KR101910399B1 - Manufacturing method of decorative sheet - Google Patents

Manufacturing method of decorative sheet Download PDF

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KR101910399B1
KR101910399B1 KR1020147009312A KR20147009312A KR101910399B1 KR 101910399 B1 KR101910399 B1 KR 101910399B1 KR 1020147009312 A KR1020147009312 A KR 1020147009312A KR 20147009312 A KR20147009312 A KR 20147009312A KR 101910399 B1 KR101910399 B1 KR 101910399B1
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layer
resin
transparent resin
film
resin layer
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KR1020147009312A
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KR20140091521A (en
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유우스케 헨미
토시유키 나카시마
유키히로 요시스에
사토시 카와무라
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도요 고한 가부시키가이샤
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2451/00—Decorative or ornamental articles

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Abstract

Wherein the surface resin layer comprises a first layer made of a polybutylene terephthalate resin or a modified polybutylene terephthalate resin on the surface side, to, after heating up to 230 ℃ difference of ΔL * value (ΔL * a) and standing minutes when Romance Colorimeter ΔL * value according to the cases, poor circulation (ΔL * b) by minutes when Romance color difference meter in the case of rapid cooling (| DELTA L * a- DELTA L * b |) of 1.0 or less, and the thickness of the first layer is in the range of 3 to 20 mu m.

Description

TECHNICAL FIELD [0001] The present invention relates to a manufacturing method of a decorative plate,

TECHNICAL FIELD [0001] The present invention relates to a decorative film for lamination on a substrate for enhancing designability of various substrates, and a decorative plate obtained using the decorative film.

Description of the Related Art [0002] In recent years, a decorative plate formed by laminating a decorative film on a substrate such as a metal plate has been widely used as a plate material used for indoor and outdoor walls of furniture, home appliances, and buildings.

As such a decorative film, for example, Patent Document 1 discloses a decorative film in which a layer composed of a colored polybutylene terephthalate resin, a printing ink layer, and a layer made of a transparent resin are laminated in order from below . In Patent Document 1, polybutylene terephthalate resin, polyethylene terephthalate resin, or modified polyethylene terephthalate resin and the like are exemplified as the transparent resin constituting the outermost layer. However, in the technique of Patent Document 1, when embossing is performed to give decorative effect to the decorative film, the transparent resin constituting the outermost surface layer is crystallized by heat at the time of embossing to cause clouding, and as a result, There is a problem of change.

Patent Document 1: JP-A-2006-62215

It is an object of the present invention to provide a decorative film which can realize excellent embossing workability while effectively preventing occurrence of color tone change caused by opacity.

The present inventors have found that, in a decorative film in which a substrate resin layer, a print layer and a surface resin layer are laminated in order, the surface resin layer is formed by a layer comprising a polybutylene terephthalate resin or a modified polybutylene terephthalate resin, And a layer made of a transparent resin having a difference in the DELTA L * value by the spectroscopic colorimeter in the case of quenching from a temperature and in a case of a cold state being in a predetermined range, and further, a layer made of a polybutylene terephthalate resin or a modified polybutylene The above object can be achieved by controlling the thickness of the layer made of the terephthalate resin to a predetermined range, and the present invention has been accomplished.

That is, according to the present invention, there is provided a laminate comprising a substrate resin layer, a print layer, and a surface resin layer laminated in this order, wherein the surface resin layer comprises a polybutylene terephthalate resin or a modified polybutylene terephthalate resin L * value (? L * a ) by a spectroscopic colorimeter in the case of heating at 230 占 폚 and then quenched on the printing layer side and? L * value (? L * a) has a second layer made of a transparent resin, not more than 1.0, a decorative film, characterized in that the thickness of the first layer in the range of 3 to 20㎛ | * b) of the difference (| ΔL * a * b -ΔL / RTI >

In the decorative film of the present invention, the transparent resin constituting the second layer is preferably a polyethylene terephthalate resin or a modified polyethylene terephthalate resin, more preferably an isophthalic acid-modified polyethylene terephthalate resin.

The decorative film of the present invention preferably further comprises an adhesive layer between the print layer and the surface resin layer.

Further, according to the present invention, there is provided a decorative plate formed by laminating any one of the decorative films on a substrate.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a decorative film which can effectively prevent the occurrence of a change in color tone due to opacity and which has excellent embossing processability, and an ornamental plate obtained by using the decorative film.

1 is a view showing a configuration of a decorative film 100 according to the present embodiment.

Hereinafter, embodiments of the present invention will be described with reference to the drawings.

1 is a view showing a configuration of a decorative film 100 according to the present embodiment. 1, the decorative film 100 according to the present embodiment is formed by sequentially forming a base resin layer 10, a print layer 20, an adhesive layer 30, and a surface resin layer 40 in this order.

The base resin layer 10 is composed of a colored resin film. The colored resin film constituting the base resin layer 10 is not particularly limited, but a colored polyester resin film in which 5 to 30% by weight of a coloring pigment is added to a polyester resin may, for example, be mentioned.

Examples of the polyester resin constituting the colored polyester resin film include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), ethylene terephthalate / ethylene isophthalate copolymer (ET / EI), butyl (BT / BI), ethylene terephthalate / cyclohexane dimethanol copolymer (ET / CHDM), and the like. These may be used alone or in combination of two or more kinds. Can be used. Examples of the coloring pigments constituting the colored polyester resin film include black or white achromatic pigments, and chromatic pigments such as red, yellow, blue and green. These pigments may be used singly or in combination of two or more Can be used together. On the other hand, the colored polyester resin film may be either in a non-drawn state or in a state of being uniaxially or biaxially stretched in a film form.

The thickness of the base resin layer 10 is preferably 15 to 300 占 퐉, more preferably 40 to 170 占 퐉.

The printing layer 20 is a layer made of a printing ink formed by applying printing ink on the base resin layer 10 described above and is composed of a beta printing layer 10 for covering the front surface of the base resin layer 10, , Or a pattern printed layer expressing the shape of a grain, a stone pattern, a surface pattern of a natural leather, a texture of a cloth, and an abstract pattern. Alternatively, the printing layer 20 may be a layer in which the beta printing layer is formed as a printing layer, and a design printed layer is superimposed thereon to improve the designability. As the printing ink for forming the printing layer 20, there can be used, for example, a cellulose derivative such as nitrocellulose, cellulose acetate or the like, or a printing ink using a polyester resin or a urethane-modified polyester resin as a vehicle . Of these, nitrocellulose-alkyd resin-based inks are preferable from the viewpoints of adhesion and thermal adhesiveness.

The adhesive layer 30 is a layer for bonding the print layer 20 and a surface resin layer 40 described later. The adhesive for forming the adhesive layer 30 is preferably an adhesive which has sufficient transparency and thus does not detract from the design properties imparted by the print layer 20 and which adheres to the print layer 20 and the surface resin layer 40 And is not particularly limited. Specific examples of the adhesive for forming the adhesive layer 30 include an adhesive such as a vinyl acetate resin, an ethylene-vinyl acetate resin, an urea resin, a urethane resin, an acrylic resin, a polyester resin, a polyester urethane resin, Adhesives, and thermosetting adhesives such as epoxy-phenol resin-based adhesives.

As shown in Fig. 1, the surface resin layer 40 is a layer composed of two layers, that is, a first transparent resin layer 41 and a second transparent resin layer 42. As shown in Fig.

The first transparent resin layer 41 is a layer constituting the outermost layer of the decorative film 100 according to the present embodiment and is made of polybutylene terephthalate (PBT) or modified polybutylene terephthalate (modified PBT) And is made of a first transparent resin. Specific examples of the modified polybutylene terephthalate include, for example, isophthalic acid-modified polybutylene terephthalate in which a part of the acid component of polybutylene terephthalate is substituted with isophthalic acid.

The decorative film 100 of the present embodiment is heated from the side of the first transparent resin layer 41 constituting the outermost layer of the decorative film 100, And is then used in a state in which the surface thereof is subjected to embossing by being compressed by an embossing roll. For this reason, in the present embodiment, as the first transparent resin layer 41 constituting the outermost layer of the decorative film 100, the first transparent resin layer 41, which is made of polybutylene terephthalate or polybutylene terephthalate having excellent embossing workability and transparency, A transparent resin is used.

On the other hand, the second transparent resin layer 42 is a layer formed between the first transparent resin layer 41 and the adhesive layer 30 as described above. The second transparent resin layer 42 has a spectral color difference The difference (|? L * a -? L * b |) between the? L * value (? L * a) by the system and the? L * value (? L * b ) when it is cold is 1.0 or less.

Here, DELTA L * a is obtained by heating the film-like second transparent resin to 230 DEG C, which is the temperature at the time of embossing the decorative film 100 described above, and then quenching it by, for example, L * value obtained by cooling to room temperature (25 占 폚) and measuring it using a spectroscopic colorimeter while putting it on a colored plate (for example, a red plate, a blue plate, or a yellow plate). Further, DELTA L * b is obtained by heating the film-like second transparent resin to 230 deg. C, which is the temperature at the time of embossing, and then slowly cooling it by leaving it at room temperature (25 deg. C), cooling it to room temperature (25 deg. L * value obtained by measuring using a colorimetric colorimeter in a state in which it is placed on a coloring plate. On the other hand,? L * a and? L * b can be calculated as the reference value of the? L * value measured by the spectroscopic colorimetric method with respect to the colored plate on which the second transparent resin is not placed.

In the present embodiment,? L * a and? L * b are all indicators of white color. For example, when cooling is carried out after heating to 230 ° C, which is the temperature for embossing, when the transparent resin is opaque The color of the printing layer is hindered, so that the values of? L * a and? L * b also tend to increase. On the other hand, difference in ΔL * value (ΔL * a) and standing ΔL * value when cooled (ΔL * b) in the case of rapid cooling after heating to a temperature of 230 ℃ when performing embossing (| ΔL * a -ΔL * b |) is smaller, it can be said that the? L * value due to the spectroscopic colorimeter is stable, regardless of the cooling condition after heating for embossing. Therefore, in the present embodiment, the second transparent as a second transparent resin constituting the resin layer (42) ΔL * a and b * ΔL of the car (| ΔL * a -ΔL * b |) is less than 1.0, preferably 0.5 or less, and more preferably 0.3 or less. This makes it possible to effectively prevent the occurrence of a change in color tone due to opacity, regardless of the cooling condition after heating for embossing.

On the other hand, specific examples of the transparent resin constituting the second transparent resin layer 42 include a polyethylene terephthalate resin or a modified polyethylene terephthalate resin. Among them, the difference between? L * a and? L * b (| * a- DELTA L * b |) is smaller, and therefore the modified polyethylene terephthalate resin is preferable because the value of DELTA L * is stable regardless of the cooling condition after heating. As the modified polyethylene terephthalate resin, an isophthalic acid-modified polyethylene terephthalate resin and a glycol-modified polyethylene terephthalate resin can be mentioned. Among them, the difference between? L * a and? L * b (| ΔL * a- ΔL * b Isotactic acid-modified polyethylene terephthalate resin is preferably used because it is smaller.

In this embodiment, the surface resin layer 40 of the decorative film 100 is formed of the first transparent resin layer 41 made of the first transparent resin made of polybutylene terephthalate or modified polybutylene terephthalate, and, of ΔL after heating up to 230 ℃, if the rapid cooling * value (ΔL * a) the difference between the standing ΔL * value (ΔL * b) when cooled (| ΔL * a -ΔL * b |) is 1.0 And a thickness of the first transparent resin layer 41 is controlled to be within a specific range. Further, the thickness of the first transparent resin layer 41 is controlled to be within a specific range. That is, the thickness t1 of the first transparent resin layer 41 is controlled in the range of 3 to 20 mu m.

According to the present embodiment, the surface resin layer 40 of the decorative film 100 is composed of two layers, that is, the first transparent resin layer 41 and the second transparent resin layer 42, The surface resin layer 40 can be formed by embossing the first transparent resin constituting the first transparent resin layer 41 and the second transparent resin constituting the second transparent resin layer 42, The effect of preventing the occurrence of color tone change due to opacity when heating for embossing can be made compatible with each other, whereby occurrence of color tone change due to opacity when embossing the decorative film 100 is effectively prevented , And can have excellent embossing processability.

Particularly, the present inventors reached the above-mentioned constitution based on the following viewpoint.

That is, when the surface resin layer 40 of the decorative film 100 is formed of only the first transparent resin layer 41 made of the above-mentioned first transparent resin, it has excellent embossing workability. On the other hand, There is a problem in that when the heating is performed, the first transparent resin is crystallized and a change in color tone due to clouding due to crystallization occurs. On the other hand, in the case where the surface resin layer 40 of the decorative film 100 is formed of only the second transparent resin layer 42 made of the second transparent resin described above, The occurrence of color tone change can be prevented, but there is a problem that the embossing workability is very low.

The present inventors have found that the surface resin layer 40 of the decorative film 100 is composed of two layers of the first transparent resin layer 41 and the second transparent resin layer 42, By setting the thickness t1 of the layer 41 to the above range, the embossing workability can be improved by the action of the first transparent resin constituting the first transparent resin layer 41 located on the outermost surface. Further, The first transparent resin layer 41 when heated for embossing is formed by the action of the second transparent resin constituting the second transparent resin layer 42 formed in the lower layer of the transparent resin layer 41 It is possible to suppress the influence of clouding caused by the crystallization of the first transparent resin. This makes it possible to effectively prevent the occurrence of a change in color tone due to turbidity when the decorative film 100 is embossed, and to have excellent embossing workability.

When the thickness t1 of the first transparent resin layer 41 constituting the surface resin layer 40 is too thick, the first transparent resin is crystallized by heating and cooling for embossing, The occurrence of a change in color tone caused by the above-mentioned phenomenon becomes remarkable. On the other hand, if the thickness t1 of the first transparent resin layer 41 is too thin, the embossability becomes extremely poor.

On the other hand, the total thickness (thickness of the surface resin layer 40) of the thickness t1 of the first transparent resin layer 41 and the thickness t2 of the second transparent resin layer 42 is preferably 15 to 300 mu m, Preferably 30 to 150 mu m. If the thickness of the surface resin layer 40 is too large, there may be a problem that the printed pattern is not clear. On the other hand, if the surface resin layer 40 is too thin, a problem that a surface scratch reaches the print layer may occur.

The difference between? L * a and? L * b (|? L * a -? L * b |) in the transparent resin constituting the second transparent resin layer 42 may be within the above range, The haze value in the case of quenching after cooling, the case of quenching and the case of quenching is preferably in the range of 0 to 60, and more preferably in the range of 35 to 55. By using the transparent resin having the haze value within the above range, it is possible to further enhance the effect of suppressing occurrence of color tone change caused by opacity when embossing is performed.

In the present embodiment, the method of forming the surface resin layer 40 on the adhesive layer 30 is not particularly limited. For example, a method of forming the first transparent resin layer 41 A method in which a film and a film of a second transparent resin to form the second transparent resin layer 42 are laminated by thermal welding or the like and the obtained laminated film is adhered onto the adhesive layer 30. On the other hand, the film of the first transparent resin and the film of the second transparent resin may be either in a non-drawn state or in a state of being uniaxially or biaxially stretched.

Then, a decoration plate can be obtained by laminating the decorative film 100 thus constructed on the base material resin layer 10 side. On the other hand, the decorative film (100) constituting the decorative plate is usually formed from the side of the first transparent resin layer (41) constituting the outermost layer of the decorative film (100) For example, at a temperature of about 230 DEG C, and the embossing process is performed by compressing the embossing roll.

The decorative film 100 and the substrate to be laminated are not particularly limited, and examples thereof include a steel plate, a tin free steel, an aluminum alloy plate, a galvanized steel plate, a zinc-cobalt-molybdenum composite coated steel plate, - A metal plate such as a nickel alloy plated steel plate, a zinc-iron alloy plated steel plate, a galvannealed galvanized steel plate, a zinc-aluminum alloy plated steel plate, a zinc-aluminum-magnesium alloy plated steel plate, a nickel plated steel plate, a copper plated steel plate or a stainless steel plate .

On the other hand, when the decorative film 100 is laminated on a base material, an adhesive layer for bonding to the base material may be formed on the surface of the base resin layer 10 in advance. As the adhesive used in this case, the same adhesive layer as the above-mentioned adhesive layer 30 can be used.

&Quot; Example &

Hereinafter, the present invention will be described in more detail with reference to Examples. However, the present invention is not limited to these examples.

≪ Example 1 >

A polybutylene terephthalate resin (PBT) film having a predetermined thickness and an isophthalic acid-modified polyethylene terephthalate resin (PET / IA) film having a predetermined thickness were thermally fused at 180 占 폚 to obtain a transparent resin film laminate. On the other hand, the thickness of the polybutylene terephthalate resin (PBT) layer in the obtained transparent resin film laminate was 5.5 mu m, and the thickness of the isophthalic acid-modified polyethylene terephthalate resin (PET / IA) layer was 33 mu m.

Then, using the obtained transparent resin film laminate, evaluation of the embossing workability and the opacity suppressing effect and evaluation of the polybutylene terephthalate resin (PBT) film and isophthalic acid modification A heating and cooling test of a polyethylene terephthalate resin (PET / IA) film was carried out.

Embossing  Processability

The obtained transparent resin film laminate was applied on a steel sheet coated with a polyester adhesive on the surface and heated to a temperature of 230 deg. C at which embossing processing was possible. Then, the embossed pattern was transferred by pressure with an embossing roll, And quenched to obtain a sample for evaluation.

Then, the obtained evaluation sample was measured for glossiness Gs (60 DEG) in accordance with JIS K5600. In this embodiment, surface roughness is measured by using an illuminometer (product name: Surfcom 1500A, manufactured by TOKYO CORPORATION), and the maximum depth of the evaluation sample ( Rmax _ sample was obtained and the embossing transfer ratio was determined according to the following formula (1).

Embossing transfer rate (%) = (maximum depth of sample for evaluation R max _ sample / maximum depth of embossing roll R max _ roll ) × 100 (One)

On the other hand, the maximum depth R max _ roll of the embossing rolls may utilize the values measured using a roughness meter.

It can be judged that the lower the glossiness Gs and the higher the embossing transfer ratio, the more excellent the embossing workability.

Cloudiness  Inhibitory effect

The obtained transparent resin film laminate was laminated on the surface of a steel sheet to which a mold release agent had been applied, heated to a temperature of 230 deg. C at which embossing was possible, and then left to stand in air at 25 deg. After cooling, the transparent resin film laminate was peeled from the steel sheet to obtain a sample for evaluation.

Separately from the above, a white base plate, a blue base plate, a red base plate and a yellow base plate were prepared. Using these spectral colorimeters (product name: CM-3500d, Minolta Co.) And the obtained value was taken as a reference value. On the other hand, the blue base plate, the red base plate and the yellow base plate were produced by applying red, indigo, and yellow inks to a white original plate, respectively. In addition, a white base plate was used as a white base plate.

Then, the evaluation sample obtained above was attached to a white base plate, a blue base plate, a red base plate, and a yellow base plate, respectively, and measurement was carried out using a spectroscopic colorimeter on each base plate to which an evaluation sample was attached , And the color difference (? E *) before and after attaching the sample for evaluation in the case of using each base plate was obtained from the obtained measurement result and the reference value measured above. It can be judged that the whitening of the transparent resin film laminate due to heating and cooling is suppressed as the color difference? E * is smaller, and the effect of suppressing the change in color tone due to opacity is high.

PBT  film, PET / IA  Heating and cooling test of film

A polybutylene terephthalate resin (PBT) film having a thickness of 40 占 퐉 and a polyethylene terephthalate resin (PET / IA) film modified with isophthalic acid were heated to a temperature of 230 占 폚. Subsequently, the sample was immediately poured into water having a temperature of 20 占 폚, quenched and quenched, and left at 25 占 폚 in air to be slowly cooled to prepare slow-cooled samples.

The quenched samples of the obtained PBT film and PET / IA film, and the slowly cooled samples of the PBT film and the PET / IA film were evaluated for the blue turbidity base plate, the red base plate and the yellowish base plate In the case of using each base plate, the value of? L * before and after attaching each sample was obtained. Further, in this embodiment, a rapidly cooled sample of the PBT film and the PET / IA film, and a slowly cooled sample of the PBT film and the PET / IA film were measured using a turbidimeter (product name: NDH2000, manufactured by Nippon Shokoku Kogyo Co., Ltd.) Measurement of tooth was performed. The measurement results of the? L * values by the spectroscopic colorimeter are shown in Table 1, and the measurement results of the haze values are shown in Table 2, respectively.

Figure 112014033605095-pct00001

Figure 112014033605095-pct00002

As shown in Table 1, the isophthalic acid-modified polyethylene terephthalate resin (PET / IA) film used in this Example had a ΔL * value (ΔL * a ) and a ΔL * value (ΔL * b ) The difference (DELTA L * a - DELTA L * b |) between the base plate and the base plate is 1.0 or less in all cases using the base plate, and the fluctuation of the? L * value of the color difference is small by the cooling condition after heating. On the other hand, in the polybutylene terephthalate resin (PBT) film used in the present embodiment, ΔL * value of the quenched sample (ΔL * a) and ΔL of the slowly cooled sample * value (ΔL * b) difference (| ΔL * a - DELTA L * b |) was 3.0 or more in all cases using each base plate, and the value of? L * due to the spectroscopic colorimeter greatly changed depending on the cooling condition after heating.

Further, as shown in Table 2, the isophthalic acid-modified polyethylene terephthalate resin (PET / IA) film used in this example had a low haze value and maintained high transparency in both the quenched and slow-cooled samples. On the other hand, it can be confirmed that the polybutylene terephthalate resin (PBT) film used in this example had high haze value and cloudiness due to crystallization in both the quenched sample and the slowly cooled sample.

≪ Example 2 >

Except that the thickness of the polybutylene terephthalate resin (PBT) layer was 9 占 퐉 and the thickness of the isophthalic acid-modified polyethylene terephthalate resin (PET / IA) layer was 28.5 占 퐉. A laminate was obtained, and the embossing workability and the opacity inhibiting effect were measured in the same manner as in Example 1.

≪ Example 3 >

Except that the thickness of the polybutylene terephthalate resin (PBT) layer was 20 占 퐉 and the thickness of the isophthalic acid-modified polyethylene terephthalate resin (PET / IA) layer was 23 占 퐉, A laminate was obtained, and the embossing workability and the opacity inhibiting effect were measured in the same manner as in Example 1.

≪ Comparative Example 1 &

A transparent resin film laminate was obtained in the same manner as in Example 1 except that an isophthalic acid-modified polyethylene terephthalate resin (PET / IA) film having a thickness of 39 mu m was used in place of the transparent resin film laminate, The embossing workability and the anti-cloudiness effect were measured.

≪ Comparative Example 2 &

Except that the thickness of the polybutylene terephthalate resin (PBT) layer was 26 占 퐉 and the thickness of the isophthalic acid-modified polyethylene terephthalate resin (PET / IA) layer was 14 占 퐉. A laminate was obtained and the anti-cloudiness effect was measured in the same manner as in Example 1.

≪ Comparative Example 3 &

Except that the thickness of the polybutylene terephthalate resin (PBT) layer was 31 占 퐉, and the thickness of the isophthalic acid-modified polyethylene terephthalate resin (PET / IA) layer was 12 占 퐉. A laminate was obtained and the anti-cloudiness effect was measured in the same manner as in Example 1.

≪ Comparative Example 4 &

A transparent resin film laminate was obtained in the same manner as in Example 1 except that a polybutylene terephthalate resin (PBT) film having a thickness of 40 占 퐉 was used in place of the transparent resin film laminate, and the embossability and The clouding inhibitory effect was measured.

Table 3 shows the measurement results of the embossing workability and the opacity inhibiting effect of Examples 1 to 3 and Comparative Examples 1 to 4.

Figure 112014033605095-pct00003

As shown in Table 1, in the case of a polybutylene terephthalate resin (PBT) layer and an isophthalic acid-modified polyethylene terephthalate resin (PET / IA) layer and the thickness of the PBT layer is in the range of 5.5 to 20 μm , The embossing workability and the effect of inhibiting the opacity at the time of heating and cooling were excellent (Examples 1 to 3). On the other hand, such a tendency can be expected when the transparent resin film laminate produced in Examples 1 to 3 is laminated on a laminate composed of a base resin layer, a printing layer and an adhesive layer to form a decorative film, The same was true in the case of a decorative plate.

On the other hand, when only the isophthalic acid modified polyethylene terephthalate resin (PET / IA) is used, the embossing workability is poor. On the contrary, when only the polybutylene terephthalate resin (PBT) is used, (Comparative Examples 1 and 4).

In addition, when the thickness of the polybutylene terephthalate resin (PBT) layer was too thick, the effect of inhibiting the opacity upon heating and cooling was lowered (Comparative Examples 2 and 3).

100 ... Decorative film
10 ... The base resin layer
20 ... Printing layer
30 ... Adhesive layer
40 ... The surface resin layer
41 ... The first transparent resin layer
42 ... The second transparent resin layer

Claims (5)

A step of laminating a base resin layer, a print layer, and a surface resin layer in this order to form a decorative film,
A step of laminating the decorative film on a metal substrate at the base resin layer side,
And embossing the surface of the surface resin layer while heating the metal substrate having the decorative film laminated thereon at a temperature of 230 占 폚,
Wherein the surface resin layer comprises a first layer made of a polybutylene terephthalate resin or a modified polybutylene terephthalate resin on the surface side and a first layer made of a polybutylene terephthalate resin the ΔL * value (ΔL * a) and the minutes in the case of standing-cold when Romance difference ΔL * value (ΔL * b) by a color difference meter by (| ΔL * a -ΔL * b |) is less than or equal to 1.0, isophthalic acid modified polyethylene terephthalate And a second layer made of a phthalate resin,
Wherein the thickness of the first layer is in the range of 3 to 20 占 퐉. The method according to claim 1,
Wherein an adhesive layer is further laminated between the print layer and the surface resin layer.
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CN103889723B (en) 2016-08-24
KR20140091521A (en) 2014-07-21

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