KR19990061389A - Hot stamping foil - Google Patents

Abstract

The present invention relates to a hot stamping foil having excellent chemical resistance and gloss including heat resistance, abrasion resistance, and alcohol resistance, and more particularly, a hot stamping in which a polyester substrate, a wax release layer, a coloring layer, a metal layer, and an adhesive layer are sequentially stacked. The foil is characterized in that the colored layer is formed of a composition comprising an isocyanate resin, 70 to 120 parts by weight of a hydroxy (OH) group-containing resin and 170 to 220 parts by weight of a thermoplastic acrylic resin based on 100 parts by weight of the isocyanate resin. .

Description

Hot stamping foil

The present invention relates to a hot stamping foil having excellent chemical resistance and gloss including heat resistance, abrasion resistance, and alcohol resistance.

Stamping foils are used to stamp metallic color patterns or letters on various substrates, such as plastic moldings, electronics, leather, wood and paper products, to give them a brilliant appearance and to increase their commercial value, usually on polyester substrate films In turn, it has a structure in which a release layer, a coloring layer (protective layer), a light reflection layer (metal layer) and an adhesive layer are laminated.

Stamping foils require a variety of physical properties depending on the substrate being stamped, and are usually stamped on plastic substrates. This process is performed at high temperatures, so the stamping foil is heat resistant, especially when the stamping foil is used on the surface of electronic products or cosmetic cases. In addition, abrasion resistance and chemical resistance are required.

Accordingly, it is an object of the present invention to improve these problems, to provide a hot stamping foil excellent in chemical resistance and gloss, including heat resistance, wear resistance, alcohol resistance.

In order to achieve the above object, in the present invention, in a hot stamping foil in which a polyester base material, a wax release layer, a coloring layer, a metal layer, and an adhesive layer are sequentially stacked, the colored layer is based on 100 parts by weight of an isocyanate resin and an isocyanate resin. A hot stamping foil is provided, which is formed from a composition comprising 70 to 120 parts by weight of a hydroxy (OH) group-containing resin and 170 to 220 parts by weight of a thermoplastic acrylic resin.

Hereinafter, the present invention will be described in detail.

In the present invention, to form a colored layer of hot stamping foil, isocyanate and a hydroxyl group-containing resin are cured to form a urethane bond.

The isocyanate resin is a trimer type of tolylene diisocyanate (TDI trimer type) is an isocyanate group content of 7.5 to 8.5%.

Examples of the hydroxy group-containing resin include methyl methacryl (MMA) copolymer resin having a hydroxy value of 70 to 80, a branched polyester resin having a hydroxy group content of 5 to 6%, and an acetyl content of 39.8% and hydroxy group. Cellulose acetate resin having a timing content of 3.5% and a Tg of 180 ° C, a linear saturated polyester resin having a Tg of 63 to 67 ° C, a hydroxyl value of 4 to 5 and a molecular weight of 18,000 to 23,000, a melting temperature (Tm) of 98 ° C And a synthetic polyketone resin having a hydroxy value of 268 may be used.

The hydroxyl group of the hydroxyl group-containing resin causes hardening reaction with isocyanate and increases heat resistance. The hydroxyl group-containing resin may be used in an amount of 70 to 120 parts by weight based on 100 parts by weight of the isocyanate resin. When the amount of the hydroxyl group-containing resin is less than 70 parts by weight, the heat resistance is insufficient and when the amount is more than 120 parts by weight, the room temperature Due to the curing reaction between the isocyanate resin and the thermosetting resin, the pot-life of the colored layer composition mixture is shortened.

The thermoplastic acrylic resin is a polymethyl methacrylate (PMMA) resin having a glass transition temperature (Tg) of 100 to 110 ° C., which is transparent and serves to maintain the gloss of the stamping foil and increase wear resistance and heat resistance. The thermoplastic acrylic resin may be used in an amount of 170 to 220 parts by weight based on 100 parts by weight of the isocyanate resin. When the amount of the acrylic resin is less than 170 parts by weight, the wear resistance and the alcohol resistance are lowered. The properties are increased but the heat resistance is lowered.

The hot stamping foil according to the present invention is coated with the colored layer composition on a polyester base film to which a wax release layer is applied in an amount of 1.5 to 2.0 g / m 2 by a conventional method, and then at 150 to 190 ° C. for 5 seconds. It can be prepared by forming a colored layer on a substrate by heat treatment for from 20 seconds, then depositing a metal layer by a conventional method on the colored layer and forming an adhesive layer thereon.

Hereinafter, the present invention will be described in more detail with reference to the following examples, but the contents of the present invention are not limited thereto.

In Examples and Comparative Examples, physical properties of the stamping foil were measured as follows.

1) Peeling level (deformation degree)

After attaching 1 cm of cello tape to the finished foil, the level of force taken when peeling was evaluated by dividing it into 1 to 10 steps. In this case, peeling is not performed at all, and in the case of peeling with a very weak force, it is 10 steps. In general, it is convenient to use when peeled off with a weak force.

2) heat resistance

The transfer temperature at which the transfer surface was quenched during stamping was measured.

3) wear resistance

After transferring the stamping foil onto the plastic substrate, a rubbing tester (Clockermeter, James H. Heal co. Ltd.) equipped with an eraser on the surface was used to reciprocate until the surface was peeled off and the metal deposition layer appeared. Was measured.

4) alcohol resistance

After transferring the stamping foil onto the plastic substrate, the number of frictions was measured until the colored layer was peeled off and the metal deposited layer appeared while rubbing the surface with gauze moistened with ethanol.

Examples 1 to 7 and Comparative Examples 1 and 2

500 g of an ester wax OP (manufactured by Hoechst) was dissolved in 200 kg of a mixed solvent of toluene and methyl ethyl ketone (mixing ratio 2: 1), coated on a polyester base film with a gravure roll, and dried at 120 ° C. for 5 seconds. I was. The colored layer composition according to the composition of Table 1 was coated on the release layer in an amount of 1.7 g / m 2, dried at 170 ° C. for 10 seconds, and aluminum was deposited thereon. A mixed adhesive liquid of acrylic and vinyl resin (mixed ratio 6: 4 ) Was coated in an amount of 1.2 g / m 2 to prepare a stamping foil.

Composition (kg) Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Comparative Example 1 Comparative Example 2 Isocyanate TR50 ¹⁾ 5.41 5.00 4.76 5.88 5.41 5.13 4.76 5.71 5.88 MMA Copolymer Resin 52-666 ²⁾ 5.41 5.00 4.76 4.12 3.78 3.59 5.71 2.86 5.88 Thermoplastic Acrylic Resin Acryloid A11 ³⁾ 9.19 10.00 10.48 10.00 10.81 11.28 9.52 11.43 8.24 toluene 16 16 16 16 16 16 16 16 16 Methyl ethyl ketone 47 47 47 47 47 47 47 47 47 Cyclohexanone 16 16 16 16 16 16 16 16 16 Dye Orange G (Orange G) ⁴⁾ One One One One One One One One One Total amount 100 100 100 100 100 100 100 100 100 ¹⁾ Aekyung Chemical ²⁾ Aekyung Chemical ³⁾ Rhom Hass ⁴⁾ Ciba Geigy

Peeling level, heat resistance, abrasion resistance and alcohol resistance of the stamping foil was measured, and the results are shown in Table 2 below.

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Comparative Example 1 Comparative Example 2 Peeling level 7 7 8 7 8 8 7 7 8 Heat resistance (℃) 180 170 170 180 160 160 180 140 190 Wear resistance (times) 92 97 106 64 70 78 104 64 35 Alcohol resistance (times) 94 100 114 69 73 85 105 72 38

As shown in Table 2, the stamping foils of Examples 1 to 7 have very good physical properties such as peeling level, heat resistance, abrasion resistance and alcohol resistance, whereas Comparative Example 1 (50 parts by weight of MMA copolymerization based on 100 parts by weight of isocyanate resin) It can be seen that the stamping foil of the resin 52-666) is low in heat resistance, and that the stamping foil of Comparative Example 2 (including 140 parts by weight of thermoplastic acrylic resin based on 100 parts by weight of isocyanate resin) has low wear resistance and alcohol resistance. .

Examples 8-14 and Comparative Examples 3 and 4

Except that in Table 1, branched polyester resin Desmophen 651 (manufactured by Bayer) was used as the hydroxyl group-containing resin instead of MMA-based acrylic copolymer resin 52-666 (Aekyung Chemical). And in the same manner as in Comparative Examples 1 and 2 to prepare a stamping foil of Examples 8 to 14 and Comparative Examples 3 and 4.

Peeling level, heat resistance, abrasion resistance and alcohol resistance of the stamping foil were measured, and the results are shown in Table 3 below.

Example 8 Example 9 Example 10 Example 11 Example 12 Example 13 Example 14 Comparative Example 3 Comparative Example 4 Peeling level 7 8 8 7 8 8 8 7 8 Heat resistance (℃) 170 160 150 170 170 150 170 130 170 Wear resistance (times) 79 84 92 53 58 65 84 54 28 Alcohol resistance (times) 80 91 94 51 64 71 88 58 28

As shown in Table 3, the stamping foils of Examples 8 to 14 had very good physical properties such as peeling level, heat resistance, abrasion resistance, and alcohol resistance, whereas Comparative Example 3 (50 parts by weight of polyester resin based on 100 parts by weight of isocyanate resin) It can be seen that the stamping foil of Desmophen 651) is low in heat resistance, and the stamping foil of Comparative Example 4 (comprising 140 parts by weight of thermoplastic acrylic resin based on 100 parts by weight of isocyanate resin) has poor wear resistance and alcohol resistance.

Examples 15-21 and Comparative Examples 5 and 6

Comparative Examples 1 to 7 except for using cellulose acetate resin CA398 (manufactured by Eastman Kodak) in place of MMA-based acrylic copolymer resin 52-666 (Aekyung Chemical) as a hydroxyl group-containing resin in Table 1 The stamping foils of Examples 15 to 21 and Comparative Examples 5 and 6 were prepared in the same manner as in Examples 1 and 2.

Peeling level, heat resistance, abrasion resistance and alcohol resistance of the stamping foil were measured, and the results are shown in Table 4 below.

Example 15 Example 16 Example 17 Example 18 Example 19 Example 20 Example 21 Comparative Example 5 Comparative Example 6 Peeling level 8 9 9 8 9 10 9 8 8 Heat resistance (℃) 170 170 160 170 160 150 170 130 180 Wear resistance (times) 82 89 95 54 63 71 91 59 29 Alcohol resistance (times) 85 94 102 58 67 77 94 60 30

As shown in Table 4, the stamping foils of Examples 15 to 21 had very good physical properties such as peeling level, heat resistance, abrasion resistance, and alcohol resistance, whereas Comparative Example 5 (50 parts by weight of cellulose acetate resin based on 100 parts by weight of isocyanate resin) It can be seen that the stamping foil of CA398) is low in heat resistance, and the stamping foil of Comparative Example 6 (including 140 parts by weight of thermoplastic acrylic resin based on 100 parts by weight of isocyanate resin) has low wear resistance and alcohol resistance.

Examples 22-28 and Comparative Examples 7 and 8

Examples 1 to 7 and except for using a linear saturated polyester resin ES100 (manufactured by SKI) instead of MMA-based acrylic copolymer resin 52-666 (Aekyung Chemical) as a hydroxyl group-containing resin in Table 1 The stamping foils of Examples 22 to 28 and Comparative Examples 7 and 8 were prepared in the same manner as in Comparative Examples 1 and 2.

Peeling level, heat resistance, abrasion resistance and alcohol resistance of the stamping foil were measured, and the results are shown in Table 5 below.

Example 22 Example 23 Example 24 Example 25 Example 26 Example 27 Example 28 Comparative Example 7 Comparative Example 8 Peeling level 7 7 8 7 7 8 8 7 8 Heat resistance (℃) 170 160 150 170 160 150 170 130 170 Wear resistance (times) 74 81 80 51 59 65 82 52 25 Alcohol resistance (times) 75 87 92 53 60 69 84 53 26

As shown in Table 5, the stamping foils of Examples 22 to 28 had very good physical properties such as peeling level, heat resistance, abrasion resistance, and alcohol resistance, whereas Comparative Example 7 (50 parts by weight of linear saturated polyether based on 100 parts by weight of isocyanate resin) It can be seen that the stamping foil of the ester resin ES100 has a low heat resistance, and that the stamping foil of Comparative Example 8 (comprising 140 parts by weight of a thermoplastic acrylic resin with respect to 100 parts by weight of the isocyanate resin) has poor wear resistance and alcohol resistance.

Examples 29-35 and Comparative Examples 9 and 10

Examples 1 to 7 except for using a synthetic polyketone resin Krumbhaar 1717 (Lawter Int.) Instead of MMA-based acrylic copolymer resin 52-666 (Aekyung Chemical) as a hydroxyl group-containing resin in Table 1 And in the same manner as in Comparative Examples 1 and 2 to prepare a stamping foil of Examples 29 to 35 and Comparative Examples 9 and 10.

Peeling level, heat resistance, abrasion resistance and alcohol resistance of the stamping foil were measured, and the results are shown in Table 6 below.

Example 29 Example 30 Example 31 Example 32 Example 33 Example 34 Example 35 Comparative Example 9 Comparative Example 10 Peeling level 7 8 8 7 7 8 8 6 7 Heat resistance (℃) 180 170 170 180 170 160 180 140 190 Wear resistance (times) 71 75 82 46 53 64 84 49 21 Alcohol resistance (times) 82 83 86 47 59 72 87 51 22

As shown in Table 6, the stamping foils of Examples 29 to 35 have very good physical properties such as peeling level, heat resistance, abrasion resistance and alcohol resistance, whereas Comparative Example 9 (50 parts by weight of synthetic polyketone based on 100 parts by weight of isocyanate resin) It can be seen that the stamping foil of the resin Krumbhaar 1717 has low heat resistance, and that the stamping foil of Comparative Example 10 (including 140 parts by weight of thermoplastic acrylic resin based on 100 parts by weight of isocyanate resin) has poor wear resistance and alcohol resistance.

The hot stamping foil of the present invention is excellent in chemical resistance and gloss including release property, heat resistance, abrasion resistance and alcohol resistance.

Claims (4)

A hot stamping foil in which a polyester base material, a wax release layer, a coloring layer, a metal layer, and an adhesive layer are laminated in this order, wherein the colored layer is 70 to 120 parts by weight of hydroxy (OH) based on 100 parts by weight of isocyanate resin and isocyanate resin. A hot stamping foil formed from a composition comprising a group containing resin and 170 to 220 parts by weight of a thermoplastic acrylic resin. The method of claim 1, The isocyanate resin is a hot stamping foil, characterized in that the content of the isocyanate group is 7.5 to 8.5% and trimer (TDI trimer type) of tolylene diisocyanate. The method of claim 1, The hydroxy group-containing resin is a methyl methacrylate (MMA) copolymer resin having a hydroxy value of 70 to 80, a branched polyester resin having a hydroxy group content of 5 to 6%, an acetyl content of 39.8% and hydroxy Cellulose acetate resin having a timing content of 3.5%, Tg of 180 ° C, linear saturated polyester resin having a Tg of 63 to 67 ° C, a hydroxyl value of 4 to 5, and a molecular weight of 18,000 to 23,000, and a melting temperature (Tm) of 98 ° C. And a hot stamping foil, characterized in that it is selected from the group consisting of synthetic polyketone resins having a hydroxy value of 268. The method of claim 1, Hot stamping foil, wherein the thermoplastic acrylic resin is a polymethyl methacrylate (PMMA) resin having a glass transition temperature (Tg) of 100 to 110 ℃.