JPH0532809A - Laminated body and manufacturing method thereof - Google Patents

Abstract

(57) [Summary] [Object] The present invention provides a laminate having a polyethylene terephthalate film or sheet as a base material and having excellent coating adhesion. [Structure] As a primer layer, an ultraviolet or electron beam curable resin having a terephthalic acid or phthalic acid ester structure in the main chain structure and a hydrogen-bonding functional group is used as a main agent, and as a side agent if necessary It is composed of a UV or electron beam curable resin composition to which a monofunctional acrylate having a hydrogen-bonding functional group is added, and is composed of a mixed system of oligoester acrylate and urethane acrylate having at least two acrylate groups as the surface protective layer,
Further, if necessary, the surface of the polyethylene terephthalate film or sheet before coating is activated to increase the bonding force at the coating interface such as hydrogen bonding force or intermolecular force.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminate having polyethylene terephthalate as a base material and a method for producing the same.

[0002]

2. Description of the Related Art In recent years, polyethylene terephthalate has been
It has come to be used in all fields. Widely used reasons include ease of molding, ease of post-processing,
Low cost mass productivity, light weight, easy coloring, anti-rust, antiseptic, impact resistance, electrical insulation, chemical resistance such as water / chemical resistance, easy transparent molding, etc. . However, it also has some drawbacks, one of which is its vulnerability. Not only is this scratched, but dust is also attached to the scratches, and the aesthetic appearance of the product is impaired. Therefore, improvement of surface scratch resistance is widely desired.

Generally, as a method for imparting scratch resistance to the surface of a plastic, there is a method of applying a coating agent having scratch resistance after curing on the surface and curing it to form a protective layer. The coating agent is classified into three types: a room temperature curable type, a thermosetting type, and a radiation curable type such as an ultraviolet ray or an electron beam.

The room-temperature curing type requires a certain amount of time for curing, and therefore tends to cause problems such as adhesion of dust to the surface during the curing process and is not very efficient in production. The thermosetting type may cause deformation of the plastic material as a base material by heating. The radiation-curable type using ultraviolet rays or electron beams takes a very short time to cure and does not heat the substrate so much. Therefore, the application of a scratch-resistant protective layer using a radiation-curable coating agent such as ultraviolet rays or electron beams has been widely used, and the method using ultraviolet rays has been widely used, especially because of the versatility of the apparatus.

[0005]

However, since the polyethylene terephthalate film or sheet had a relatively stable surface, that is, a chemically inert surface, it was formed using an ultraviolet ray or electron beam curable resin composition. There is a drawback that the adhesive force at the coating interface between the protective coating film and the polyethylene terephthalate film or sheet is weak, that is, the adhesiveness of the coating film is poor and peeling is easy. The present invention is for solving such a problem.

That is, the present invention is based on the above-mentioned problems, and a laminate having a protective coating film excellent in coating film adhesion formed on a polyethylene terephthalate substrate (which is often in the form of a film or a sheet). The purpose is to provide.

[0007]

Specifically, the surface of a polyethylene terephthalate substrate has a main chain structure of terephthalic acid or an ester structure of phthalic acid, and an ultraviolet ray or an electron having a hydrogen-bonding functional group. A primer layer composed of a UV-curable or electron beam-curable resin composition containing a monofunctional acrylate having a hydrogen-bonding functional group as a main agent and a ray-curable resin as a main agent, and at least an acryloyl group. It is a laminate having a surface protection layer made of a mixed system of two or more oligoester acrylates and urethane acrylates.

In order to form such a laminate, after the surface of polyethylene terephthalate is activated, it has terephthalic acid or an ester structure of phthalic acid in the main chain structure and has a hydrogen-bonding functional group. A primer layer composed mainly of an ultraviolet or electron beam curable resin composition is applied, and then a surface protective layer composed of a mixture of oligoester acrylate and urethane acrylate having at least two acryloyl groups is applied, and the ultraviolet or electron A method for producing a laminate, which is characterized by being cured by irradiation with rays, is adopted. Of course, it is a desirable embodiment to add a monofunctional acrylate having a hydrogen-bonding functional group to the primer layer as an auxiliary agent.

The ultraviolet and electron beam curable resins having a terephthalic acid or an ester structure of phthalic acid in the main chain structure and having a hydrogen bonding property include the following.

CH ₂ = CHCOO- (a)-(b)-(c) CH ₂ = CHCOO- (a)-(b)-(c) -OH CH ₂ = CHCOO- (a)-(b)- _{(c) -COOH CH 2 = CHCOO-} (a) - (b) - (a ') - OCOCH = CH 2

[0011] However, (a)-(b) and (b)-(c) are ester bonds.

Monofunctional UV or electron beam curable resins having hydrogen-bonding functional groups include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate,
2-hydroxybutyl acrylate, etc. may be mentioned.

Examples of the activation treatment of the surface of the polyethylene terephthalate film and sheet include flame treatment, ozone treatment, corona treatment, ultraviolet irradiation treatment, electron beam irradiation treatment, radiation irradiation treatment, plasma treatment and the like.

Examples of the coating method of the coating agent include an air doctor coater, a blade coater, a rod coater, a knife coater, a squeeze coater, a reverse roll coater, a gravure coater, a kiss coater, and spray coating. The coating amount is such that the film thickness after curing is about 1 to 50 μm, preferably about 1 to 10 μm.

As a UV irradiation device, a high pressure mercury lamp,
Examples of the metal halide lamp include, but are not particularly limited to. Further, as the irradiation device, a cold mirror, an infrared cut filter, or the like may be attached. As an electron beam irradiation device, an area beam system, a curtain beam system,
A broad beam method, etc. may be mentioned, but not particularly limited.

[0016]

The present invention increases the adhesive force between the polyethylene terephthalate base material and the protective coating film by increasing the bonding force at the coating interface such as hydrogen bonding force or intermolecular force by the above means for solving. Thus, a polyethylene terephthalate laminate having excellent coating film adhesion can be obtained.

[0017]

EXAMPLES The present invention will be described in detail below based on examples.

Example 1 A gravure coater was coated with a coating composition having the following composition (a) as a primer layer on one surface of a polyethylene terephthalate film (Lumirror T # 50 manufactured by Toray Industries, Inc.) having a thickness of 50 μm. Then, the coating is applied so that the film thickness after drying and curing is about 1 μm. Composition (a):

[0019]

[Chemical 1]

Further, as a surface protective layer, the following composition
The coating agent comprising (b) is applied with a gravure coater so that the film thickness after drying and curing will be 1-2 μm. Composition (b):

[0021]   Urethane acrylate (manufactured by Negami Kogyo Co., Ltd .: Art Resin UN-730HC) 30 parts   Oligoester acrylate (manufactured by Toagosei Chemical Industry Co., Ltd .:                   Aronix M-8030) 70 copies   Radical generator (Darocur 1173 (Merck)) 5 parts                                                       105 copies

After coating, the ultraviolet irradiation device (eye
Graphics Co., Ltd .: Metal halide lamp 120
W / cm, 2 lights), irradiation dose is about 400mJ
/ cm ²The energy is used to cure the coating film.

The polyethylene terephthalate film having the surface protective layer obtained as described above was excellent in surface scratch resistance and adhesiveness to the substrate.

Example 2 On one side of a polyethylene terephthalate film having a thickness of 50 μm (manufactured by Toray Industries, Inc .: Lumirror T # 50), a coating agent having the following composition (c) was used as a primer layer with a gravure coater. The coating is performed so that the film thickness after drying and curing is about 1 μm. Composition (c):

[0025]

[Chemical 2]

Further, as a surface protective layer, the following composition
The coating agent consisting of (d) is applied with a gravure coater so that the film thickness after drying and curing will be 1-2 μm. Composition (d):

[0027]   Urethane acrylate (manufactured by Negami Kogyo Co., Ltd .: Art Resin UN-730HC)                                                                 30 copies   Oligoester acrylate (Toagosei Chemical Industry Co., Ltd .: Aronix   M-8030) 70 copies                                                       100 copies

After coating, the coating film is passed under irradiation of an electron beam irradiation device (Curetron, manufactured by Nisshin High Voltage Co., Ltd.) to cure the coating film with energy of irradiation dose of about 4.0 Mrad.

The polyethylene terephthalate film having the surface protective layer obtained as described above was excellent in surface scratch resistance and adhesiveness to the substrate.

Example 3 One side of a polyethylene terephthalate film having a thickness of 50 μm (manufactured by Toray Industries, Inc .: Lumirror T # 50) was attached to an electron beam irradiation device (manufactured by Nisshin High Voltage Co., Ltd .: Curetron). It is passed under irradiation and a surface activation treatment is performed with an energy of irradiation dose of about 10 Mrad.

On one side of a polyethylene terephthalate film having a thickness of 50 μm (Lumirror T # 50 manufactured by Toray Industries, Inc.), as a primer layer, a coating composition having the following composition (e) was dried and cured by a gravure coater. Thickness is about 1 μm
Apply it to the extent. Composition (e):

[0032]

[Chemical 3]

Further, as a surface protective layer, the following composition
The coating agent comprising (f) is applied by a gravure coater so that the film thickness after drying and curing will be 1 to 2 μm. Composition (f)

[0034]   Urethane acrylate (Negami Kogyo Co., Ltd .: Art Resin UN-730HC)                                                                30 copies   Oligoester acrylate (Toagosei Chemical Industry Co., Ltd .: Aronix    M-8030) 70 parts   Radical generator (Darocur 1173 (Merck)) 5 parts                                                       105 copies

After coating, an ultraviolet irradiation device (made by Eye Graphics Co., Ltd .: metal halide lamp 12)
0 W / cm, 2 lights), irradiation dose is about 400
The coating film is cured with energy of mJ / cm ² .

The polyethylene terephthalate film having the surface protective layer obtained as described above was excellent in surface scratch resistance and adhesiveness to the substrate.

Example 4 One side of a 50 μm thick polyethylene terephthalate film (Toray Industries, Inc .: Lumirror T # 50) was irradiated with an electron beam irradiation device (Nisshin High Voltage Co., Ltd .: Curetron). The surface is passed through the lower part and the surface is activated with an energy of an irradiation dose of about 10 Mrad.

On one side of a polyethylene terephthalate film (Lumirror T # 50 manufactured by Toray Industries, Inc.) having a thickness of 50 μm, as a primer layer, a coating agent having the following composition (g) was dried and cured by a gravure coater. Thickness is about 1 μm
Apply it to the extent. Composition (g):

[0039]

[Chemical 4]

Further, as a surface protective layer, the following composition
The coating agent consisting of (h) is applied by a gravure coater so that the film thickness after drying and curing is 1 to 2 μm. Composition (h):

[0041]  Urethane acrylate (manufactured by Negami Kogyo Co., Ltd .: Art Resin UN-730HC)                                                                 30 copies  Oligoester acrylate (Toagosei Chemical Industry Co., Ltd .: Aronix   M-8030) 70 parts                                                       100 copies

After coating, the coating film is passed under irradiation of an electron beam irradiation device (Curetron, manufactured by Nisshin High Voltage Co., Ltd.) to cure the coating film with an energy of irradiation dose of about 4.0 Mrad.

The polyethylene terephthalate film having the surface protective layer obtained as described above was excellent in surface scratch resistance and adhesiveness to the substrate.

<Comparative Example> Hereinafter, the effect of the present invention will be described in more detail in a comparative example.

Comparative Example 1 A polyethylene terephthalate film having a protective coating film was obtained in the same manner as in Example 1 except that the primer layer was not applied.

Comparative Example 2 A polyethylene terephthalate film having a protective coating film was obtained in the same manner as in Example 2 except that the primer layer was not applied.

Comparative Example 3 A polyethylene terephthalate film having a protective coating film was obtained in the same manner as in Example 3 except that the primer layer was not applied.

Comparative Example 4 A polyethylene terephthalate film having a protective coating film was obtained in the same manner as in Example 4 except that the primer layer was not applied.

[0049]

EFFECT OF THE INVENTION Polyethylene terephthalate film having the surface protective layer obtained in Example 1, Example 2, Example 3, Example 4, Comparative Example 1, Comparative Example 2, Comparative Example 3, and Comparative Example 4. The coating adhesion of each surface protection layer of 100
After making a grid of × 100, a peel test with a force of ∠45 ° and a force of 5 kgf / cm ² and a repeated peel test 10 times were evaluated. Further, the surface scratch resistance was measured by using a Taber abrasion tester (manufactured by Toyo Seiki Seisakusho Co., Ltd.) with CS-10 and a weight of 500.
A wear test was performed under the conditions of g and 500 rotations, and the degree of wear was evaluated by the haze degree.

[0050]

[Table 1]

As shown in the above results, in Example 1, Example 2, Example 3, and Example 4, that is, according to the present invention, the protective coating film of polyethylene terephthalate is excellent in surface scratch resistance and coating film adhesion. was gotten.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location C09D 133/08 PKU 7242-4J // C08L 67:03

Claims (4)

[Claims] 1. A main component of an ultraviolet ray or electron beam curable resin composition having a terephthalic acid or an ester structure of phthalic acid in the main chain structure and a hydrogen-bonding functional group on the surface of a polyethylene terephthalate substrate. And a surface protection layer made of a mixed system of an oligoester acrylate having at least two acryloyl groups and a urethane acrylate. 2. The laminate according to claim 1, wherein a monofunctional acrylate having a hydrogen-bonding functional group is added to the primer layer as an auxiliary agent. 3. An ultraviolet or electron beam curable resin composition having a terephthalic acid or an ester structure of phthalic acid in its main chain structure and having a hydrogen-bonding functional group after activating the surface of polyethylene terephthalate. A primer layer consisting of a base material is applied, and then a surface protective layer consisting of a mixture of oligoester acrylate and urethane acrylate having at least two acryloyl groups is applied, and then cured by irradiation with ultraviolet rays or electron beams. A method for producing a laminated body characterized by the above. 4. The method for producing a laminate according to claim 3, wherein the primer layer is added with a monofunctional acrylate having a hydrogen-bonding functional group as an auxiliary agent.