radiation curable resin coating layer. The surface protective layer 3 is made of a three-dimensional crosslinked cured film formed by curing the IIj curable resin.
It has excellent adhesion properties. If the heating temperature is too low, the adhesion of the surface protective layer 3 will decrease; if it is too high, if a thin film with a low softening point is used as the base material 2, the base material 2 will shrink. Easy to occur. For this reason, it is usually preferable to heat to a temperature of about 30 to 100°C, particularly preferably 40 to 80°C.

As a heating method, heating method (using hot air), method of heating by contacting with a heating device, and known heating method may be used, but in particular, the base material on which the ionizing radiation-curable resin coating layer is formed. The most preferable method for preventing shrinkage of the base material 2 is to partially or almost completely wrap the base material 2 around the surface of a hot roll and heat it.

In the present invention, the base material 2 can be cut into a desired size, but the length of the long base material 2 wound into a roll is used. While rolling out, the ionizing radiation curable resin is applied onto the base material 2, and then the process of curing the ionizing radiation curable resin while heating is performed continuously, and the long scratch-resistant composite film is continuously wound into a sheet shape. Preferably, it is manufactured.

The present invention will be explained in more detail by giving specific examples below.

Example 1 A 50μ thick polyester film (
A polyester acrylate-based ultraviolet curable resin paint (Seikabeam PHC, manufactured by Dainichiseika Chemical Co., Ltd.) was coated on one side of the sample by a gravure coating method using Toshi Lumirror T-60). Type 3a coatings with coating thicknesses of 1μ, 2μ, and 10μ were prepared. Next, each film substrate coated with an ultraviolet curable resin coating was wound approximately halfway around the surface of a roll rotating at a surface speed of 5 m/min, and was heated by the roll and irradiated with ultraviolet rays to cure the ultraviolet curable resin. Ultraviolet irradiation was carried out at 160 W/set at 12.5 cm above the roll.
The experiment was carried out using two ultraviolet lamps with cm output. In addition, the heating by the roll was performed at a roll surface temperature of 30℃, 50℃, 1
The test was carried out at 00°C.

Scratch resistance 1 of each composite film obtained as above
When testing the adhesion of the protective layer in Table [III] under the following conditions, it was found that UV-curable resin paints with a coating thickness of 1μ tended to have 1)2+ adhesion a little more easily than those with a coating thickness of 2μ and 10μ. In addition, although it was observed that the adhesion of the surface protective layer on rolls heated at 30°C tended to be slightly lower than those heated at 50°C and 100'C, both had sufficient scratch resistance. The protective layer had excellent adhesion.

Scratch resistance test conditions The surface of the surface protective layer was coated with steel wool #0O00 for 20 minutes.
It was rubbed several times and observed for scratches.

Adhesion test conditions for surface protective layer Nichiban cello tape (industrial type) with a width of 24
It was pasted onto a surface protective layer that had been cyclically cut using a cutter, and the surface was rubbed back and forth with a cotton cloth 10 times to make it adhere. Thereafter, this was left in a room for 1 minute, and when the tape was suddenly pulled upward from the front side and peeled off, it was observed whether or not the surface protection layer 9 was stuck to the tape and peeled off.

Comparative Example 1 A film base coated with an ultraviolet curable resin coating to a thickness of 1 μ, 2 μ, and 10 μ in the same manner as in Example 1 was wound around the same roll surface as in Example 1, and the film was coated without heating the roll. The ultraviolet curing resin was cured by irradiating ultraviolet rays at a roll surface temperature of 10° C. and 20° C., respectively.

Scratch resistance of each composite film obtained as above 9
The adhesion of the surface protective layer was tested under the same conditions as in Example 1, but it was found that the scratch 2 surface protective layer peeled off severely and 1) it scratched the surface protective layer had poor adhesion.

〔Effect of the invention〕

As explained above, the composite film of the present invention has a surface protective layer consisting of a three-dimensional cross-linked cured film made by curing ionizing radiation-curable resin, so the surface protective layer has excellent heat resistance and is resistant to scratches. When the composite film of the present invention, which has scratch resistance, is used as a base material for decorative materials, the aesthetic appearance of decorative materials such as interior materials and light-shielding films can be maintained for a long period of time. In addition, the method for manufacturing the scratch-resistant composite film of the present invention employs a method in which the ionizing radiation-curable resin coating layer is hardened, and the base material is heated together with the coating layer while irradiating ionizing radiation. Distortion due to curing shrinkage of the curable resin is prevented, and a soaked scratch-resistant composite film having a surface protective layer with excellent adhesion can be produced.

[Brief explanation of drawings]

The drawings show one embodiment of the present invention, and FIG.
FIG. 2 is a longitudinal cross-sectional view showing an embodiment of the scratch-resistant composite film JAITi'. 1-------1 Scratch resistant composite film 2---------
−1 Synthetic resin film base material 3 −−−−Surface protective layer Patent applicant: Dai Nippon Printing Co., Ltd. Agent Patent attorney: Hosoi
Isamu 1: Akira Kieijima/l raw λ hikiaisuru A 2: Gope 14 quotient 1 μm charge 3: Protect your friend A

Claims (3)

[Claims] (1) A scratch-resistant composite film comprising a synthetic resin film base material and a surface protective layer made of a three-dimensional crosslinked cured film of an ionizing radiation-curable resin provided on one or both sides of the base material. . (2) After forming an ionizing radiation-curable resin coating layer on one or both sides of a synthetic resin film base material, ionizing radiation is irradiated while heating the base material together with the coating layer to harden the ionizing radiation-curable resin and surface A method for producing a scratch-resistant composite film, which comprises forming a protective layer. (3) The method for producing a scratch-resistant composite film according to claim 2, wherein the base material on which the ionizing radiation-curable resin coating layer is formed is at least partially wound around the surface of a hot roll and heated.