JPH08332690A - Composite laminated resin film - Google Patents

Abstract

PURPOSE: To obtain a lightweight film having strength and rigidity by laminating synthetic paper composed of a stretched thermoplastic resin laminated film on the single surface or both surfaces of a support layer of a non-stretched thermoplastic resin layer film containing an inorg. fine powder in a specific ratio. CONSTITUTION: A support layer A with a wall thickness of 200-500μm having non- stretched thermoplastic resin layers a<2> , a<2> ' containing 20-60wt.% of an inorg. fine powder laminated thereto is formed on both surfaces of the core layer a of a<1> non- stretched thermoplastic resin film containing 0-3wt.% of an inorg. fine powder. Composite synthetic paper B with a wall thickness of 30-300μm formed of paper like layers b<2> , b<2> ' each composed of a stretched thermoplastic resin film containing 8-65wt.% of an inorg. fine powder and a base material layer b<1> is laminated to the single surface or both surfaces of the support layer so that the paper like layers b<2> , b<2> ' form an outer surface to obtain a composite laminated resin film with a wall thickness of 250-800μm and density of 0.70-1.1g/cm<3> . The sum of the wall thicknesses of the resin layers a<2> , a<2> ' is set to a ratio of 0.3-1 with respect to the wall thickness of the core material layer a<1> . By this constitution, the lightweight composite laminated resin film prevented from the lowering of rigidity can be obtained.

Description

Detailed Description of the Invention

[0001]

INDUSTRIAL APPLICABILITY The present invention is useful as a paper such as a playing card, a document file, a hanging sign, a mount, a flower label to be inserted in a flowerbed or a flowerpot, and is capable of being printed and written and having a wall thickness of 250. The present invention relates to a composite laminated resin film having a thickness of up to 800 μm.

[0002]

2. Description of the Related Art Conventionally, playing cards, document files,
The following physical properties are required for a thick synthetic paper used as a hanging sign, a mount, a flower label to be inserted into a flowerbed or a flowerpot, and the like. ． Good printability and writability. ． It must be concealed so that the characters printed on the front side cannot be seen through from the back side. ． Water resistance and strength to the extent that it will not be deformed or damaged by wind and rain or strong winds when hanging the sign with wire. ． Thick and rigid enough to prevent curling. And it is more preferable that it is lightweight.

In fact, in the above playing card paper, a uniaxially stretched film of a thermoplastic resin containing about 50% by weight of an inorganic fine powder is used as a paper layer (b ² ), and a biaxially stretched resin film is used as a base material layer. The thickness formed as (b ¹ ) is 150μ
m two-layer synthetic paper (B) is used, and these paper-like layers (b ² )
A card paper having a thickness of 302 μm, which is pasted with a liquid adhesive containing titanium oxide so that the side forms the outer surface, has been put into practical use. However, since this card paper is a laminated product of a stretched resin film, when it is used as a hanging sign for outdoor use, stress concentrates in the orientation direction of the film due to strong wind, so it tends to tear and break. There are drawbacks. Therefore, as a thick synthetic paper which prevents damage due to a strong wind and has high rigidity and bending elastic modulus, the inventors of the present invention commercially available synthetic paper composed of a stretched film having a density of 0.77 to 0.80 g / cm ^3. Then, it was examined to bond an unstretched film containing a large amount of inorganic fine powder. However,
This product contains a large amount of inorganic fine powder and has a specific gravity of usually 1.4 to 7.8. Therefore, the density of the bonded product exceeds 1.1 g / cm ³ and it is lightweight. Improvement is desired.

[0004]

DISCLOSURE OF THE INVENTION The present invention is based on the above items
It has good printability and writability, can not see through the printed characters (concealment), has water resistance and strength, is thick, has rigidity, and Another object of the present invention is to provide a lightweight composite laminated resin film.

[0005]

[Means for Solving the Problems]

[Summary of the Invention] The present inventors have conducted intensive studies in view of the above problems, and as a result, have formed an inorganic fine powder-containing unstretched thermoplastic resin film to be laminated on synthetic paper into a multilayer structure of three or more layers, It was found that the rigidity does not decrease even if the content of the inorganic fine powder in the layer is reduced, and the present invention has been completed. That is, the composite laminated resin film of the present invention has 20 to 20% of the inorganic fine powder on both surfaces of the core material layer (a ¹ ) made of an unstretched thermoplastic resin film containing the inorganic fine powder in a proportion of 0 to 3% by weight. The unstretched thermoplastic resin layers (a ² ) and (a ^{2 ′} ) contained in the proportion of 60% by weight have a thickness of 200-
A uniaxially stretched film of a thermoplastic resin containing an inorganic fine powder in a proportion of 8 to 65% by weight on one or both sides of a support layer (A) made of a thermoplastic resin laminated film of 500 μm in a paper-like layer (b ² ). , (B ^{2 ′} ) and a biaxially stretched thermoplastic resin film formed as the base material layer (b ¹ ) has a wall thickness of 30 to 300.
Multi-layer synthetic paper (B) having a thickness of 25 μm was laminated integrally so that the paper-like layers (b ² ) and (b ^{2 ′} ) side form the outer surface.
A composite laminated resin film having a density of 0 to 800 μm and a density of 0.70 to 1.1 g / cm ³ , wherein the unstretched thermoplastic resin layers (a ² ) and (a ^{2 ′} ) of the support layer (A) are The sum of the wall thicknesses is characterized by occupying a ratio of 0.3 to ^{1 with} respect to the wall thickness of the core material layer (a ¹ ).

[0006]

[Function] Support layer made of unstretched thermoplastic resin film
The presence of (A) improves the tear resistance of the composite laminated resin film. In addition, the core material layer (a
^By adjusting the wall thickness ratio without substantially mixing the inorganic fine powder in ¹ ), it was possible to obtain a lightweight composite laminated resin film in which reduction in rigidity was prevented.

[Detailed Description of the Invention] [I] Composite Laminated Resin Film (1) Structure The composite laminated resin film 1 of the present invention is as shown in FIG.
Support layer made of unstretched thermoplastic resin laminated film (A)
The synthetic paper (B) made of a stretched thermoplastic resin laminated film is attached to one or both sides of the above. (2) Support layer (A) The thermoplastic resin laminated film used for this support layer (A) is a non-stretched thermoplastic resin core material layer (a ¹ ) Thermoplastic resin layer (a ² ), (a ^{2 '} )
Is a laminated film in which (a) Core Material Layer (a ¹ ) The core material layer (a ¹ ) is a thermoplastic resin (a ¹ ) film containing substantially no inorganic fine powder. The meaning of substantially not containing the inorganic fine powder is that it contains not only the thermoplastic resin (a ¹ ) film containing no inorganic fine powder but also some inorganic fine powder. Is also good. Specifically, the inorganic fine powder has a quantitative range of 3% by weight or less, preferably 0 to 2% by weight. If the core layer (a ¹ ) contains a relatively large amount of inorganic fine powder, the weight cannot be reduced.

(B) Inorganic fine powder-containing unstretched thermoplastic resin layer (a ² ), (a ^{2 ′} ) Above inorganic fine powder-containing unstretched thermoplastic resin layer (a ² ), (a ^{2
2 '} ) is a thermoplastic resin (a ² ) containing 20 to 60% by weight, preferably 45 to 60% by weight, of inorganic fine powder.
, (A ^{2 '} ) is not oriented by stretching. Further, the inorganic fine powder-containing unstretched thermoplastic resin layer (a
² ) If the content of the inorganic fine powder of (a ^{2 '} ) is less than 20% by weight, the rigidity of the composite laminated resin film cannot be improved. Further, if the content of the inorganic fine powder exceeds 60% by weight, the support layer (A) having a uniform thickness cannot be obtained.

(C) Laminated layer The thermoplastic resin laminated film used for these support layers (A) is a non-stretched thermoplastic resin (a ² ), containing inorganic fine powder in a proportion of 20 to 60% by weight. a ^{2 ′} ) and a thermoplastic resin (a ¹ ) substantially containing no inorganic fine powder,
Each is melt-kneaded with a separate extruder, supplied to one co-extrusion die, by co-extrusion from the co-extrusion die, inorganic fine powder containing unstretched thermoplastic resin layer (a ² )
, (A ^{2 ′} ) and the thermoplastic resin layer (a ¹ ) substantially containing no inorganic fine powder are laminated to produce a support layer (A). Alternatively, one thermoplastic resin film may be manufactured in advance, and then another thermoplastic resin film may be melt-laminated and laminated on the other thermoplastic resin film. Further, a thermoplastic resin layer that does not substantially contain these inorganic fine powders
(a ¹ ) and inorganic fine powder containing unstretched thermoplastic resin (a ² ) (a
A resin film having a different inorganic fine powder content or a different inorganic fine powder content may be present between ^{2 '} )).

[0010 (d) The thickness core material layer (a ¹⁾ relative to the thickness (core layer (a ¹⁾ the thickness of 1 to the in), the other inorganic fine powder 20 to 60 wt%
Unstretched thermoplastic resin layer (a ² ), (a ^{2 '} )
The sum of the thickness (Ta ² + Ta ^{2 ')} is 0.3 to 1, preferably prepared so that 0.5 to 1. The core material layer (a ¹ ) and the inorganic fine powder-containing unstretched thermoplastic resin layers (a ² ) and (a ^{2 '} )
And the wall thickness ratio [(Ta ² + Ta ^{2 '} ) / (Ta ¹ )] is 0.3.
If it is less than 1, a composite laminated resin film having good rigidity cannot be obtained, and if it exceeds 1, it becomes difficult to obtain a composite laminated resin film having a density of 1.1 g / cm ³ or less. Therefore, the thickness of the core material layer (a ¹⁾ (Ta ¹⁾ is generally 100 to
350 .mu.m, preferably 150 to 250 [mu] m, the front and back layers ^{(a 2), (a 2} ') the thickness sum of (Ta ² + Ta ^2') are each generally 50 to 250 [mu] m, preferably 50~125μm
Is. Non-stretched thermoplastic resin laminated film (a ² ) /
The thickness of the support layer (A) composed of (a ¹ ) / (a ^{2 ′} ) is 200
˜500 μm, preferably 300 to 500 μm.

[0011] (e) Material thermoplastic resin above unstretched thermoplastic resin laminate support layer made of a film
Examples of the thermoplastic resin used in (A) include low-density, medium-density, and high-density polyethylene, polypropylene, ethylene-propylene copolymer, ethylene or propylene / other α
Examples thereof include olefin resins such as olefin copolymers, polystyrene, styrene resins such as acrylonitrile / styrene copolymers, acrylonitrile / butadiene / styrene resins, polyethylene terephthalate, polyamides and the like. Among these, it is preferable to use inexpensive polypropylene or high-density polyethylene. These resins may be used in combination of two or more kinds, or may be a laminated body of different resins.

Inorganic fine powder Inorganic fine powder-containing unstretched thermoplastic resin layer (a ² ), (a ^{2 ′} )
Examples of the inorganic fine powder used in the above include heavy calcium carbonate, calcined clay, burmculite, titanium oxide, barium oxide, silica stone, talc, mica, diatomaceous earth and the like. These may be used in combination of two or more. The particle size of these inorganic fine powders is generally 0.03 to 15 μm, preferably 0.1 to 5 μm.

(3) Multi-layer synthetic paper (B) (a) Structure The multi-layer synthetic paper (B) attached to the support layer (A) made of the above-mentioned non-stretched thermoplastic resin laminated film is, for example, , The wall thickness is generally 30 to 300 μm, preferably 60 to 150 μm
And a biaxially stretched thermoplastic resin film having pores (voids) is used as the base material layer (b ¹ ), and one or both surfaces of the base material layer contains inorganic fine powder in a proportion of 8 to 65% by weight. A uniaxially stretched film of a plastic resin is laminated as a paper-like layer (b ² ). The multilayered synthetic paper (B), thus the substrate layer (b ¹⁾ in paper-like layer (b ²⁾ be of a laminated two-layer structure, also, the base layer (b ¹⁾ thermoplastic resin uniaxially stretched paper-like layer of the film on the front and back surfaces of the (b ^2), (b ^{2 ')} be of a laminated three-layer structure (JP-b-46-40794), and the paper-like layer ( B ² ), (b ^{2 ′} ) and the base material layer (b ¹ ), the other resin film layers (b ³ ), (b ^{3 ′} ) are present in the three to seven layers of synthetic paper (Japanese Patent Publication 50-29738, Japanese Patent Publication No. 57-
No. 149363, Japanese Patent Publication No. 56-126155, Japanese Patent Publication No. 57-181829), or the back side thereof is a metal salt of propylene / ethylene copolymer or ethylene / (meth) acrylic acid copolymer (Na, Li). , Zn, K), chlorinated polyethylene, or the like, may be a synthetic paper having three or more layers in which a heat seal layer formed of a resin having a melting point lower than that of the resin forming the base material layer (b ¹ ) is laminated. Such a multi-layer synthetic paper (B) is known as described in JP-B-46-40794, JP-A-57-149363, JP-A-57-181829 and the like. Specifically, at Oji Yuka Synthetic Paper Co., Ltd., "Yupo FPG, TPG,
It is already sold under the product name of "KPG, SG".

[0014] substrate layer used in the extension Shin multilayered synthetic paper (B) (b ¹⁾ is an inorganic fine powder 0-45 wt%, preferably the resin a thermoplastic resin film containing 10 to 30 wt% At a temperature lower than the melting point of 3.5 to 10 times in the longitudinal direction, preferably 4 to 7
It is a stretched resin film having a large number of fine rugby ball-shaped pores (voids) inside the film obtained by stretching the film 3.5 times to 20 times, preferably 4 to 12 times in the transverse direction. Also, a paper-like layer laminated on such a base material layer (b ¹ ).
^{(b 2), (b 2} ') is 8-65% by weight of an inorganic fine powder on one or both sides of the substrate layer (b ^1), preferably a thermoplastic resin film the resin containing 15 to 55 wt% At a temperature lower than the melting point of 3.5 to 20 times in the longitudinal direction, preferably 4 to 12 times.
A uniaxially stretched film obtained by stretching twice, and when the content of the inorganic fine powder is 8% by weight or more, the film has a large number of fine long holes (voids) and the film surface is It is a uniaxially stretched resin microporous film that has cracks and is excellent in printability and writability.

The length of the voids (voids) is about the particle size of the inorganic fine powder × stretching ratio. This multilayer synthetic paper (B) has fine voids (pores) inside the film, and the porosity is 10 to 60%, preferably 15 to 50%, calculated by the following formula. % Makes it lightweight (density 0.68 to 1.1 g / cm ³ ).
The result is a strong synthetic paper. ρ ₀ : Density of film before stretching ρ: Density of film after stretching

The thickness of the thick multilayer synthetic paper base layer in (B) (b ¹⁾ is generally 20 to 200 [mu] m, preferably 50 to 150 [mu] m, also, the paper-like layer (b ^2), (b The wall thickness of ^{2 '} ) is generally 0.5 to 100 µm, preferably 0.5 to 50 µm. The overall thickness of this multi-layer synthetic paper (B) is generally 3
It is 0 to 300 μm, preferably 60 to 150 μm.
Moreover, the thickness of the base material layer (b ¹ ) is preferably 40 to 99%, particularly preferably 50 to 99% of the total thickness of the multilayer synthetic paper (B).
It preferably accounts for 80%. As the inorganic fine powder and the thermoplastic resin used in the multilayer synthetic paper (B), those mentioned in the section of the support layer (A) can be used.

Sticking method Various sticking methods are available for sticking the multi-layer synthetic paper (B) on one or both sides of the support layer (A) which is a non-stretched thermoplastic resin laminated film. However, for example, the following methods (1) to (4) are preferable. The resin composition for the support layer (A) composed of the unstretched laminated resin film is melt-kneaded in the extruder, and the heat is utilized while being extruded from the co-extrusion die and still in the molten state, and the metal is coated on one side. Multi-layer synthetic paper from roll or rubber roll
A thermal laminating method in which (B) is pressure-welded. A support layer (A) made of unstretched laminated resin film and a multi-layer synthetic paper (B) are used as a hot-melt adhesive or solvent-type adhesive.
There is a method of pasting with (C). At this time, a publicly known adhesive hot melt adhesive layer may be provided on the upper layer of the unstretched laminated resin film (A) by a coextrusion method, or a multilayer synthetic paper (B) having a hot melt adhesive layer may be used. .

[0018] Using the contact adhesive the adhesive (C), on one side or both sides of a support layer made of non-stretched laminate resin films (A), is used multilayered synthetic paper (B) when bonding together Examples of hot melt adhesives include low density polyethylene, linear low density polyethylene, ethylene / vinyl acetate copolymer (preferably ethylene / vinyl acetate copolymer having a vinyl acetate content of 12% by weight or less), ethylene / acrylic acid. Copolymer (preferably ethylene / acrylic acid copolymer having an ethylene content of 65 to 94% by weight), ethylene / methacrylic acid alkyl ester copolymer, ionomer (metal salt of ethylene / acrylic acid copolymer, or ethylene -Methacrylic acid copolymer metal salt), ethylene-propylene copolymer, ethylene-propylene-butene-1 copolymer, vinyl chloride-vinyl acetate Examples thereof include a nyl copolymer and the like. These may be used in combination of two or more. Examples of solvent-based adhesives include polyether polyol / polyisocyanate adhesives and polyester polyol / polyisocyanate adhesives. These may be used in combination of two or more.

(4) Thickness Ratio The thickness ratio of the support layer (A) and the multilayer synthetic paper (B) is set so that the density of the composite laminated resin film is 1.1 g / cm ³ or less. It The thickness of such an adhesive layer is generally 1 to 30 μm, preferably 1 to 20 μm. Specifically, the coating type adhesive is 1 to 20 g /
It is applied in an amount of m ² , preferably 2-8 g / m ² . Hot melt type adhesive is melt extrusion laminated,
It is heat-sealed to a thickness of 30 μm, preferably 8 to 20 μm. When the multi-layer synthetic paper (B) is attached to one side of the support layer (A), the thickness ratio of both is (T (A) / T (B)) is 1.2.
-10, preferably 2 to 5, and when the multilayer synthetic paper (B) is attached to both sides of the support layer (A), T (A) / (T
(B) + T (B ')) is 0.7 to 3.8, preferably 1 to 3.

(5) Printing (D) At least the paper-like layer (b ² ) on the side of the multilayer synthetic paper (B) of the composite laminated resin film is optionally subjected to gravure printing, offset printing, screen printing or the like. In particular, the one using a multicolor printing ink is preferable from the viewpoint of appearance.

[0021]

EXAMPLES The present invention will be described in detail below with reference to examples of the present invention. [I] Evaluation Physical properties in the examples were evaluated by the following methods. (1) Offset printing property Offset printing ink "TSP" manufactured by Toyo Ink Mfg. Co., Ltd.
-400 "(trade name) and an offset four-color printer manufactured by Komori Printing Co., Ltd. are used to perform four-color (black, blue, red, yellow) flat plate offset printing on the surface side of the synthetic laminated resin film synthetic paper. The ink transferability and ink adhesion were evaluated by the following methods. Ink transferability The dot portion of each color was visually evaluated with magnifying paper (30 times) on magnified paper and dot reproduction. Halftone dot reproducibility 100-75%: Good (○) 75-50%: Slightly bad (△) 50-0%: Poor (x) Ink adhesion Nichiban Co., Ltd. adhesive tape "Cellotape" (product Name)
Was strongly adhered to the printed surface and quickly peeled off along the printed surface, and the degree of ink detachment from the paper surface was visually judged. Ink residue rate 100 to 95%: Good (○) 95 to 80%: Slightly bad (△) 80 to 0%: Poor (x)

(2) Pencil writing Pencil "Mitsubishi 9800" HB (trade name) manufactured by Mitsubishi Pencil Co., Ltd.
Was used and evaluated with a normal writing pressure (200 g). In addition,
The criteria for evaluation were that those of sufficient density were good, and those of which sufficient density could not be written even when the writing pressure was increased were regarded as poor. (3) Tear strength Tear strength was measured according to JIS P-8116. (4) Taber stiffness The Taber stiffness was measured according to JIS P-8125. (5) Flexural modulus The flexural modulus was measured according to JIS K-7203. (6) Density Density was measured according to JIS P-8118. (7) Opacity Opacity was measured according to P-8138.

[II] Experimental Example Example 1 Production of multi-layer synthetic paper (B) (1) 81% by weight of polypropylene (melting point about 164-167 ° C.) with melt flow rate (MFR) 0.8 g / 10 min
High density polyethylene 3% by weight and average particle size 1.5μ
m, a composition (B ¹ ) in which 16% by weight of calcium carbonate having a specific gravity of 2.7 was mixed by an extruder set at a temperature of 270 ° C., then extruded into a sheet, and further cooled at 60 ° C. by a cooling device. It cooled to temperature and the non-stretched sheet was obtained. Then, this sheet was heated again to a temperature of 150 ° C., and then stretched 5 times in the longitudinal direction to obtain a 5 times longitudinally stretched film. (2) Polypropylene having a MFR of 0.4 g / 10 min (melting point of about 164-167 ° C.) 54% by weight and an average particle size of 1.5 μ
Composition of (B ² ) in which 43% by weight of calcium carbonate, 0.8 μm in particle diameter, and 3% by weight of titanium oxide having a specific gravity of 4.3 are mixed.
Was kneaded in another extruder, extruded into a sheet with a die, and extruded on both sides of the 5 × longitudinally stretched film obtained in the step (1) above to laminate, then 6
After cooling to a temperature of 0 ° C, the three-layer laminate [(B ² ) / (B ¹ ) /
(B ² )] was obtained. The three-layer laminate is then reapplied for about 15 minutes.
It is heated to a temperature of 5 ° C, stretched 7.5 times in the transverse direction using a tenter, annealed at a temperature of 163 ° C, cooled to a temperature of 60 ° C again, and the ears are slit to form three pieces. Thickness of layer structure (uniaxial stretching / biaxial stretching / uniaxial stretching) 6
0 μm [(b ² ) / (b ¹ ) / (b ^{2 ′} ) = 16 μm / 28 μm
/ 16 μm] to obtain a multilayer synthetic paper (B) composed of a laminated film (porosity 33%).

After coating the surface of this three-layer laminated film with a corona discharge,
0.05 g / m ² solid solution on both surfaces of coating solution
It was coated and dried to have a wall thickness of about 0.1 μm, and wound up. The composition of the coating agent aqueous solution was as follows. (a) Mitsubishi Chemical Corporation aqueous solution polyacrylic antistatic polymer "ST-1100" (

[0025]

Embedded image

100 parts by weight (b) Epichlorohydrin adduct of water-soluble polyamine polyamide (Kymene 557 manufactured by Dick Hercules Co., Ltd.)
H "): 25 parts by weight

Printing Multilayer synthetic paper coated with such a primer (thickness 6
On the surface of 0.1 μm), characters and patterns were offset printed using commercially available four color inks.

Production of non-stretched resin film support (A) On the other hand, propylene homopolymer [melt flow rate (M
FR) 5.0 g / 10 min "Mitsubishi Polypro FY4" (trade name)] 56 parts by weight, and a composition (A ² ) in which 44 parts by weight of calcium carbonate having a particle size of 1.5 μm and a specific gravity of 2.7 are blended,
A composition in which 98 parts by weight of a propylene homopolymer [MFR 2.3 g / 10 minutes, “Mitsubishi Polypro FY6C” (trade name)] is mixed with 2 parts by weight of titanium oxide having a particle size of 0.8 μm and a specific gravity of 4.3 (A ¹ ) and 220 with separate extruders
After melt-kneading at a temperature of ℃, supply into one die,
After stacking (A ² ) / (A ¹ ) / (A ² ) in the die, it is extruded and the white layer of the three-layer structure [(a ² ) / (a ¹ ) / (a ^{2 ′} )] A support (A) composed of a stretched resin laminated film was obtained (thickness: 60 μm / 160 μm / 60 μm).

Production of composite laminated resin film White non-stretched resin laminated film support (A) obtained by extruding from the above die on the surface of the printed multilayer synthetic paper (B) which is not the printing surface While the film is still in the softened state, the non-stretched resin laminated film support (A) is thermally laminated so that the printed multi-layer synthetic paper layer (B) (thickness 60.1 μm) / support Body layer (A) (wall thickness 28
0 μm) / multi-layer synthetic paper layer (B) (thickness 60.1 μm) to obtain a composite laminated resin film (thickness 400.2 μm). The physical properties of this product are shown in Table 1.

Comparative Example 1 In Example 1, the support layer (A) was replaced by a propylene homopolymer "Mitsubishi Polypropylene" instead of the one having a three-layer structure.
A single-layer film (meat) extruded from a flat die at a temperature of 220 ° C. was obtained by mixing 23 parts by weight of calcium carbonate having a particle size of 1.5 μm and 2 parts by weight of titanium oxide with 77 parts by weight of “FY6C” (trade name), and kneading the mixture. A composite laminated film having the physical properties shown in Table 2 was obtained in the same manner as in Example 1 except that the thickness was 280 μm).

Comparative Example 2 In Example 1, the support layer (A) was replaced by a propylene homopolymer “Mitsubishi Polypropylene” instead of the one having a three-layer structure.
54 parts by weight of “FY6C” (trade name), 44 parts by weight of calcium carbonate having a particle diameter of 1.5 μm and 2 parts by weight of titanium oxide were melt-kneaded and extruded from a flat die at a temperature of 220 ° C. A composite laminated film having the physical properties shown in Table 2 was obtained in the same manner as in Example 1 except that (thickness 280 μm) was used.

Comparative Example 3 Multi-layer synthetic paper "YUPO FPG1" manufactured by Oji Yuka Synthetic Paper Co., Ltd.
Table 2 shows the physical properties of a composite synthetic paper (thickness: 302 μm) obtained by laminating two sheets of 50 ”(trade name) with a polyether polyol / polyisocyanate adhesive (thickness: 2 μm).

Example 2 Production of multi-layer synthetic paper (B) (1) Melt flow rate (MFR) 0.8 g / 10 min polypropylene (melting point about 164-167 ° C.) 81% by weight
High density polyethylene 3% by weight and average particle size 1.5μ
composition containing 16% by weight of calcium carbonate (B ¹ )
Was kneaded with an extruder set at a temperature of 270 ° C.,
It was extruded into a sheet shape and further cooled to a temperature of 60 ° C. by a cooling device to obtain an unstretched sheet. Then, this sheet was heated again to a temperature of 150 ° C., and then stretched 5 times in the longitudinal direction to obtain a 5 times longitudinally stretched film. (2) Polypropylene having a MFR of 0.4 g / 10 min (melting point of about 164-167 ° C.) 54% by weight and an average particle size of 1.5 μ
m composition of calcium carbonate (46% by weight)
After (B ² ) was kneaded in another extruder, it was extruded into a sheet by a die, and extruded on both sides of the 5 × longitudinally stretched film obtained in the step (1) above, then 60 Cooled to a temperature of ℃ ℃ and laminated three layers [(B ² ) / (B ¹ ) / (B ² ).
] Was obtained. Then, the three-layer laminate is again heated to about 155 ° C.
And heat it to the temperature of 7.5 ° C using a tenter to the lateral direction.
Double stretching and annealing treatment at a temperature of 163 ° C.
Cooled to a temperature of 0 ° C, slit the ears, and have a three-layer structure (uniaxially stretched / biaxially stretched / uniaxially stretched) with a wall thickness of 90 μm [(b
² ) / (b ¹ ) / (b ^{2 ′} ) = 20 μm / 50 μm / 20 μ
m], a multi-layer synthetic paper (B) made of a laminated film (porosity 33%) was obtained.

Primer coating After the surface of this three-layer laminated film was subjected to corona discharge treatment,
The aqueous solution of the coating agent used in Example 1 was applied on both surfaces so that the solid content was 0.05 g / m ² on one side (thickness of about 0.1 μm), dried, and wound up.

Manufacture of non-stretched resin film support (A) Propylene / ethylene random copolymer "Mitsubishi Polypro FX-4" (trade name) (A ³ ), propylene homopolymer (MFR5 ) manufactured by Mitsubishi Chemical Corporation. 0.0 g / 10 minutes "Mitsubishi Polypro FY4": trade name) 56 parts by weight, particle size 1.5 μ
m composition of calcium carbonate (44 parts by weight) (A ² ).
And 98 parts by weight of a propylene homopolymer (MFR 2.3 g / 10 minutes "Mitsubishi Polypro FY6C": trade name),
The composition (A ¹ ) containing 2 parts by weight of titanium oxide was melt-kneaded at a temperature of 220 ° C. in separate extruders, respectively,
It is supplied into one die, laminated in the die, and then extruded to form a five-layer structure [(a ³ ) / (a ² ) / (a ¹ ) / (a ^{2 ′} ) /
(a ^{3 ′} )] of a white non-stretched resin laminated film (A) was obtained (thickness 3 μm / 55 μm / 140 μm / 5
5 μm / 3 μm).

Production of Composite Laminated Resin Film White non-stretched resin laminated film support (A) obtained by extruding from the above die on the surface of the printed multilayer synthetic paper (B) which is not the printing side. While still in the softened state, the non-stretched resin laminated film support (A) is thermally laminated to obtain a printed multilayer synthetic paper layer.
(B) (wall thickness 90.1 μm) / support layer (A) (wall thickness 256
μm) / multi-layer synthetic paper layer (B) (thickness 90.1 μm) to obtain a composite laminated resin film (thickness 436.2 μm). The physical properties of this product are shown in Table 1.

Example 3 In Example 1, when the composite laminated resin film was produced, the support layer (A) made of the unstretched thermoplastic resin laminated film obtained by extrusion from the die was still kept in the softened state. Among them, a multilayer synthetic paper (B) in which printing is performed only on one surface of the support (A) composed of the unstretched thermoplastic resin laminated film
Thermally laminating the side not printed, the printing / multi-layer synthetic paper (B) (wall thickness 90.1 μm) / support layer (A) made of non-stretched thermoplastic resin laminated film (wall thickness 280
μm) composite laminated resin film (thickness 370.1
μm) was obtained. The physical properties of this product are shown in Table 1.

[0038]

[Table 1]

[0039]

[Table 2]

[0040]

The composite laminated resin film of the present invention has the support layer (A) composed of the unstretched thermoplastic resin laminated film, so that the tear resistance of the composite laminated resin film is improved, Moreover, since the thickness ratio was adjusted without substantially mixing the inorganic fine powder in the core layer (a ¹ ) of the support layer (A), the decrease in rigidity could be prevented. A lightweight composite laminated resin film can be obtained.

[Brief description of drawings]

FIG. 1 is a cross-sectional view of a composite laminated resin film of an example of the present invention.

[Explanation of symbols]

1 composite laminate resin film A support layer A ¹ composition a ¹ core layer a ^2, a ^{2 'unstretched} thermoplastic resin layer a ^3, a ^3' non-oriented thermoplastic resin layer A ² composition A ³ composition B multilayered synthetic paper B ¹ composition B ² composition b ¹ substrate layer b ^2, b ^{2 'paper-like} layer C adhesive layer D printing

Claims (1)

[Claims] 1. A core material layer (a ¹ ) comprising an unstretched thermoplastic resin film containing an inorganic fine powder in a proportion of 0 to 3% by weight.
A thermoplastic resin laminated film having a wall thickness of 200 to 500 μm in which non-stretched thermoplastic resin layers (a ² ) and (a ^{2 ′} ) containing 20 to 60% by weight of inorganic fine powder are laminated on both surfaces of A uniaxially stretched film of a thermoplastic resin containing an inorganic fine powder in a proportion of 8 to 65% by weight as a paper-like layer (b ² ) or (b ^{2 ′} ) on one or both sides of the support layer (A) , A biaxially stretched thermoplastic resin film as a base material layer (b ¹ ) and a multi-layer synthetic paper (B) having a wall thickness of 30 to 300 μm, a paper-like layer
The (b ² ), (b ^{2 ′} ) sides are integrally bonded so as to form the outer surface, the thickness is 250 to 800 μm, and the density is 0.70.
It is a composite laminated resin film of ~ 1.1 g / cm ³ ,
An unstretched thermoplastic resin layer (a ² ) of the support layer (A),
The sum of the wall thicknesses of (a ^{2 ′} ) is 0 with respect to the wall thickness of the core layer (a ¹ ).
A composite laminated resin film, characterized by occupying a ratio of 3 to 1.