JP2002173538A - Resin film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin film having excellent printability by which the phenomenon of the surface becoming uneven can be prevented even if the offset printing by using a general-purpose quick drying offset ink is applied. SOLUTION: This resin film is characterized in that the film has a layer (A) comprising 0-85 wt.% polyolefin-based resin, 15-100 wt.% amorphous resin and 0-70 wt.% inorganic fine powder and/or organic filler.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin film excellent in printability, which prevents a phenomenon in which a film in an offset ink becomes uneven due to a vehicle in offset ink when offset printing is performed. This resin film is useful as a material for poster paper, wrapping paper, labels, book covers, signs, and the like.

[0002]

2. Description of the Related Art Instead of natural pulp papermaking, a biaxially stretched film of polypropylene containing 5 to 40% by weight of inorganic fine powder is used as a base layer, and the inorganic fine powder is contained on the front and back surfaces of 8 to 65% by weight. A synthetic paper in which a uniaxially stretched polypropylene film is formed as a paper-like layer has been proposed and put into practical use (US Pat. No. 4,318,950;
JP-B-46-40794, JP-B-60-3617
No. 3, JP-B-62-35412, etc.). Usually, offset printing, so-called lithography, can easily perform multicolor printing, and is therefore used for printing on paper, polyethylene terephthalate film, polyamide film, coated paper, and the like. In particular, general-purpose dry offset ink is shown in Fig. 1.
And the composition shown in Table 1.

[0003]

[Table 1]

[0004] The vehicle shown in FIG. 1 is a liquid component of the printing ink, which disperses a pigment to impart fluidity to the ink. It functions to smoothly move to the printing surface via the blanket and to change to a solid after printing and to fix the pigment to the printing surface. In particular, in recent years, it has been required to shorten the drying time of the offset ink in order to improve the printing speed. Therefore, a resin and a mineral oil (a high-boiling petroleum-based solvent) are blended in a drying oil as a vehicle for the ink. Fast drying inks are used.

[0005] However, when printing is performed on a synthetic paper made of a polyolefin film or a stretched film of a polyolefin containing inorganic fine powder using these quick-drying offset inks, it is used as a quick-drying offset ink. The polyolefin itself swells due to the vehicle (especially a high-boiling petroleum solvent such as mineral oil) in the offset ink, and the surface of the printed film partially becomes uneven, so that it is difficult to actually use the film. Therefore, as an offset ink for polyolefin films,
A special offset ink containing no mineral oil at the expense of quick drying is used.

However, such a special offset ink for a polyolefin film has a long drying time,
Since printing shops and ink manufacturers are limited, the emergence of a polyolefin film that can use a general-purpose oxidation polymerization type (dry oil type) offset ink has been desired. In other words, in general printing companies, high-quality paper, pulp-based paper such as coated paper, offset printing using a commercially available quick-drying ink, if you try to print the polyolefin film or synthetic paper, Only then had to switch to a special non-absorbable offset ink for printing. Since the switching of ink requires a lot of time and labor, general printing companies do not actively print polyolefin films such as synthetic paper, which is a polyolefin film or polyolefin synthetic paper. This has been one factor that has hindered its spread to offset printing.

On the other hand, attempts have been made so far to add an amorphous resin to a polyolefin resin and use it for a part of a multilayer film (Japanese Patent Application Laid-Open No. 8-333466). However, the problem that the vehicle (particularly a high boiling point petroleum solvent such as mineral oil) in the offset ink reaches the base layer and swells the entire film (hereinafter, abbreviated as “solvent attack”) has not been solved. Was.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems of the prior art. That is, an object of the present invention is to solve the problem of providing a resin film having excellent printability and preventing a phenomenon in which the surface becomes uneven even when offset printing is performed using a general-purpose quick-drying offset ink.

[0009]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, a non-crystalline resin and an inorganic fine powder or an organic filler are blended in an appropriate ratio to a polyolefin resin. As a result, the present inventors have found that a resin film having excellent printability can be obtained, and have completed the present invention. The present invention has a (A) layer containing 0 to 85% by weight of a polyolefin resin, 15% by weight or more and less than 100% by weight of an amorphous resin, and 0 to 70% by weight of an inorganic fine powder and / or an organic filler. It is intended to provide a characteristic resin film.

In the resin film of the present invention, a layer (B) containing 40 to 100% by weight of a polyolefin resin, 0 to 60% by weight of an inorganic fine powder and / or an organic filler is laminated on at least one surface of the layer (A). Preferably, the amorphous resin used for the resin film is a cyclic olefin-based resin. Further, the polyolefin-based resin of the layer (A) is preferably a propylene-based resin, an ethylene-based resin, or a mixture thereof. Further, a resin film in which a pigment coat layer is provided on at least one surface of the outermost layer is preferable.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the resin film of the present invention will be described in detail. In this specification, “to” means a range that includes numerical values described before and after it as a minimum value and a maximum value, respectively. The resin film of the present invention contains 0 to 85% by weight of a polyolefin resin, 15% to less than 100% by weight of an amorphous resin, and 0 to 70% by weight of an inorganic fine powder and / or an organic filler (A).
Layer as an essential component, (A) on at least one side of the layer,
(A) / (B), (A) / (B) / (A) containing a layer (B) containing 40 to 100% by weight of a polyolefin resin, and 0 to 60% by weight of an inorganic fine powder and / or an organic filler;
A configuration in which the pigment coating layer is provided on the outermost layer surface and a configuration in which the pigment coating layer is provided in the configuration of (B) / (A) / (B) are also included. Therefore, the method of manufacturing the resin film and the pigment coat layer will be described after describing the layer (A) and the layer (B).

(A) Layer The (A) layer of the resin film of the present invention comprises 0 to 85% by weight of a polyolefin resin and 15% by weight or more of an amorphous resin.
% By weight, inorganic fine powder and / or organic filler 0
７０70% by weight. The type of the polyolefin resin used for the layer (A) is not particularly limited. For example, ethylene, propylene, 1-butene, 1-hexene, 1-heptene, 1-octene, 4-methyl-1-pentene, 3-
Homopolymers of α-olefins having 2 to 8 carbon atoms such as methyl-1-pentene;
Different copolymers can be used. The copolymer may be a random copolymer or a block copolymer. Specifically, the density is 0.89 to 0.97 g / cm ³ , and the melt flow rate (190 ° C., 2.16 kg load) is 0.2 to 20.
g / 10 minutes of an ethylene-based resin such as a branched polyethylene or a linear polyethylene; a melt flow rate (230 ° C.,
2.16 kg load) 0.2 to 20 g / 10 min propylene homopolymer, (4-methyl-1-pentene) homopolymer, propylene / ethylene copolymer, propylene / 1
-Butene copolymer, propylene / ethylene / 1-butene copolymer, propylene / 4-methyl-1-pentene copolymer, propylene / 3-methyl-1-pentene copolymer, poly (1-butene), Propylene resins such as poly (4-methyl-1-pentene) and propylene / ethylene / 3-methyl-1-pentene copolymer are exemplified. Among these, propylene homopolymer, propylene / ethylene random copolymer, and high-density polyethylene are preferable because they are inexpensive and have good moldability.

The polyolefin resin used in the layer (A) has a melting point (peak temperature of a DSC curve) of 130 to 130.
Those at 210 ° C. are more preferred. Among them, the melting point (D
Peak temperature of the SC curve) is 155 to 174 ° C, and the melt flow rate (JISK7210) is 0.5 to 15
g / 10 minutes, and a propylene homopolymer having a crystallinity of 45 to 70% can be preferably used. Further, the melting point (peak temperature of the DSC curve) is 120 to 135 ° C.
The melt flow rate (JIS K6760) is 0.5 to 10 g / 10 min, and the crystallinity is 65 to 95.
%, And a high-density polyethylene having a density of 0.945 g / cm ³ or more can also be suitably used. In addition,
In the layer (A), one of the above-mentioned polyolefin resins may be selected and used alone, or two or more may be selected and used in combination.

The inorganic fine powder used in the layer (A) preferably has an average particle size of 0.01 to 6 μm, more preferably 0.05 to 4 μm, and more preferably 0.07 to 4 μm.
Those having a thickness of from 2 to 2 μm are particularly preferred. The organic filler used in the layer (A) has an average dispersed particle size of 0.01 to 6%.
μm is preferred, and particularly preferably 0.05 to 4 μm, and particularly preferably 0.07 to 2 μm.

Examples of the inorganic fine powder include heavy calcium carbonate, precipitated calcium carbonate, calcined clay, talc, titanium oxide, barium sulfate, aluminum sulfate, silica, zinc oxide, magnesium oxide, and diatomaceous earth. Further, surface-treated products of the above-mentioned inorganic fine powder with various surface-treating agents can also be exemplified. Among them, heavy calcium carbonate, precipitated calcium carbonate, talc and their surface-treated products, clay and diatomaceous earth are preferred. More preferred are surface treatment products of various surface treatment agents such as heavy calcium carbonate and precipitated calcium carbonate. Examples of the surface treating agent include resin acids, fatty acids, organic acids, sulfate ester type anionic surfactants, sulfonic acid type anionic surfactants, petroleum resin acids, and salts thereof such as sodium, potassium, and ammonium, or These fatty acid esters, resin acid esters, waxes, paraffins and the like are preferable, and nonionic surfactants, diene polymers, titanate coupling agents, silane coupling agents, phosphoric acid coupling agents, and the like are also preferable. Examples of the sulfate ester type anionic surfactant include long-chain alcohol sulfate,
Polyoxyethylene alkyl ether sulfates, sulfated oils and the like, and salts thereof such as sodium and potassium.Examples of the sulfonic acid type anionic surfactant include alkylbenzenesulfonic acid, alkylnaphthalenesulfonic acid, paraffinsulfonic acid, and the like. α-olefinsulfonic acid, alkylsulfosuccinic acid and the like, and salts thereof such as sodium and potassium. Further, as the fatty acid, for example, caproic acid, caprylic acid,
Pelargonic acid, capric acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, hebenic acid, oleic acid, linoleic acid, linolenic acid, eleostearic acid, and the like.Examples of the organic acid include maleic acid. And sorbic acid. Examples of the diene polymer include polybutadiene and isoprene. Examples of the nonionic surfactant include a polyethylene glycol ester type surfactant. These surface treatment agents can be used alone or in combination of two or more.

Examples of the organic filler include polyethylene terephthalate, polybutylene terephthalate, polyamide, polycarbonate, polyethylene naphthalate, polystyrene, melamine resin, polyethylene sulphite, polyimide, polyethyl ether ketone, polyphenylene sulphite and the like. Among them, it is preferable to use an organic filler which has a higher melting point or glass transition temperature than the polyolefin resin used and is incompatible.

In the layer (A), one of the above-mentioned inorganic fine powders or organic fillers may be selected and used alone, or two or more may be selected and used in combination. Is also good. When using two or more types in combination,
You may mix and use an organic filler and an inorganic fine powder.

As the amorphous resin used in the layer (A), a resin having a glass transition temperature of 70 to 170 ° C. is more preferably used. Glass transition temperature of amorphous resin is 70 ℃
If the temperature is lower than this, the moldability such as sticking to a roll tends to deteriorate, and if it is higher than 170 ° C., the processability tends to deteriorate.

Examples of the type of the amorphous resin include a cyclic olefin-based resin. The cyclic olefin-based resin may be used alone or in combination of two or more. The cyclic olefin-based resin is a ring-opened polymer derived from a cyclic olefin-based monomer represented by the following general formula (1), a hydride of the polymer or copolymer, and a compound represented by the following general formula (1). It is preferably selected from the group consisting of the cyclic olefin-based monomer and the addition polymer of ethylene.

Embedded image

In the general formula (1), n is 0 or a positive integer, and R ^{1 to} R ¹² are each independently a hydrogen atom,
Represents an atom or group selected from the group consisting of a halogen atom and a hydrocarbon group, R ^{9 to} R ¹² may be bonded to each other to form a monocyclic or polycyclic group, and The polycyclic group may have a double bond, and R ⁹ and R ¹⁰ or R ¹¹ and R ¹² may together form an alkylidene group.

As such a cyclic olefin monomer,
For example, see, for example, JP-A-2-227424,
JP-A-2-276842, JP-A-5-97719
Report, JP-A-7-41550, JP-A-8-7221
No. 0 is used.
Can be Specifically, the following cyclic olef
And vinyl monomers. For example, Bisik
B [2.2.1] hept-2-ene derivative, tetracycline
B [4.4.0.1^2,5. 1^7,10] -3-Dodecene induction
Isomer, hexacyclo [6.6.1.1]^3,6. 1^10,13. 0
^2,7. 0^9,14-4-Heptadecene derivative, octacycline
B [8.8.0.1^2,9. 1^4,7. 1^11,18. 1^13,16. 0
^3,8. 0^12,17] -5-docosene derivative, pentacyclo
[6.6.1.1^3,6. 0^2,7. 0^9,14] -4-Hexade
Cene derivatives, heptacyclo-5-eicosene derivatives,
Butacyclo-5-heneicosene derivative, tricyclo
[4.3.0.1^2,5] -3-decene derivatives, trisic
B [4.4.0.1^2,5] -3-undecene derivatives, pe
Nantacyclo [6.5.1.1^3,6. 0^2,7. 0^9,13] -4
-Pentadecene derivatives, pentacyclopentadecadiene
Derivative, pentacyclo [7.4.0.1^2,5. 1^9,12.
0^8,13] -3-pentadecene derivative, heptacyclo
[8.7.0.1^3,6. 1^10,17. 1^12,15. 0^2,7. 0
^11,16] -4-eicosene derivative, nonacyclo [10.
9.1.1^4,7. 1^13,20. 1^15,18. 0^3,8. 0^2,10. 0
^12,21. 0^14,19] -5-pentacosene derivative, pentacy
Black [8.4.0.1 ^2,5. 1^9,12. 0^8,13] -3-f
Xadecene derivative, heptacyclo “8.8.0.
1^4,7. 1^11,18. 1^13,16. 0^3,8. 0^12,17-5-f
Noneicosene derivative, nonacyclo [10.10.1.1]
^5,8. 1^14,21. 1^16,19. 0^2,11. 0^4,9. 0^{13 ,twenty two}. 0
^15,20] -5-hexacocene derivative, 1,4-methano-
1,4,4a, 9a-tetrahydrofluorene derivative,
1,4-methano-1,4,4a, 5,10,10a-f
Xahydroanthracene derivative and cyclopentadie
And n-acenaphthylene adduct.

More specifically, for example, bicyclo [2.
2.1] Hept-2-ene, 6-methylbicyclo [2.
2.1] Hept-2-ene, 5,6-dimethylbicyclo
[2.2.1] Hept-2-ene, 1-methylbicyclo
[2.2.1] Hept-2-ene, 6-ethylbicyclo
[2.2.1] Hept-2-ene, 6-n-butylbishi
Black [2.2.1] hept-2-ene, 6-isobutyl
Bicyclo [2.2.1] hept-2-ene, 7-methyl
Bicyclo [2.2.1] hept-2-ene;
Black [2.2.1] hept-2-ene derivative;
Black [4.4.0.1^2,5. 1^7,10-3-dodecene,
8-methyltetracyclo [4.4.0.1^2,5.
1^7,10] -3-dodecene, 8-ethyltetracyclo
[4.4.0.1^2,5. 1^7,10] -3-dodecene, 8-
Propyltetracyclo [4.4.0.1^2,5. 1^7,10]
-3-dodecene, 8-butyltertracyclo [4.4.
0.1^2,5. 1^{7,1 0}] -3-dodecene, 8-isobutyl
Tetracyclo [4.4.0.1^2,5. 1^7,10] -3-do
Decene, 8-hexyltetracyclo [4.4.0.1
^2,5. 1^7,10] -3-dodecene, 8-cyclohexylte
Toracyclo [4.4.0.1^2,5. 1^{7,1 0}] -3-Dode
Sen, 8-stearyltetracyclo [4.4.0.1
^2,5. 1^7,10] -3-dodecene, 5,10-dimethylte
Toracyclo [4.4.0.1^2,5. 1^{7 ,Ten}] -3-Dode
Sen, 2,10-dimethyltetracyclo [4.4.0.
1^2,5. 1^7,10] -3-dodecene, 8,9-dimethylte
Toracyclo [4.4.0.1^2,5. 1^7,10] -3-Dode
Sen, 8-ethyl-9-methyltetracyclo [4.4.
0.1^2,5. 1^7,10] -3-dodecene, 11,12-di
Methyltetracyclo [4.4.0.1^2,5. 1^7,10]-
3-dodecene, 2,7,9-trimethyltetracyclo
[4.4.0.1^2,5. 1^7,10] -3-dodecene, 9-
Ethyl-2,7-dimethyltetracyclo [4.4.0.
1^2,5. 1^7,10] -3-dodecene, 9-isobutyl-
2,7-dimethyltetracyclo [4.4.0.1^2,5.
1^7,10] -3-dodecene, 9,11,12-trimethyl
Tetracyclo [4.4.0.1^2,5. 1^{7,1 0}] -3-do
Decene, 9-ethyl-11,12-dimethyltetracyclic
B [4.4.0.1^2,5. 1^7,10] -3-dodecene, 9
-Isobutyl-11,12-dimethyltetracyclo
[4.4.0.1^2,5. 1^7,10-3-dodecene, 5,
8,9,10-tetramethyltetracyclo [4.4.
0.1^2,5. 1^7,10] -3-dodecene, 8-ethylidene
-9-methyltetracyclo [4.4.0.1^2,5. 1
^7,10] -3-dodecene, 8-ethylidene-9-ethylte
Toracyclo [4.4.0.1^{2, Five}. 1^7,10] -3-Dode
Sen, 8-ethylidene-9-isopropyltetracyclo
[4.4.0.1^2,5. 1^7,10] -3-dodecene, 8-
Ethylidene-9-butyltetracyclo [4.4.0.1
^2,5. 1^7,10] -3-dodecene, 8-n-propylidene
Tetracyclo [4.4.0.1^2,5. 1^7,10] -3-do
Decene, 8-n-propylidene-9-methyltetracycline
B [4.4.0.1^2,5. 1^7,10] -3-dodecene, 8
-N-propylidene-9-ethyltetracyclo [4.
4.0.1.^{2, Five}. 1^7,10] -3-dodecene, 8-n-p
Lopylidene-9-isopropyltetracyclo [4.4.
0.1^2,5. 1^7,10] -3-dodecene, 8-n-propyl
Ridene-9-butyltetracyclo [4.4.0.
1^2,5. 1^7,10] -3-dodecene, 8-isopropylide
Tetracyclo [4.4.0.1^2,5. 1^7,10] -3-
Dodecene, 8-isopropylidene-9-methyltetracy
Black [4.4.0.1^2,5. 1^{7 ,Ten}-3-dodecene,
8-isopropylidene-9-ethyltetracyclo [4.
4.0.1.^2,5. 1^7,10] -3-Dodecene, 8-Isop
Lopylidene-9-isopropyltetracyclo [4.4.
0.1^2,5. 1^7,10] -3-dodecene, 8-isopropylene
Ridene-9-butyltetracyclo [4.4.0.
1^2,5. 1^7,10] -3-dodecene, 8-chlorotetracy
Black [4.4.0.1^2,5. 1^7,10-3-dodecene,
8-bromotetracyclo [4.4.0.1^2,5.
1^7,10] -3-dodecene, 8-fluorotetracyclo
[4.4.0.1^2,5. 1^7,10-3-dodecene, 8,
9-dichlorotetracyclo [4.4.0.1^2,5. 1
^7,10] -3-dodecene, tetracyclo [4.4.
0.1^2,5. 1^7,10] -3-dodecene derivative;
Black [6.6.1.1^3,6. 1^10,13. 0^2,7. 0^9,14]
-4-heptadecene, 12-methylhexacyclo [6.
6.1.1^3,6. 1^10,13. 0^2,7. 0^{9,1 Four}] -4-hep
Tadecene, 12-ethylhexacyclo [6.6.1.1
^3,6. 1^{Ten ,13}. 0^2,7. 0^9,14-4-heptadecene,
12-isobutylhexacyclo [6.6.1.1^3,6.
1^10,13. 0^2,7. 0^9,14-4-heptadecene, 1,
6,10-trimethyl-12-isobutylhexacyclo
[6.6.1.1^3,6. 1^10,13. 0^2,7. 0^9,14] -4
Hexacyclo [6.6.1.1], such as heptadecene,
^{Three , 6}. 1^10,13. 0^2,7. 0^9,14] -4-Heptadecene induction
Conductor; octacyclo [8.8.0.1^2,9. 1^4,7. 1
^11,18. 1^13,16. 0^3,8. 0^12,17] -5-docosene, 1
5-methyloctacyclo [8.8.0.1^2,9. 1^4,7.
1^11,18. 1^13,16. 0 ^3,8. 0^12,17] -5-docosene,
15-ethyloctacyclo [8.8.0.1^{2, 9}.
1^4,7. 1^11,18. 1^13,16. 0^3,8. 0^12,17] -5-do
Octacyclo [8.8.0.1] such as cocene^2,9. 1
^4,7. 1^11,18. 1^13,16. 0^3,8. 0^12,17] -5-doko
Sen derivative; pentacyclo [6.6.1.1^3,6.
0^2,7. 0^9,14] -4-Hexadecene, 1,3-dimethyl
Lupentacyclo [6.6.1.1^3,6. 0^2,7. 0 ^9,14]
-4-hexadecene, 1,6-dimethylpentacyclo
[6.6.1.1^{3, 6}. 0^2,7. 0^9,14] -4-Hexade
Sen, 15,16-dimethylpentacyclo [6.6.
1.1^3,6. 0^2,7. 0^9,14] -4-Hexadecene, etc.
Of pentacyclo [6.6.1.1^3,6. 0^2,7. 0^9,14]
-4-hexadecene derivative; heptacyclo [8.7.
0.1^2,9. 1^4,7. 1^11,17. 0^3,8. 0^12,16] -5
Eicosene, heptacyclo [8.8.0.1^2,9.
1^4,7. 1^11,18. 0^3,8. 0^12,17] -5-Hen Eikose
Heptacyclo-5-eicosene derivatives such as
Is a heptacyclo-5-heneicosene derivative;
B [4.3.0.1^2,5] -3-decene, 2-methylt
Licyclo [4.3.0.1^2,5] -3-decene, 5-me
Tiltricyclo [4.3.0.1^2,5-3-decene,
Tricyclo [4.3.0.1^2,5] -3-decene
Derivative; tricyclo [4.4.0.1^2,5] -3-un
Decene, 10-methyltricyclo [4.4.0.
1^2,5] -3-undecene, tricyclo [4.
4.0.1.^2,5] -3-undecene derivative; pentacyclo
B [6.5.1.1^3,6. 0^2,7. 0^9,13] -4-penta
Decene, 1,3-dimethylpentacyclo [6.5. 1.
1^3,6. 0^2,7. 0^9,13-4-pentadecene, 1,6-
Dimethylpentacyclo [6.5.1.1^3,6. 0^2,7. 0
^9,13] -4-pentadecene, 14,15-dimethyl pen
Tacyclo [6.5.1.1^3,6. 0^2,7. 0 ^9,13] -4-
Pentacyclo [6.5.1.1] such as pentadecene,
^3,6. 0^2,7. 0^9,13] -4-pentadecene derivative; pen
Tacyclo [6.5.1.1^3,6. 0^2,7. 0^9,13] -4,
A diene compound such as 10-pentadecadiene;
Cyclo [7.4.0.1^2,5. 1^9,12. 0^8,13] -3-
Pentadecene, methyl-substituted pentacyclo [7.4.0.
1^2,5. 1^9,12. 0^8,13-3-pentadecene, etc.
Pentacyclo [7.4.0.1^2,5. 1^9,12. 0^8,13]
-3-pentadecene derivative; heptacyclo [8.7.
0.1^3,6. 1^10,17. 1^12,15. 0^2,7. 0^11,16] -4
-Eicosene, dimethyl-substituted heptacyclo [8.7.
0.1^3,6. 1^10,17. 1^12,15. 0^2,7. 0^11,16] -4
Heptacyclo [8.7.0.1, e.g.
^3,6. 1^10,17. 1^12,15. 0^2,7. 0^11,16] -4-A
Cocene derivative; nonacyclo [10.9.1.1]^4,7. 1
^13,20. 1^15,18. 0^3,8. 0^2,10. 0^12,21. 0^14,19]
-5-pentacocene, trimethyl-substituted nonacyclo [1
0.9.1.1^4,7. 1^13,20. 1^15,18. 0^3,8.
0^2,10. 0^12,21. 0^14,19] -5-pentacocene, etc.
Nonacyclo [10.9.1.1]^4,7. 1^13,20. 1
^15,18. 0^3,8. 0 ^2,10. 0^12,21. 0^14,19] -5-Pen
Tacocene derivative; pentacyclo [8.4.0.1^2,5.
1^9,12. 0^8,13] -3-Hexadecene, 11-methylpe
Nantacyclo [8.4.0.1^2,5. 1^9,12. 0^8,13]-
3-hexadecene, 11-ethyl-pentacyclo [8.
4.0.1.^2,5. 1^9,12. 0^8,13] -3-Hexadece
10,11-dimethyl-pentacyclo [8.4.
0.1^2,5. 1^9,12. 0^8,13-5-hexadecene,
Which pentacyclo [8.4.0.1^2,5. 1^9,12. 0
^8,13] -3-Hexadecene derivative; heptacyclo [8.
8.0.1^4,7. 1^11,18. 1 ^13,16. 0^3,8. 0^12,17]
-5-heneicosene, 15-methyl-heptacyclo
[8.8.0.1^4,7. 1^11,18. 1^13,16. 0^3,8. 0
^12,17] -5-Hen-eicosene, trimethyl-heptasi
Black [8.8.0.1^4,7. 1^11,18. 1^13,16. 0^{Three , 8}.
0^12,17Heptacyclo, such as 5-heneicosene
[8.8.0.1^4,7. 1^11,18. 1^13,16. 0^3,8. 0
^12,17] -5-heneicosene derivative; nonacyclo [1
0.10.1.1.^5,8. 1^14,21. 1^16,19. 0^2,11. 0
^4,9. 0^13,22. 0^{1 5,20}-6-hexacocene, etc.
Nonacyclo [10.10.1.1^5,8. 1^{14, twenty one}. 1
^16,19. 0^2,11. 0^4,9. 0^13,22. 0^15,20] -6-hex
Sacocene derivative; pentacyclo [6.5.1.1^3,6.
0^2,7. 0^9,13] -4,11-pentadecadiene, methyl
-Substituted pentacyclo [6.5.1.1^3,6. 0^2,7. 0
^9,13] -4,11-pentadecadiene, trimethyl substitution
Pentacyclo [4.7.0.1^2,5. 0^{8 ,13}. 1^9,12]
-3-pentadecene, pentacyclo [4.7.0.1
^2,5. 0^8,13. 1^9,12] -3,10-Pentadecadie
Methyl-substituted pentacyclo [4.7.0.1^2,5. 0
^8,13. 1^9,12] -3,10-pentadecadiene, methyl
Substituted heptacyclo [7.8.0.1^3,6. 0^2,7. 1
^10,17. 0^11,16. 1^12,15] -4-Eicosene, trim
Tyl-substituted heptacyclo [7.8.0.1^3,6. 0^2,7. 1
^10,17. 0^11,16. 1^12,15-4-Eicosene, tetra
Methyl substituted heptacyclo [7.8.0.1^3,6. 0^2,7.
1^10,17. 0^11,16. 1^12,15-4-Eicosene, bird
Cyclo [4.3.0.1^2,5] -3,7-decadiene
(I.e., dicyclopentadiene), 2,3-dihydride
Rhodicyclopentadiene, 5-phenyl-bicyclo
[2.2.1] Hept-2-ene (that is, 5-fe
Nyl-2-norbornene), 5-methyl-5-phenyl
-Bicyclo [2.2.1] hept-2-ene, 5-ben
Zyl-bicyclo [2.2.1] hept-2-ene, 5-
Tolyl-bicyclo [2.2.1] hept-2-ene, 5
-(Ethylphenyl) -bicyclo [2.2.1] hept
-2-ene, 5- (isopropylphenyl) -bicyclo
[2.2.1] Hept-2-ene, 8-phenyl-tet
Lacyclo [4.4.0.1^2,5. 1^{7 ,Ten}] -3-Dodece
8-methyl-8-phenyl-tetracyclo [4.
4.0.1.^2,5. 1^7,10] -3-dodecene, 8-benzyl
Le-tetracyclo [4.4.0.1^2,5. 1^7,10] -3
-Dodecene, 8-tolyl-tetracyclo [4.4.0.
1^2,5. 1^7,10] -3-dodecene, 8- (ethylphenyi)
Ru) -tetracyclo [4.4.0.1^2,5. 1^7,10]-
3-dodecene, 8- (isopropylphenyl) -tetra
Cyclo [4.4.0.1^2,5. 1^7,10] -3-Dodece
8,9-diphenyl-tetracyclo [4.4.0.
1^2,5. 1^7,10] -3-dodecene, 8- (biphenyl)
-Tetracyclo [4.4.0.1^2,5. 1^7,10] -3-
Dodecene, 8- (β-naphthyl) -tetracyclo [4.
4.0.1.^2,5. 1^7,10] -3-dodecene, 8- (α-
Naphthyl) -tetracyclo [4.4.0.1^2,5. 1
^7,10] -3-dodecene, 8- (anthracenyl) -tet
Lacyclo [4.4.0.1^2,5. 1^7,10] -3-Dodece
, 11-phenyl-hexacyclo [6.6.1.1
^3,6. 0^2,7. 0^9,14-4-heptadecene, 6- (α-
Naphthyl) -bicyclo [2.2.1] -hept-2-e
, 5- (anthracenyl) -bicyclo [2.2.1]
-Hept-2-ene, 5- (biphenyl) -bicyclo
[2.2.1] -Hept-2-ene, 5- (β-naphthy
Ru) -bicyclo [2.2.1] -hept-2-ene,
5,6-diphenyl-bicyclo [2.2.1] -hept
-2-ene, 9- (2-norbornen-5-yl) -ca
Rubazole, 1,4-methano-1,4,4a, 4b,
5,8,8a, 9a-octahydrofluorenes; 1,
4-methano-1,4,4a, 9a-tetrahydrofluoro
Len, 1,4-methano-8-methyl-1,4,4a, 9
a-tetrahydrofluorene, 1,4-methano-8-c
Loro-1,4,4a, 9a-tetrahydrofluorene,
1,4-methano-8-bromo-1,4,4a, 9a-te
1,4-methano-1,4,4 such as trahydrofluorene
a, 9a-tetrahydrofluorenes; 1,4-methano
-1,4,4a, 9a-tetrahydrodibenzofuran
And 1,4-methano-1,4,4a, 9a-tetrahydride
Locarbazole, 1,4-methano-9-phenyl-1,
1,4 such as 4,4a, 9a-tetrahydrocarbazole
-Methano-1,4,4a, 9a-tetrahydrocarbazo
1,4-methano-1,4,4a, 5,10,1
1,4-methano such as 0a-hexahydroanthracene
-1,4,4a, 5,10,10a-hexahydroan
Toracenes; 7,10-methano-6b, 7,10,10
a-tetrahydrofluorancenes; cyclopentadie
Of cyclopentadiene to the adenyl-acenaphthylene adduct
11,12-benzo-pentacyclo
[6.5.1.1^3,6. 0^2,7. 0^9,13] -4-pentade
Sen, 11,12-benzo-pentacyclo [6.6.
1.1^3,6. 0^2,7. 0^9,14] -4-Hexadecene, 1
4,15-benzo-heptacyclo [8.7.0.
1^2,9. 1^4,7. 1^11,17. 0^{Three , 8}. 0^12,16] -5-A
Cocene, cyclopentadiene-acenaphthylene adduct
And so on. These cyclic olefin monomers
Can be used alone or in combination of two or more
Can be used.

The hydrides of the cyclic olefin rediffused polymer are described in, for example, JP-A-60-26024 and JP-A-6-26024.
As described in JP-A-3-218727 and JP-A-63-23201, cyclic olefins are polymerized by using a polymerization catalyst made of a metal compound or the like, and hydrogen generally used for hydrogenation of olefin compounds is used. It can be obtained by, for example, a method of hydrogenating by a known method using an oxidation catalyst or the like. As a method for producing a random copolymer with ethylene, for example, as described in JP-A-60-168708, there is a method of polymerizing using a catalyst comprising a vanadium compound and a halogen-containing organoaluminum compound. . In this case, the ethylene fraction is 40 to 9
0% is desirable.

(A) a polyolefin resin in the layer,
The mixing ratio of the amorphous resin, the inorganic fine powder and / or the organic filler is 0 to 85% by weight of the polyolefin resin,
The amount of the amorphous resin is 15% by weight or more and less than 100% by weight, and the inorganic fine powder and / or the organic filler is 0 to 70% by weight. When the proportion of the amorphous resin is less than 15% by weight, the effect of preventing the solvent attack becomes insufficient. A preferred compounding ratio is 20 to 80% by weight of the polyolefin resin, 20 to 80% by weight of the amorphous resin, and 0 to 60% by weight of the inorganic fine powder and / or the organic filler. 30-70% by weight of resin,
The amorphous resin is 30 to 70% by weight, and the inorganic fine powder and / or the organic filler is 0 to 50% by weight.

Although not wishing to be bound by any theory, since the layer (A) contains an amorphous resin, the (A) layer (particularly a high-boiling petroleum solvent such as mineral oil) in the offset ink is used to form the (A) layer. It is considered that unevenness does not occur because the swelling of the layer itself is suppressed and the resin film itself does not easily swell. For this reason, general-purpose quick-drying (dry oil type) offset inks can be used for the resin film of the present invention. (A) The thickness of the layer is preferably 0.5 to 400 μm,
More preferably, it is 00 μm.

(B) Layer The (B) layer of the resin film of the present invention contains 40 to 100% by weight of a polyolefin resin, and 0 to 60% by weight of an inorganic fine powder and / or an organic filler. The type of the polyolefin resin used for the layer (B) is not particularly limited, and examples thereof include the polyolefin resin used for the layer (A). In particular, it is preferable to use a propylene homopolymer, a propylene / ethylene copolymer, a high-density polyethylene, or a mixture thereof. Among them, the melting point (peak temperature of the DSC curve) is 155 to 1
74 ° C. and a melt flow rate (JIS K721
0) is 0.5 to 20 g / 10 min, and the crystallinity is 45
A propylene homopolymer having a content of about 70% can be preferably used. Melting point (peak temperature of DSC curve)
Is 120 to 135 ° C. and the melt flow rate (JI
SK6760) is 0.5 to 10 g / 10 min, the crystallinity is 65 to 95%, and the density is 0.945 g / c.
High-density polyethylene having an m ³ or more can also be suitably used. In the layer (B), one of the polyolefin-based resins may be selected and used alone, or two or more may be selected and used in combination.

The inorganic fine powder used in the layer (B) preferably has an average particle size of 0.01 to 10 μm, more preferably 0.05 to 8 μm, and the organic filler has an average dispersed particle size. Is preferably from 0.01 to 10 μm, and more preferably from 0.05 to 8 μm. Examples of the inorganic fine powder include heavy calcium carbonate, light calcium carbonate, calcined clay, talc, titanium oxide, barium sulfate, aluminum sulfate, silica, zinc oxide, magnesium oxide, and diatomaceous earth.

Examples of the organic fine powder include polyethylene terephthalate, polybutylene terephthalate, polyamide, polycarbonate, polyethylene naphthalate, polystyrene, melamine resin, polyethylene sulphite, polyimide, polyethyl ether ketone, polyphenylene sulphite and the like.

The layer (B) contains one of the above fine powders.
Species may be selected and used alone, or two or more may be selected and used in combination. When two or more kinds are used in combination, an organic filler and an inorganic fine powder may be mixed and used.

The mixing ratio of the polyolefin resin and the inorganic fine powder and / or the organic filler in the layer (B) is as follows:
Polyolefin resin is 40 to 100% by weight, and inorganic fine powder and / or organic filler is 0 to 60% by weight.
It is. A preferred compounding ratio is 50 to 95% by weight of the polyolefin resin and 5 to 50% by weight of the inorganic fine powder and / or the organic filler. More preferably, the polyolefin resin is 65 to 90% by weight, and the inorganic fine powder and / or the organic filler is 10 to 90% by weight.
35% by weight.

The thickness of the layer (B) is preferably from 0.5 to 600 μm, more preferably from 1 to 400 μm.

Production of Resin Film The production method of the resin film of the present invention is not particularly limited.
What is manufactured by any method is included in the scope of the present invention as long as it satisfies the requirements described in the claims. Hereinafter, a preferred method for producing the resin film of the present invention will be described. The resin film of the present invention comprises a resin composition for the (A) layer and (B)
The resin compositions for the layers are separately melt-kneaded, and the desired layer configuration [(A), (A) / (B), (A) / (B) / (A),
(B) / (A) / (B)] to obtain a sheet.

Alternatively, the resin composition for the layer (A) or the layer (B) is melt-kneaded and extruded in the form of a sheet. Then, at least one surface of the film is coated with the layer (A) or the layer (B). Is melt-kneaded to obtain a desired layer constitution [(A), (A) / (B), (A) / (B) / (A),
(B) / (A) / (B)] to obtain a sheet.
The thickness of the resin film is generally 50 to 800 μm.

In this specification, the expression “(B) / (A)” means a structure in which the (B) layer is formed on one surface of the (A) layer. At this time, a layer other than the (A) layer and the (B) layer may be formed between the two layers. Such a layer can be appropriately selected according to the use and function of the resin film.

For example, in order to further add the paper-like feeling of the resin film, a polyolefin-based material containing 2 to 55% by weight of an inorganic fine powder and / or an organic filler is provided between the (A) layer and the (B) layer. The resin layer can be preferably formed as the intermediate layer (C). In addition, this intermediate layer
A small amount of a low-melting resin such as a propylene-based copolymer, a high-density polyethylene, or an ethylene-vinyl acetate copolymer may be contained. The types of the inorganic fine powder, the organic filler, and the polyolefin resin used for the intermediate layer (C) are not particularly limited.
For example, inorganic fine powders, organic fillers, and polyolefin-based resins used in the above-mentioned (A) layer can be exemplified.

The surface of the resin film is subjected to a corona discharge treatment or a flame treatment for improving the offset printability, or to a polyethyleneimine, butylated polyethyleneimine, hydroxypropylated polyethyleneimine, hydroxyethylated polyethyleneimine, 3-
Selected from the group consisting of dihydroxypropylated polyethyleneimine, poly (ethyleneimine-urea), ethyleneimine adducts such as polyamine polyamides, epichlorohydrin adducts such as polyamine polyamides, acrylic emulsions, and tertiary or quaternary nitrogen-containing acrylic resins. A water-soluble primer may be applied.

In order to further improve the suitability for offset printing of the resin film of the present invention, a pigment coat layer can be provided on at least the surface to be printed. The pigment coat layer can be formed by performing pigment coating according to a general coated paper coating method. Pigment coating agents used in pigment coating include clay, talc, calcium carbonate, magnesium carbonate, aluminum hydroxide used in ordinary coated paper,
A latex containing 30 to 80% by weight of a pigment such as silica, calcium silicate, or plastic pigment and 20 to 70% by weight of an adhesive can be used.

The adhesive used at this time includes SBR (styrene-butadiene copolymer rubber),
MBR (methacrylate / butadiene copolymer rubber)
Latex, acrylic emulsion, starch, PV
A (polyvinyl alcohol), CMC (carboxymethylcellulose), methylcellulose and the like can be mentioned. Further, a dispersant such as a special sodium polycarboxylate such as an acrylic acid / sodium acrylate copolymer and a cross-linking agent such as a polyamide urea resin can be added to these compounding agents. These pigment coating agents are generally 1
It is used as a water-soluble coating agent having a solid content of 5 to 70% by weight, preferably 35 to 65% by weight.

As means for applying such a coating agent to a resin film, specifically, coating methods such as gravure coating, Meyer bar coating, roll coating, blade coating, size press coating, etc. Means can be employed. The coating amount is generally 0.01 to 20 g / m ² , preferably 0.1 to 20 g / m ² .
It can be ¹ to 15 g / m ² .

[0040]

The present invention will be described more specifically with reference to the following Examples and Test Examples. Materials, reagents,
The ratio, operation, and the like can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the following specific examples.

Examples 1 to 11 A mixture of 80% by weight of propylene homopolymer (β2) shown in Table 2 and 8% by weight of high-density polyethylene (γ) was mixed with 12% by weight of calcium carbonate (E). Was blended to obtain a composition (B). Separately, the composition (A) was prepared by mixing the amorphous resin, polyolefin-based resin and inorganic fine powder shown in Table 3 in the amounts shown in Table 3. These compositions (A) and (B) were each melt-kneaded in a separate extruder set at 270 ° C., and laminated inside the die so that (A) / (B) / (A) was obtained. Co-extruded from one die, cooled by a cooling device, subjected to corona discharge treatment on the surface,
(A) / (B) / (A) [Thickness of each film was 25 μm / 150 μm / 25 μm, respectively] to obtain a multilayer resin film having a three-layer structure. This manufacturing method was repeated by changing the types and amounts of the amorphous resin, the polyolefin-based resin, and the inorganic fine powder of the layer (A) as described in Table 3, and the 11 types of resin films of Examples 1 to 11 I got In addition,
Details of the amorphous resin, polyolefin resin and inorganic fine powder used are as described in Table 2.

Example 12 A mixture of 87% by weight of the propylene homopolymer (β2) described in Table 2 as the layer (B) and 8% by weight of the high-density polyethylene (γ) was mixed with calcium carbonate (E). A multilayer resin film having a three-layer structure was obtained in the same manner as in Example 5 except that 5% by weight was blended.

Example 13 As a layer (B), a mixture of 55% by weight of a propylene homopolymer (β2) shown in Table 2 and 15% by weight of a high-density polyethylene (γ) was mixed with calcium carbonate (E). Example 5 except that 30% by weight was blended.
In the same manner as in the above, a multilayer resin film having a three-layer structure was obtained.

Example 14 A mixture of 80% by weight of a propylene homopolymer (β2) shown in Table 2 and 8% by weight of a high-density polyethylene (γ) was mixed with calcium carbonate (E).
The composition (B) was obtained by blending 12% by weight. Separately, the composition (A) was prepared by mixing the amorphous resin, polyolefin-based resin and inorganic fine powder shown in Table 3 in the amounts shown in Table 3. Further, a composition (C) was prepared by mixing 50% by weight of a propylene homopolymer (β1) shown in Table 2 with 50% by weight of calcium carbonate (E). These compositions (A), (B) and (C)
After melt-kneading in separate extruders set at 0 ° C. and laminating inside the die so as to be (A) / (C) / (B) / (C) / (A), from one die Co-extrusion, cooled by a cooling device, subjected to corona discharge treatment on the surface,
(A) / (C) / (B) / (C) / (A) [The thickness of each film is 20 μm / 30 μm / 100 μm /
30 μm / 20 μm] to obtain a multilayer resin film having a five-layer structure.

Example 15 A composition (A) was prepared by mixing the amorphous resin, polyolefin resin and inorganic fine powder shown in Table 2 in the amounts shown in Table 4. The composition (A) is melt-kneaded in a separate extruder set at 270 ° C., extruded from one die, cooled by a cooling device,
The surface was subjected to a corona discharge treatment to obtain (A) a resin film having a single-layer structure with a film thickness of 250 μm.

Example 16 A composition (A) was prepared by mixing the amorphous resin, polyolefin resin and inorganic fine powder shown in Table 2 in the amounts shown in Table 4. Separately, 50% by weight of propylene homopolymer (β1)
Composition (B) obtained by mixing 40% by weight of calcium carbonate (E) with a mixture of 10% by weight of high-density polyethylene (γ)
I got These compositions (A) and (B)
After melt-kneading with separate extruders set in the above, and laminating inside the die so as to be (B) / (A) / (B),
(B) / (A) / (B) Co-extrusion from one die, cooling with a cooling device, and corona discharge treatment on the surface
[The thickness of each film is 25 μm / 200 μm, respectively.
/ 25 μm] to obtain a multilayer resin film having a three-layer structure.

(Examples 17 to 25) Examples 2 to 5, 12
16 to 50% by weight of light calcium carbonate (C), 10% by weight of kaolin clay (F), 35% by weight of (G) silica composite acrylic emulsion (G) % And a specially modified polyvinyl alcohol (H) of 5% by weight to prepare a water-soluble coating agent (compounding values indicate the solid content), and 10 g / m ^2.
And dried at 105 ° C. for 1 minute to obtain a coated film. In this case, as for light calcium carbonate (C) and kaolin clay (F), special sodium polycarboxylate (I) is used as a dispersant with light calcium carbonate (C) or kaolin clay (F) 100.
0.5 parts by weight with respect to 100 parts by weight of a specially modified polyvinyl alcohol (H) and 100 parts by weight of a specially modified polyvinyl alcohol (H) with a polyamide urea resin (J) as a crosslinking agent. Used.

(Test Example) With respect to the resin films obtained in Examples 1 to 25, the applicability of offset printing (concavity and convexity by actual printing, ink drying property) was evaluated in the following procedure. The results are shown in Tables 3 to 6.

(1) Concavities and convexities due to printing on the actual machine The resin film to be evaluated is dried in four colors by a four-color offset printing machine (0F-4, manufactured by Mitsubishi Heavy Industries, Ltd.) (Super Tech, manufactured by T & K TOKA Co., Ltd.). Sumi,
Indigo, red, and yellow) were continuously printed on 1,000 sheets so that the transfer amount of each color was 1.5 g / m ^2, and the printed matter was left in a stacked state. After the ink was dried, the unevenness of the film formed by the printed portion and the unprinted portion was determined by sensory evaluation according to the following evaluation criteria. Judgment criteria ○: No irregularities △: Irregularities are observed ×: Irregularities are severe

(2) Ink Drying Property The resin film to be evaluated is dried in four colors using a four-color offset printing machine (0F-4, manufactured by Mitsubishi Heavy Industries, Ltd.) (Super Tech Black, manufactured by T & K TOKA Co., Ltd.). ,
Indigo, red, and yellow) are printed continuously for 1000 sheets so that the transfer amount of each color is 1.5 g / m ² , the printed matter is left in a stacked state, sampled at predetermined time intervals, and dried. It was determined according to the following criteria. Criterion 5: Very fast 4: Fast 3: Not a problem 2: Slightly slow 1: Very slow

[0051]

[Table 2]

[0052]

[Table 3]

[0053]

[Table 4]

[0054]

[Table 5]

[0055]

[Table 6]

[0056]

The resin film of the present invention can effectively prevent a phenomenon in which the film becomes uneven due to the vehicle in the offset ink when offset printing is performed.
Therefore, the resin film of the present invention has extremely excellent printability. Therefore, the resin film of the present invention is useful as a material for poster paper, wrapping paper, labels, book covers, signboards and the like.

[Brief description of the drawings]

FIG. 1 shows a basic composition of an offset printing ink.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (reference) C08L 45/00 C08L 45/00 65/00 65/00 101/00 101/00 F term (reference) 4F071 AA15 AA15X AA16 AA20 AA21 AA21X AA29 AA32 AA54 AB21 AB26 AH19 BB06 BC01 4F100 AA00A AA00B AA08A AA08H AK01A AK01B AK01H AK02A AK02J AK03A AK03B AK04A AK04J AK07A AK21A AK21H AL01A AL05A AL06A AL06H BA01 BA02 BA03 BA06 BA07 BA15 CA23A CA23B CC00C DE01A GB90 JA12A JL01 YY00A YY00B 4J002 BB03W BB03X BB05W BB12W BB15W BB17W BC03Y BE02Y BG01Y BK00X BP02W BP03W CC18Y CF06Y CF07Y CF08Y CG00Y CL00Y CM04 CN02Y DE076 DE106 DE136 DE236 DG046 DJ006 DJ016 DJ036 DJ046 FD01Y FD016

Claims (5)

[Claims] 1. A polyolefin-based resin of 0 to 85% by weight,
A resin film having a layer (A) containing 15% by weight or more and less than 100% by weight of an amorphous resin, and 0 to 70% by weight of an inorganic fine powder and / or an organic filler. 2. A layer (B) containing 40 to 100% by weight of a polyolefin resin, 0 to 60% by weight of an inorganic fine powder and / or an organic filler is laminated on at least one surface of the layer (A). The multilayer resin film according to claim 1, wherein 3. The resin film according to claim 1, wherein the amorphous resin is a cyclic olefin resin. 4. The resin film according to claim 1, wherein the polyolefin resin of the layer (A) is a propylene resin, an ethylene resin, or a mixture thereof. 5. The resin film according to claim 1, wherein a pigment coat layer is provided on at least one outermost layer of the resin film.