JPS61215053A - Dummy bark-shaped laminate - 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 pseudo-skin-like laminate having a printed or vapor-deposited layer and having an uneven pattern formed on its surface.

[Conventional technology and problems]

Conventionally, leather-like synthetic paper made from a stretched plastic film containing a filler (for example, Japanese Patent Publication No. 51742/1983) has been proposed as a pseudo-skin-like material made of a stretched plastic film. This leather-like synthetic paper has a base layer/
Both skin layers contain filler and have a two-layer structure in which voids are formed by stretching, which are then rubbed or embossed.

However, since such leather-like synthetic paper has a layer of voids formed by stretching on the nine surfaces, one surface layer is porous and cannot be rubbed easily.
The 9 surface becomes brittle and breaks due to the formation of irregularities such as embossing, and the surface treatment such as printing easily peels off, making it difficult to repair in practical use.
This is a problem as it may lead to destruction of the laminate.

In addition, 9 bonded films in which the surface layer is a non-porous layer with unevenness and the base layer is a stretched plastic film layer containing a filler (for example, Japanese Patent Laid-Open No. 59-49971
Publication No. 2) has also been proposed.

However, such a bonded film cannot be printed or printed on its surface layer.
Even if a vapor deposited layer is provided, adhesion is not sufficient.

Furthermore, when a concave-convex pattern formation process such as rolling or embossing is performed, there is a problem in that one layer peels off.

The present invention aims to provide a pseudo-skin-like laminate that does not suffer from such problems, that is, has excellent adhesion between vapor deposited/printed layers and resin layers.

[Means to solve the problem]

The present invention mainly consists of an ethylene-propylene copolymer of the following types (A), (B) I (C), and has an orientation coefficient of 7.0 or less, and a printed/evaporated layer (3). ) is laminated with a plastic film layer (4) on one side of the printed/evaporated film, and the other side is filled with 10 to 4 fillers.
A stretched polyolefin film layer (1) containing 0 weight coefficient and having an apparent specific gravity of 0.2 to 0.07 is laminated, and the layer (1)
) is a laminate in which a flexible base sheet (5) is laminated on the outer surface of the layer (1), and at least nine layers (2) of the layer (1).
and a pseudo-skin-like laminate in which a concavo-convex pattern is formed on the layer (3).

(A) A block copolymer with an ethylene component of 10 to 50% by weight and the rest consisting of propylene as a main component with a content of 100 to 1% by weight.
Ethylene-propylene copolymer having 6 or more melting peaks at 65°C.

(B) A block copolymer containing 10 to 50% by weight of ethylene and propylene as the main component, with a melting peak of 126°C or higher, lower than 140°C, and 140°C or higher of 160°C.
℃ and below, and the heat of fusion H at each peak
1, H2 is 06≦H/ (H.

An ethylene-propylene copolymer that satisfies the relationship: +H2)≦07.

(C) An ethylene-propylene copolymer which is a random copolymer having an ethylene component of 1 to 15% by weight and whose time to peak in a DSC isothermal crystallization curve at 120°C is 9 minutes or less.

It is characterized by:

(abbreviated as ilm (1)) is formed by forming voids around the filler by stretching, preferably biaxial stretching.

The apparent specific gravity of the comb is small, it is light, and the mechanical strength is 1.

It maintains dimensional stability, and also forms an opaque outer layer that is flexible and does not easily lose the unevenness caused by permanent deformation.

Further, the resin component of the film (1) may be one mainly composed of a well-known polyolefin, but preferably contains at least 50% by weight of a polypropylene resin, and other components include polypropylene resin, ethylene-
Propylene copolymer (random, block) resin, polyethylene resin, etc. may also be included.

As the filler contained in the film (1), well-known fillers can be used, and specifically, calcium carbonate, magnesium carbonate, magnesium oxide, alumina, aluminum silicate, kaolin, kaolinite, talc, clay, diatomaceous earth, Single or mixtures of inorganic particles such as dolomite, titanium oxide, and zeolite are used. The amount of filler added is 10 to 40% by weight, preferably 15 to 6% by weight.
If it is less than 10% by weight, void formation by stretching is insufficient and unevenness cannot be formed. The film (1) also contains various additives 9 such as heat stabilizers and antioxidants.

A compensator, an antistatic agent, a nucleating agent, a coloring agent, etc. may be added.

The apparent specific gravity of the film (1) must be between 0.2 and 0.7.

If it exceeds 0,7'0, unevenness will be formed.
When 5) is laminated, it is not preferable because it is difficult to form sharp unevenness. Also, if it is less than 0 or 20, the film (1)
The layers are brittle, and the film (1) layer breaks as a laminate, making it unpractical and undesirable. The thickness of the film (1) layer is preferably 30 to 200 nm.

Next, the ethylene-propylene copolymer layer (2) (hereinafter simply referred to as film (2)) has good adhesion to printing, vapor-deposited metal, etc.
It has a tough surface without peeling or breaking, and can also provide the film (1) with mechanical strength 9 and surface abrasion resistance.

The ethylene-O-propylene copolymer layer used in the film (2) is mainly composed of one of the following (A), (B), and (C), and has an orientation coefficient in the length direction and width direction. Both are 7.0 or less, preferably 2.5 or less in the vertical direction and 6.5 or less in the horizontal direction.

Note that the lower limit of the orientation coefficient is about 10, although it is not particularly limited. When the orientation coefficient exceeds ZO, the adhesion of printing and vapor deposition decreases, which is not preferable.

(A) Ethylene component is 10 to 50 hereditary, and the rest is a block copolymer mainly composed of propylene with 100 to 16
The apex of the melting peak at 5°C is 6 or more points, preferably 120
An ethylene-propylene copolymer having at least one point in each of three ranges: "C or more and less than 10o", 160°C or more and less than 150°0, and 15D'a or more and 165°C or less.

(B) A block copolymer mainly composed of propylene with an ethylene component of 10 to 50% by weight, with a melting peak of 126°C or more and less than 140°C, 140'0 or more and 160°C
Each peak has one point below, and the heat of fusion H1, H
An ethylene-propylene copolymer satisfying the relationship 03≦H/(H1+H2)≦07.

The above-mentioned specific ethylene-propylene block copolymer has a uniform matte gloss with 9 rough surfaces.

It maintains excellent adhesion properties for printing and vapor deposition.
Outside these ranges, these properties will not be obtained and the matte property will deteriorate.1 Not only will the appearance deteriorate due to unevenness of the surface, but also a uniform film will not be formed when composited with a film etc. by coextrusion, resulting in so-called lamination failure. I like it.

The above block copolymers (A) and (B) may be a blend of both, or a homopolymer of seasonal olefin.

Other copolymers may also be blended. However, it is preferable that the blending ratio is 50 layers.

CC) A random copolymer with ethylene components of 1 to 15, which has an ethylene 0 propylene copolymer with a time to the peak of the DSC isothermal crystallization curve at 120°C of 9 minutes or less, preferably 7 minutes or less, more preferably 5 minutes or less. Polymer. There are around five schools that do not have a minimum limit of one hour.

The above-mentioned specific ethylene-O-propylene-0 random copolymer has two surfaces with smooth gloss and maintains excellent adhesion properties in printing and vapor deposition, and these properties cannot be obtained outside this range, so it is preferable. .

For example, if the ethylene component is below 1, printing.

The adhesion of vapor deposition cannot be maintained, and if the layer is placed over 15 layers, it is difficult to maintain a smooth surface and the appearance deteriorates.

If the time to the peak of the DSC isothermal crystallization line at 120°0 exceeds 9 minutes, a metal vapor deposited layer (3) with sufficient surface gloss may be added to the surface of the film (2) while maintaining adhesive strength. ) cannot be obtained. In addition, the metal vapor deposition layer (
The surface gloss of 3) is the same as that of random copolymer film (2).
Depends on the surface gloss level.

Although it is better to lower the film temperature during stretching as much as possible, the degree of orientation also increases, making it difficult to maintain the above-mentioned orientation coefficient value. The surface gloss of film (2) is
The surface gloss decreases as the stretching temperature increases, depending on the crystallization process during which the film exits the tenter is cooled in air before being wound up. However, if the crystallization rate at 120° C. is increased, the size of the generated crystals becomes finer, and the surface glossiness improves regardless of the stretching temperature. 120°0
As methods for increasing the crystallization rate, there are a method of increasing the crystallization temperature by blending a polymer with a high crystallization temperature, such as polypropylene, or a method of adding a nucleating agent.

When blending polymers with high crystallization temperatures.

Since the orientation coefficient also increases, if the amount of blending is large, it is necessary to adjust the amount by 110-100 degrees. When blending polypropylene, it is preferably 30 wt% or less.

When adding a nucleating agent, examples of the nucleating agent include aluminum benzoate, 1,3,2.4 dibenzylidene-D-sorbitol, and low melting point nucleating agents such as 1,3,2.4 dibenzylidene-D-sorbitol. Organic nucleating agents are not preferred because they bleed out onto the film surface and reduce the adhesion of the deposited film.

The random copolymer (C) may be blended with an olefin homopolymer or other copolymer, but the blending ratio is preferably 40 times under the atmosphere.

In addition, the above-mentioned fillers and additives may be added to the film (2), but from the viewpoint of wear resistance and surface strength, it is preferable that the amount of filler added is less than 5 layers, more preferably More preferably, substantially no filler is added.

The film (2) is printed and the vapor deposited layer (3) is provided so that the wetting tension per surface is 36 dynes/
cm or more is preferable, and 34 dynes/cm or more is more preferable. As a surface treatment method to obtain this surface wetting tension,
Corona discharge treatment in air can be applied, but carbon dioxide gas,
A method of corona discharge treatment in nitrogen gas is effective.

The printed/deposited layer refers to a layer that has been printed and/or subsequently deposited.Specifically, it refers to a layer that has been printed and/or subsequently deposited.Specifically, it includes colored pattern printing using gravure, offset, screen printing, etc., or direct printing of various metals using vacuum deposition, sputtering, etc. Can be formed by adhesion.

Furthermore, combinations of these methods and transfer of plastic thin films can also be applied.

Plastic film (4) is polyolefin.

Polyester, polyvinyl chloride, polyurethane.

It is preferable to use a homopolymer such as polymethyl methacrylate as the main component, and when a copolymer component is included, the random copolymer component is less than one polymer.

When the block copolymerization component is 10 times the number of blocks, the blending ratio is preferably 40 times or less.

Note that the thickness is preferably 5 to 50 μm.

Films (1), (2), (4), printed/evaporated layers (
3) The apparent specific gravity of the entire laminated film is 0.8 or less, more preferably 0.0 from the viewpoint of uneven pattern formation.
75 or less is desirable, and from the point of view of mechanical strength of the film, 03
Above, more preferably 04 or above.

The flexible base sheet (5) is a fabric 9 made of, but not limited to, synthetic fibers, natural fibers, etc. For example, nonwoven fabric, woven fabric 9
Knitted fabrics are preferred. Paper made from natural pulp 9 For example, Western paper, Japanese paper, adhesive function (thermal).

Plastic sheets with adhesion using high frequency, etc., such as polyethylene, polypropylene, vinyl chloride,
Vinyl acetate copolymers, ionomers, etc. may also be applied. In addition. The thickness is not particularly limited, but is 20μ to 5mm.
(In the case of textile products, place the product on one machine, place an office-use plastic ruler on top of it, and make the gap between the nine machines and the ruler the thickness).

Adhesion of these flexible base sheets (5) requires adhesive strength that will not peel off during the formation of uneven patterns and during practical use.2 Usually, synthetic resin adhesives such as urethane and acrylic, or rubber adhesives are used. Applicable. Also.

Adhesion can also be made by extrusion lamination or by using a molten resin such as polyethylene, polypropylene, or vinyl acetate copolymer.

The laminate of the present invention has an uneven pattern formed on at least three layers: film (1), film (2), and printed/evaporated layer (3).

Note that the uneven pattern is formed by known methods, such as creasing, embossing, and crepe.

A concavo-convex pattern of an arbitrary shape is formed by a method such as pleating. Wrinkle processing.

Synthetic leather, machine-like, tanno plastic rolling, hand-stamping, and embossing are applied to synthetic leather.

Crepe processing is a process that produces crepe paper with embossing rolls and plates that are applied to leather, paper, metal foil, etc.

Pleating processing can be applied to pleating clothing, etc.

The formation of these uneven patterns does not necessarily require application of heat, but processing can be carried out while applying heat in order to make the flexible base sheet (5) and plastic film (4) more flexible.

The following will be explained based on nine drawings. FIGS. 1 and 2 show an example of a cross-sectional view of the laminate of the present invention, in which (1) is a stretched polyolefin film layer in which 10 to 40 weight fillers are engaged, and (2) is the above-mentioned ethylene-propylene layer. Polymer layer, (3) is a printed/evaporated layer, (4) is a plastic film layer, and (5) is a flexible base sheet.

(4j * (5)' indicates an adhesive layer when laminating a plastic film and a flexible base sheet, respectively.

Figure 1 shows (2) of a laminate of films (1) and (2).
When the printed/evaporated layer (3) is directly present on the surface of
FIG. 2 shows a case where there is a printed/evaporated layer (3) on the inside of the plastic film (4) via the film (2) layer. These laminates have a surface unevenness pattern.

In addition, in Figure 2, the film (1) and adhesive (4)
' Another film, preferably a film (2), may be provided between the film and the film.

Next, an example of a method for producing a pseudo-skinned laminate according to the present invention will be described.

Method [■] A composite stretched polyolefin film consisting of a stretched polyolefin film (1) containing a filler and an ethylene-propylene copolymer layer (2) was obtained, and printing or vapor deposition (3) was directly applied to the surface of the (2) layer. On top of the printing or vapor deposition (3) is a synthetic resin such as urethane or acrylic.

A transparent plastic film (4) is laminated via an adhesive layer (41) such as a rubber adhesive or molten resin.

Furthermore, a flexible base sheet (5) is bonded to the outer surface of the film (1) layer via an adhesive layer (5) to form a laminate.Next, this laminate is rubbed to form a surface unevenness pattern. A pseudo-skin-like laminate is obtained (see Fig. 1).

Method (II) The surface of the plastic film (4) having the film (2) layer is printed or vapor-deposited (3) directly on the surface of the (2) layer, and the adhesive layer ( 4f
A flexible base sheet (5) is further laminated on the opposite side of layer (1) via an adhesive layer (55), and then rubbed to form a pseudo-skin-like material with a surface unevenness pattern. A laminate can be obtained (see FIG. 2).

in this case. In order to impart strength to the stretched film (1), it may be a laminated film with other polyolefins, such as polypropylene.

Method [■] Printing or vapor deposition (3) is applied to the composite stretched film of (1) / (2), and the uneven pattern is formed by rolling, etc., or the plastic film is laminated (4), and then the uneven pattern is formed by rolling, etc. The flexible substrate sheet (5) may be bonded to the respective formed materials.

The orientation coefficient of the film (2) varies greatly depending on manufacturing conditions. Not only the stretching ratio but also the film temperature and raw material characteristics during stretching are important factors in determining the orientation coefficient. That is, the orientation coefficient of the film (2) is significantly lowered by increasing the film temperature during stretching to a temperature higher than the melting point of the film (2) (generally 110 to 140° C. for ethylene propylene copolymers and ethylene) or higher.

Film (2) is polyolefin (1) containing filler
laminated film or plastic film (4
) is made as a laminated film. Therefore, in order to obtain the orientation coefficient of the present invention, it is necessary to stretch at a temperature close to the melting point of the polymer used in film (1) or (4) (about 161° C. for crystalline polypropylene). This requirement may be satisfied by the heating section for lateral stretching in sequential longitudinal and lateral biaxial stretching, and by the heating section for simultaneous biaxial stretching.

Furthermore, the degree of orientation of the film (2) varies greatly depending on the raw material characteristics of the ethylene-propylene copolymer film (2), particularly differences in melt index and ethylene component ratio.

That is, in order to lower the degree of orientation, it is preferable to increase the melt index and the ethylene component ratio.

[Measurement method and evaluation method of characteristics]

Next, a method for measuring characteristic values in the present invention will be described.

(1) Top of melting peak and heat of fusion Perkin
-Differential scanning calorimeter Model D manufactured by Elmer
Using the SC-2 model, a 5 mg sample was heated to 280'a at a heating rate of 20'O7 minutes and held for 5 minutes.

A so-called second-run melting curve is taken when the sample is cooled at the same rate and then heated again.

Examples are shown in FIGS. 3 and 4. Among the melting peaks, the melting peak on the low temperature side is pt, and the melting peak on the high temperature side is P2.
shall be. Further, the apex of each melting peak, that is, the minimum point of the peak is defined as A and B, and the temperature at the peak is respectively Tmj
, Tm2.

The method for determining the next ζζ heat of fusion is shown by the first peak P1 in FIG. First, the starting point T1 and the ending point T2 of the absorption are connected by a straight line (broken line C in FIG. 6) to form a baseline. The intersection of the complementary line of the linear part in the first half of the peak and the baseline is T5.The intersection of the complementary line of the straight part in the latter half of the peak with the baseline is T6. ),
Let the heat of fusion be Hl. Similarly, the heat of fusion H2 at the second peak P2 is determined.

However, as shown in Figure 4, the ending point T2 of the first peak Pl and the starting point T3 of the second peak P2 overlap and become one point, and if it deviates from the baseline C connecting T1 and T4, it is perpendicular to the 9th point. The intersection with base line C lowered to T9
Then, the area is determined by connecting the straight line part of the second half of the peak (the first half of the peak in the case of the second peak P2) and T9, and considering the line as a complementary line.

(2) Orientation coefficient The orientation coefficient is calculated using polarized light rays parallel to the plane of incidence.
Calculated from the TR spectrum.

An overview of the measurement conditions is as follows.

Device: FT-IR device FTS-15E/D (DIGI
LAB lNC1) In the spectrum measured at an incident angle of 60°, bands that can be attributed to ethylene and propylene are observed. Furthermore, since the measurement uses polarized light, the band intensity assigned to π in the vertical direction of the film and to S in the horizontal direction appears relatively strong. The orientation coefficient is the peak 842-(yr) of polypropylene and soscm
(5) (7) Calculated as an integrated intensity ratio.

(3) Peak of DSC isothermal crystallization curve Using a differential scanning calorimeter Model DSC-2 manufactured by Perkin-Elmer, 5 mg of sample was
The temperature was raised to 280°C at a heating rate of °C/min, held for 5 minutes, and then cooled at the same rate, and an isothermal crystallization curve was taken at 120°0.

The peak refers to the inflection point of this curve.

Note that the time until the peak is 120% during the cooling process of the sample.
It refers to the time from the time when 'a' is reached until the peak occurs.

(4) Apparent density: Use a new automatic hydrometer manufactured by Toyo Seiki, type I)-1 (the liquid used during measurement is water).

Measurements were made with the liquid temperature at 20°C.

(5) Surface roughness Ra Ru.

(6) Glossiness Based on JIS-Z-8471 method 2 (GS (60°)
The higher this value, the more glossy 9 reflective, and vice versa? The lower the color, the more glossy it is.

(7) Vapor deposition film adhesion and printability Vapor deposition after laminating Chiban ■) on cellophane adhesive tape to the vapor deposition surface and printing surface and peeling off at 180°.

Evaluation was made in 5 levels (index) shown in Table 9 based on the adhesion area of the print.

Table 1 (8) Surface wetting tension ;r　I　S-, measured based on -6768.

〔Example〕

Next, examples and comparative examples will be shown.

Example 1 (1) M. Engineering (melt index, ASTM-DI
Based on 238 () 1.0 polypropylene resin and a resin containing 20 parts by weight of calcium carbonate with a particle size of 1.7μ and M
・Engineering 40. Ethylene component 26 heavy economy.

For propylene component 77, the apex of the DSC melting peak was 123°C and 148°C (maximum peak).

Ethylene-propylene block copolymer resin polymerized at 6 points at 158°C was coextruded and molded using a two-layer die in the vertical direction (130'a, 3.5 times).

It was sequentially biaxially stretched and heat-set in the horizontal direction (160°C, 9 times), and one side (the side of the ethylene O propylene block copolymer layer) was subjected to corona discharge treatment in an atmosphere containing carbon dioxide gas, and the other side was Corona discharge treatment in air, 90μ
A laminated film was obtained.

This biaxially stretched film consists of an 8μ ethylene/propylene block copolymer layer and an 82μ polypropylene layer containing a filler. It was 68 dynes/C.

In addition, the Young's modulus of the laminated film is 67 in the vertical direction 103.
mm, horizontal direction 180 gussets/mm, light transmittance 15
(Young's modulus is a tensile speed of 20 cm/
Determine the strength and elongation characteristics in minutes, and calculate from the slope of the proportional part. Light transmittance is based on JIS-6714).

(2) Approximately 60 OA of aluminum was deposited on the ethylene/propylene block copolymer layer of the laminated film obtained in (1) above using a vacuum deposition method. Also, Dainichiseika Co., Ltd. A
P Ace Beni was gravure printed.

The adhesion of the deposited and printed laminated film to the printing ink was examined using cellophane tape (manufactured by Chiban ■), a peel test, hand detection, and wrinkle processing.

In both vapor deposition and printing, fine, sharp wrinkle-like patterns with a matte luster were obtained without destroying the laminated film or peeling off the various surface treatments using cellophane tape and hand probing.

(3) A 20 μm biaxially oriented polypropylene film (“Torefan #YM11” manufactured by Tanishi ■) was pressure-bonded and laminated with a urethane adhesive on the vapor-deposited and printed laminated film obtained in (2) above. Then, a cotton canvas No. 9 cloth was laminated to the non-printing surface using urethane adhesive, and a clamping machine Y or S type manufactured by Yamasa Giken ■ was used at room temperature 0.
A laminate with a 9-surface unevenness pattern was obtained by rolling at 5 m/min. The apparent specific gravity of the filler-containing film was 0.60.

Fine, irregular wrinkles with a height of 0.020 + nm (difference between peaks and valleys measured using a dial gauge with a sharp tip) or more can be produced without destroying the printed or vapor-deposited layer or the laminate. A similar pattern was obtained. Further, even when a tension of 5 bags/3 cm was applied, the uneven pattern did not disappear.

Further, no breakage was observed in the 5 [1-time abrasion test (load: 200 g, single vibration type abrasion tester) with 1 surface≠240 sandpaper.

Comparative Example 1-1 (1) In Example 1, the amount of calcium carbonate added was 7%.
Then, vapor deposition and printing were carried out in the same manner as in Example 1 (2) on a surface porous film manufactured without laminating the ethylene-propylene copolymer, and the vapor deposited film and ink were tested by cellophane tape peeling test and manual wrinkle processing. The adhesion was investigated.

The vapor deposited and printed layers were easily peeled off and the surface porosity was destroyed (rating: Grade 1 in both cases).

Further, the printed and vapor deposited layers were easily destroyed when the surface was abraded 10 times with sandpaper of +-240 (load: 200 g, single vibration type abrasion tester).

(2) Using the vapor-deposited and printed synthetic paper obtained in (1) above, as in Example 1-(3), a 20P biaxially oriented polypropylene film (Trefan YMj, i manufactured by Bunshishi ■) was used.
A No. 9 cotton canvas cloth was bonded to the non-evaporated and non-printed surface with a urethane adhesive, and then rolled at room temperature at 0.5 m/min using a clamping machine YS type manufactured by Yamasa Giken (filler-containing film). The apparent specific gravity was 0.76)
.

The vapor deposition and printing layers were peeled off, and only rough and gentle unevenness (0, OL mm or less) was obtained.

Comparative Example 1-2 The ethylene/propylene block copolymer component was 3% by weight of the ethylene component of M@I child 3, the apex of the DSC melting peak was 125°C, 141°C, and 160°C (maximum peak), and the others were as in Example A laminated film was obtained in the same manner as in (1) and (2) of 1, and its adhesion properties were examined during vapor deposition, printing, peeling with cellophane tape, and rolling and wrinkling.

Furthermore, in the same manner as in Example 1 (3), a laminated product of biaxially oriented polyurethane, fin film, and canvas was subjected to rolling processing, and its destruction as a carcass was examined.

Vacuum-deposited with cellophane tape, manual wrinkle processing, printing peeled off (class 6 and 4, respectively), and rubbed laminates were also vapor-deposited,
The printed layer had peeled off.

Table 2 shows the raw material characteristics, film surface characteristics, and failure status of the laminate during rolling for the ethylene-propylene block copolymers of Example 1 and Comparative Example 1-2.

Example 2 (1) A resin in which 25 weight of calcium carbonate with a particle size of 17 μm is engaged with a polypropylene resin of M, 1 1.0,
M, I2,0, ethylene component 20 heavy economy, propylene component 80, the top of the DSC melting peak is 160°
There are two points at 0°144'a, H1/(H2+N2
) is 0.432 by coextrusion using a two-layer die, molding, and vertical direction (
160"C135 times), horizontal direction (160"C1,9 times) sequentially biaxially and heat fixed, 9 double-sided corona discharge treatment,
A 90μ laminated film was obtained. This biaxially stretched film consisted of a 7 μm ethylene-propylene block copolymer layer and an 83 μm polypropylene layer containing filler, and had a wet tension of 38 dynes/cm on each of the 9 sides.

(2) Similar to (2) of Example 1, the laminated film obtained in (1) above was subjected to a 9-point test for adhesion between the vapor deposited film of the ethylene/propylene block copolymer layer and the printing ink. Furthermore, the laminate was rubbed in the same manner as in (3) of Example 1 (the apparent specific gravity of the filler-containing film was 0).
．． 58).

In both vapor deposition and printing, a fine, sharply wrinkled pattern (similar to Example 1) with a matte luster was obtained without peeling or destruction of the laminate by cellophane tape and manual creasing.

Comparative Example 2-1 The apex of the DSC melting peak was 126°C when the ethylene component was placed at 20% air and the propylene component was 80% by weight.

Located at two points at 147°q, H1/(H2+N2)
A laminated film was obtained using the ethylene-propylene block copolymer resin having 0259 in the same manner as in (1) and (2) of Example 2, and the adhesion was obtained by vapor deposition and printing in the same manner as in (3) of Example 1. I looked into gender. The laminate was rolled.

Both vapor deposition and printing were judged to be removable with cellophane tape: 4 for each
Even in the manual inspection test, each surface treatment layer peeled off slightly. In addition, the surface was uneven, resulting in a poor appearance. The laminate was also destroyed by the vapor deposition and printing layers.

Comparative Example 2-2 The apex of the melting peak of D S'C was 162°C when the ethylene component was placed at 20% air and the propylene component was 80% by weight.

There are two points at 158℃ w J/("1+H2) is o
A laminated film was obtained using the ethylene-O-propylene block copolymer resin in 750 in the same manner as in Example 2 (], ), (2), and the adhesion of each film during vapor deposition and printing was examined.

In addition, the laminate was rolled in the same manner as in Example 1 (3).

Both vapor deposition and printing were judged to be removable with cellophane tape: 4 for each
Grade) 9 The surface treatment layer was slightly peeled off even in the hand detection test. In addition, the uneven pattern was uneven and some laminates were missing. The laminate was also destroyed by the vapor deposition and printing layers.

Example 2. Table 6 shows the raw material characteristics, film surface characteristics, and failure status of the laminate during rolling of the ethylene/propylene block copolymer layer of Comparative Example 2-1.2-2.

Example 3 (1) A resin in which 25 weight of calcium carbonate with a particle size of 1°7μ is engaged with a polypropylene resin of M, I 1.0 and 1
Coextruding an ethylene O propylene random copolymer resin with M, I6.5, ethylene component 25 weight ratio, propylene component 97.5 weight ratio, DSC 120'O isothermal crystallization curve peak of 1 minute using a two-layer die, Mold, vertical direction (1
25°C, 40x), biaxial and heat-set sequentially in the horizontal direction (160°0,9x), one side corona discharge treated, 90μ
A laminated film was obtained. This biaxially stretched film consisted of an 8 micron ethylene 6 propylene random copolymer layer and an 82 micron polypropylene layer containing a filler, and had a wet tension of 68 dynes/eIN on each of the nine sides.

The length direction of the ethylene/propylene random copolymer layer (
The orientation coefficients in the MD) and transverse directions (TD) were each 1.5.41.

(Similar to (2) of Example 1, the laminated film obtained in Section 21L (1) was subjected to a one-shot test for adhesion between the vapor-deposited film of the ethylene-propylene random copolymer layer and the printing ink. As in (3) of Example 1, the laminate was rolled (the apparent specific gravity of the filler-containing film was 0.5
8).

In both vapor deposition and printing, a glossy, fine, acute-angled wrinkled pattern (same as Example 1) was obtained without peeling or destruction of the laminate, using cellophane tape and manual creasing.

Comparative Example 3-1 (1) The stretching temperature in the horizontal direction of Example B was changed to 145°C, but the other conditions were the same, and the wetting tension on both sides was 68 dynes/C.
A 90μ laminated film of ff1 was obtained.

(2) The laminated film obtained in (1) above was subjected to a 9-point test for adhesion between the vapor deposited film and printing ink in the same manner as in (2) of Example 1. Furthermore, the laminate was rolled in the same manner as in (3) of Example 1 (the apparent specific gravity of the filler-containing film was 0.52).

Both vapor deposition and printing were peeled with cellophane tape, and each surface treatment layer was peeled off in the 9 hand testing (grade 6 for each). The laminate was also destroyed by the vapor deposition and printing layers.

Comparative Example 6-2 (1) M, I 7.0. Ethylene component quadruple economy,
An ethylene-propylene random copolymer with a DSC 120°C isothermal crystallization curve having a peak of 10 minutes was prepared in Example B (1).
, same as (2), 9 sides, wet tension 38 dynes/
A 90μ laminated film of Cm was obtained.

(2) The laminated film obtained in (1) above was subjected to a 9-point test for adhesion between the vapor deposited film and printing ink in the same manner as in (2) of Example 1. Furthermore, as in (3) of Example 1, the laminate was rolled.

Both vapor deposition and printing did not peel off with cellophane tape (rating: 5th grade for each).Each surface treatment layer did not peel off even in a semi-naked test, and although the adhesion was strong, the surface unevenness was uneven and the appearance was poor.

Example 3. Table 4 shows the film surface characteristics of the ethylene-propylene random copolymer layer of Comparative Example 3-1.3-2 and the state of failure as a laminate during rolling.

〔Effect of the invention〕

The present invention provides the following effects as a pseudo-skin laminate.

(b) Because the adhesion strength of the printed/evaporated layer is strong, peeling from the printed/evaporated layer is likely to occur.

(b) Excellent ability to form sharp unevenness and maintain the uneven pattern.

(c) Excellent surface wear resistance and friction resistance.

Note that the laminate of the present invention can be used in the sewing processing field such as bags, bags, and clothing miscellaneous goods, in the construction material field such as wall materials and flooring materials, and in the field of books, stationery, and furniture. Furnishings, etc.

For decoration, interior decoration, plastic, metal.

It can be used by pasting onto wood, inorganic materials, etc. However, it is not limited to these uses.

[Brief explanation of drawings]

FIGS. 1 and 2 are cross-sectional views of the pseudo-skin-like laminate of the present invention, and FIGS. 3 and 4 are views showing DSC melting curves. 1: Polyolefin film containing filler 2: Ethylene-propylene copolymer layer 3: Printed/evaporated layer 4 Niblastic film layer 5: Flexible base sheet 425': Adhesive layer P1: Melting peak on low temperature side P2: High temperature Side melting peak A: Vertex of melting peak of Pl: Vertex of melting peak of P2 Patent applicant Toshi Co., Ltd. )

Claims (1)

[Claims] The layer (2) is mainly composed of one of the following (A), (B), and (C) ethylene propylene copolymers and has an orientation coefficient of 7.0 or less, and a printed/evaporated layer ( 3) is laminated with a plastic film layer (4) on one side of the printed/deposited film.
, a stretched polyolefin film layer containing 10 to 40% by weight of filler on the other side and having an apparent specific gravity of 0.2 to 0.7 (
1) are laminated, and a flexible base sheet (5) is further laminated on the outer surface of the layer (1), and at least the layer (1), the layer (2), and the layer (3) A pseudo-skin-like laminate in which a concavo-convex pattern is formed. (A) A block copolymer with an ethylene component of 10 to 50% by weight and the rest being propylene as a main component and 100 to 165% by weight.
An ethylene/propylene copolymer that has three or more melting peaks at °C. (B) A block copolymer with an ethylene component of 10 to 50% by weight and propylene as the main component, with one melting peak at 126°C or higher and lower than 140°C, and one at 140°C or higher and lower than 160°C. and the heat of fusion H_1 at each peak,
H_2 is 0.3≦H_1/(H_1+H_2)≦0.7
An ethylene-propylene copolymer that satisfies the following relationship. (C) An ethylene-propylene copolymer which is a random copolymer containing 1 to 15% by weight of ethylene and whose time to peak in a DSC isothermal crystallization curve at 120°C is 9 minutes or less.