JP2002316394A - Polyolefin resin laminated film - Google Patents

Abstract

(57) [Problem] To provide a laminated film made of a polyolefin-based resin having excellent adhesion to an ultraviolet curable ink and excellent cutting performance in an automatic cutter operation. SOLUTION: Tensile modulus (JIS K 7127) is 6
A polyolefin-based film in which a 0.3 to 3 μm-thick primer layer containing a polyurethane resin containing a polycarbonate polyurethane resin as a main component is laminated on at least one surface of a polyolefin-based resin film having a thickness of 100 to 1200 MPa and a thickness of 30 to 500 μm. Resin laminated film.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminated film made of a polyolefin-based resin used for a base film or the like for indications such as stickers and labels. For details, rolls (rolls) similar to polyvinyl chloride resin films
Polyolefin resin lamination that can be handled as a form, has excellent adhesion with various ink cured films such as ultraviolet curable ink, excellent non-curl properties, long-term weather resistance, and especially excellent half-cutting properties in various automatic cutter operations It is about a film.

[0002]

2. Description of the Related Art Conventionally, films made of polyvinyl chloride resin have been widely used as films for printing. However, poor adhesion with an ink cured film due to migration of a plasticizer, transfer problems of printed matter, blocking (film-to-film). However, it is not always satisfactory because there are problems such as the fact that it becomes impossible to easily peel off due to adhesion) and that it is necessary to incinerate in a special high-temperature furnace when incinerated.

In the field of markings such as labels and stickers,
Polyethylene resin film for label with corona-treated surface (Japanese Patent No. 2916328), Polypropylene resin film for label with corona-treated surface
(Japanese Patent Laid-Open No. 11-242440) has been proposed, but the effect of corona treatment expires when the film is stored until the secondary processing. Therefore, when performing the printing process after temporarily storing the film,
There is a problem that the adhesion stability of the ink is lacking. Also,
In recent years, there has been a tendency for solvent-free UV curable inks to be frequently used as printing inks for the purpose of reducing environmental impact, and the corona treatment alone cannot maintain the adhesion to the ink cured film.
It has been pointed out that the printed layer is peeled off and the quality is significantly impaired.

Further, in the case of the above-mentioned polyethylene resin film, since the heat resistance is poor, it is necessary to carry out solvent drying at a high temperature condition when the surface of the film is subjected to primer processing in order to improve the adhesion of the ink. It is difficult, and there is a problem that a blocking phenomenon due to poor drying easily occurs.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a laminated film made of a polyolefin resin suitable for printing without the above-mentioned problems. It is excellent in transferability, adhesion and non-curl properties of various printing inks such as curable inks, and can be cut or half-cut (half-cut) in various shapes in automatic cutter work with a flat blade or rotary blade attached. "Indicates that the liner made of paper or film is laminated on the back surface of the base film via an adhesive material, and refers to cutting only the base film without cutting the liner.) It is an object of the present invention to provide a polyolefin-based resin laminated film which does not cause a defect trouble in a remaining portion.

[0006]

According to the present invention, there is provided (1) a tensile modulus (JIS K 7127) of 600 to 1200 MPa.
A polyolefin resin film having a thickness of 30 to 500 μm, and a primer layer having a thickness of 0.3 to 3 μm containing a polyurethane resin containing a polycarbonate polyurethane resin as a main component is laminated on at least one surface of the film. Laminated film made of polyolefin resin,
(2) The polypropylene resin laminated film according to the above (1), wherein the polyolefin resin film is a laminated film composed of a homopropylene polymer and a random propylene copolymer, and (3) the polyolefin resin film. A laminated film having an inner layer, an intermediate layer and an outer layer, wherein the inner layer contains 25 to 75% by weight of a homopropylene polymer and 75 to 25% by weight of a random propylene copolymer. The laminated film made of a polypropylene-based resin according to the above, wherein the (4) polyolefin-based resin film is a laminated film having an inner layer, an intermediate layer and an outer layer, wherein the intermediate layer contains 5 to 20% by weight of titanium oxide, and The thickness is 50 times the total thickness of the laminated film.
% Or more of the polyolefin resin laminated film according to any one of the above (1) to (3), and (5) the polycarbonate polyurethane resin is a polymer of a polycarbonate diol and an aliphatic and / or alicyclic diisocyanate. (1) to (4), which are mainly composed of polycarbonate polyurethane having a hydroxyl group at a molecular terminal and having a weight average molecular weight of 15,000 to 150,000.
Wherein the (6) primer layer comprises a polycarbonate polyurethane resin and (a) an adduct of an aliphatic, alicyclic or aromatic diisocyanate or (b) an isocyanurate polymer (1) to (1) to which any one or more of them are reacted and the tensile modulus is 300 MPa or less.
(5) The polyolefin resin laminated film according to any one of (5) and (7) the primer layer has an average particle diameter of 0.1 to
The polyolefin-based resin laminated film according to any one of the above (1) to (6), comprising 5 μm of an inorganic powder,
(8) The polyolefin resin laminated film according to any one of the above (1) to (7), wherein the polyolefin resin film is an aged film, (9) any of the above (1) to (8) The present invention is directed to a display substrate comprising a polyolefin-based resin laminated film described in (1).

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The polyolefin resin laminated film of the present invention is a polyolefin resin film having a tensile modulus (JIS K7127) of 600 to 1200 MPa (hereinafter referred to as "base film"). Is laminated.

The tensile modulus of the base film is 600 MPa.
If it is less than this, the rigidity becomes too low, the workability at the time of primer treatment of the base film becomes worse, it causes the occurrence of wrinkles and creases, and the cutting failure frequently occurs when punching into various label shapes by automatic cutter work. And the workability deteriorates remarkably. On the other hand, if the tensile modulus exceeds 1200 MPa, the rigidity becomes too high, which may deteriorate not only the workability in the primer treatment and the like, but also the non-curlability and cold shock resistance after commercialization.

The tensile modulus of the present invention is 600 to 1200M.
As a method for obtaining a base film of Pa, a method of preparing a composition of a polyolefin-based resin or an annealing treatment (for example, if the obtained film does not satisfy the above tensile elastic modulus after forming a polyolefin-based resin film, The temperature of the film is set to 60 to 150 ° C., and the film is kept in that state for about 2 seconds to 10 minutes and then cooled, or subjected to an aging treatment (for example, stored in an insulated room at 35 ° C. or more and 35 to 50 ° C. for 1 day or more). And a method of promoting or completing crystallization of the resin constituting the film so as to satisfy the above tensile modulus.

As the base film, a film containing a polypropylene resin as a main component is preferable. In particular, 60 to 100% by weight of a polypropylene resin and 40% by weight of another synthetic resin are used.
What consists of ０0% by weight is preferred. Examples of the polypropylene resin include a propylene homopolymer and / or a copolymer. Examples of the copolymer include a random copolymer or a block copolymer of propylene and ethylene or another α-olefin, or a propylene graft copolymer having a polyolefin copolymer as a trunk polymer. . As the α-olefin copolymerizable with propylene, those having 4 to 12 carbon atoms are preferable, for example, 1-butene, 1-pentene,
-Hexene, 1-heptene, 1-octene, 4-methyl-1-pentene, 1-decene and the like, and one or a mixture of two or more thereof is used. The mixing ratio of the α-olefin is 1 to 10% by weight, especially 2
It is preferable to set it to 6% by weight.

Examples of the polyolefin copolymer for the backbone polymer of the propylene graft copolymer include ethylene-propylene rubber, ethylene-butene rubber, and ethylene-propylene-diene rubber. As the polypropylene-based resin, it is preferable to use a random copolymer because of the excellent transparency and flexibility of the film, and a resin composed of a homopropylene polymer and a random propylene-based copolymer is particularly preferable.

The homopolypropylene polymer preferably has a melt flow rate of 0.1 to 30 (g / 10 minutes). In consideration of processability, two or more kinds having different melt flows within the above range are combined. It is more preferred to use. Examples of the above-mentioned other synthetic resin used by mixing with the polypropylene-based resin include a polyethylene-based resin, an olefin-based thermoplastic elastomer, a diene-based rubber, and a styrene-based thermoplastic elastomer.

Examples of the polyethylene resin include a homopolymer of ethylene and / or a copolymer of ethylene and another monomer copolymerizable therewith (low-density polyethylene (LDPE)). , Linear low density polyethylene (LLDPE), high density polyethylene (HDP)
E), an ethylene-α-olefin copolymer (metallocene-based polyethylene) obtained by polymerization using a metallocene-based catalyst).

Examples of the olefin-based thermoplastic elastomer include propylene-based thermoplastic elastomers such as low-crystalline propylene homopolymer having a heat of crystal fusion (ΔH) of 100 g / J or less, ethylene-propylene copolymer rubber,
Examples include ethylene-propylene non-conjugated diene rubber, ethylene-butadiene copolymer rubber, and low density metallocene-based polyethylene. In the present invention, the heat of crystal fusion (ΔH) refers to a DSC chart when a resin is once melted to a melting point or higher using a differential scanning calorimeter (DSC) and then cooled at a rate of 10 ° C./min. It is a value calculated from the upper crystal peak area.

As the diene rubber, isoprene rubber,
Butadiene rubber, butyl rubber, propylene-butadiene rubber, acrylonitrile-butadiene rubber, acrylonitrile-isoprene rubber, and the like. Examples of the styrene-based thermoplastic elastomer include styrene-butadiene copolymer rubber, styrene-butadiene block copolymer, and styrene-isoprene copolymer rubber. Among them, styrene-butadiene-based thermoplastic elastomers such as styrene-butadiene copolymer rubber and styrene-butadiene block copolymer are preferable. The styrene-based thermoplastic elastomer is preferably hydrogenated.

The base film of the present invention can be exemplified by a film in which the homopropylene polymer is more than 25% by weight and less than 100% by weight, and the random propylene copolymer is 0% by weight or more and less than 75% by weight. . In addition, a film comprising 0 to 25% by weight of a homopropylene polymer and 75 to 100% by weight of a random propylene-based polymer is subjected to an annealing treatment or an aging treatment (for example, at 35 ° C.
(Stored in a warm room at 5 to 50 ° C. for one day or more) to promote or complete the crystallization of the resin to increase the tensile modulus of the film to 600 to 1200 MPa.

The base film may further include a synthetic resin other than the above, an antioxidant, an ultraviolet absorber,
Additives which are usually added to polyolefin resin films, such as light stabilizers, slip agents (lubricants), anti-blocking agents, pigments, colorants, fillers, nucleating agents, antistatic agents, flame retardants, etc. Can be added in a range that does not impair.

Examples of the antioxidant include phenol-based, sulfide-based, phosphorus-based, and isocyanurate-based antioxidants. Among them, a phenolic antioxidant is preferable because of its excellent antioxidant effect, and a combination use of a phenolic antioxidant and a phosphorus antioxidant is particularly preferable because thermal stability is improved. Examples of phenolic antioxidants include 2,6-di-t-butyl-4-methylphenol,
2,6-di-isopropyl-4-ethylphenol,
2,6-di-t-amyl-4-methylphenol, 2,
6-di-t-octyl-4-n-propylphenol,
2,6-di-cyclohexyl-4-n-octylphenol, 2-isobutyl-4-ethyl-5-t-hexylphenol, 2-cyclohexyl-4-n-butyl-6
-Isopropylphenol, styrenated mixed cresol, dl-α-tocopherol, t-butylhydroquinone, 2,2′-methylenebis (4-methyl-6-t-butylphenol), 4,4′-butylidenebis (3-methyl-6 -T-butylphenol), 4,4'-thiobis (3-methyl-6-t-butylphenol), 2,
2'-thiobis (4-methyl-6-t-butylphenol), 2,2'-methylenebis [6- (1-methylcyclohexyl) -p-cresol], 2,2'-ethylidenebis (4,6-di -T-butylphenol), 1,
1,3-tris (2-methyl-4-hydroxy-5-t
-Butylphenyl) butane, 2,2'-thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N, N'-hexamethylenebis (3,5-di -Tert-butyl-4-hydroxy-hydrocinnamide), 3,5-di-tert-butyl-4-hydroxybenzylphosphonate-diethyl ester, tris (4-tert-butyl-2,6-dimethyl-3-hydroxybenzyl) Isocyanurate, 2,4-bis (n-octylthio) -6- (4-hydroxy-3,5-di-t
-Butylanilino) -1,3,5-triazine, bis (3,5-di-t-butyl-4-hydroxybenzylphosphonate ethyl) nickel, bis [3,3-bis (3-
t-butyl-4-hydroxyphenyl) butyric acid] glycol ester, N, N'-bis [3- (3,
5-di-tert-butyl-4-hydroxyphenyl) propionyl] hydrazine, 2,2'-oxamidobis [ethyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], pentaerythrityl -Tetrakis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate), bis [2-tert-butyl-4-methyl-6- (3-tert-butyl-5-methyl-2)
-Hydroxybenzyl) phenyl] terephthalate,
3,9-bis [1,1-dimethyl-2- [β- (3-t
-Butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, 2,2-bis [4
-[2- (3,5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy)] ethoxyphenyl] propane and stearyl-β- (4-hydroxy-3,5-di-tert-butylphenol) propionate and the like Β-
(3,5-di-t-butyl-4-hydroxyphenyl)
And alkyl propionate.

Examples of the sulfide-based antioxidants include dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, and dioctdecyl 3,3'-thiobispropionate. . Examples of the phosphorus antioxidants include bis (2,4-di-t-butylphenyl) pentaerythritol-di-phosphite and bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol-diphenyl. -Phosphite, bis (2,4,6-tri-t-butylphenyl) pentaerythritol-di-phosphite, methylenebis (2,4
-Di-t-butylphenyl) octyl phosphite, tris (nonylphenyl) phosphite, tris (2,4
-Di-t-butylphenyl) phosphite, tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylene-di-phosphonite, tetrakis (2,4
-Di-t-butyl-5-methylphenyl) -4,4'-
Biphenylene-di-phosphonite, 2-[[2,4,
8,10-tetrakis (1,1-dimethylethyl) dibenzo [d, f] [1,3,2] dioxafespepin 6-yl] oxy] -N, N-bis [2-[[2, 4,
810-tetrakis (1,1 dimethylethyl) dibenzo [d, f] [1,3,2] dioxafespepin-6
-Yl] oxy] -ethyl] ethanamine and the like.

The isocyanurate-based antioxidants include:
Tris- (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate and the like. The addition amount of the antioxidant is usually 0.01 to 5 parts by weight per 100 parts by weight of the resin component in the base film. Examples of the ultraviolet absorber include a benzophenone-based, benzotriazole-based, triazine-based, and cyanoacrylate-based ultraviolet absorber.

As the benzophenone-based ultraviolet absorber,
2,2'-dihydroxybenzophenones such as 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone and 2,2 ', 4,4'-tetrahydroxybenzophenone UV absorbers, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-methoxy-2 '
-Carboxybenzophenone, 2-hydroxy-4-benzoyloxybenzophenone, 2-hydroxy-5
2-hydroxybenzophenone ultraviolet absorbers such as chlorobenzophenone, 2-hydroxy-4-methoxy-5-sulfonebenzophenone, 2,4-dihydroxybenzophenone, bis- (2-methoxy-4-hydroxy-5-benzoylphenyl) Methane and the like can be mentioned.

As the benzotriazole-based ultraviolet absorber, 2- [2′-hydroxy-3 ′-(3 ″, 4 ″,
5 ", 6" -tetrahydrophthalimidomethyl) -5 '
-Methylphenyl] benzotriazole, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl)
Phenyl] -2H-benzotriazole, 2,2-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol] and the like.

Examples of the triazine-based UV absorber include 2-
(4,6-bis (2,4-dimethylphenyl) -1,
3,5-triazin-2-yl) -5- (octyloxy) phenol, 2- (4,6-diphenyl-1,3,3)
5-triazin-2-yl) -5- (octyloxy) phenol, 2- (4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl) -5-
(Hexyloxy) phenol, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-((methyl) oxy) phenol, 2- (4,6-diphenyl-1,3,3) 5-triazin-2-yl) -5-((hexyl) oxy) -phenol and the like.

Examples of the cyanoacrylate-based ultraviolet absorber include 2-ethyl-hexyl-2-cyano-3,3-diphenylacrylate, ethyl-2-cyano-3,3-diphenylacrylate, octyl-2-cyano-3, 3
-Diphenyl acrylate and the like. The amount of the ultraviolet absorber is usually 0.01 to 10 parts by weight, preferably 0.05 to 10 parts by weight per 100 parts by weight of the resin component in the base film.
5 parts by weight.

As the light stabilizer, 4-acetoxy-2,
2,6,6-tetramethylpiperidine, bis (2,2,
6,6-tetramethyl-4-piperidinyl) adipate, bis (2,2,6,6-tetramethyl-4-piperidinyl) sebacate, bis (1-n-octoxy-2,
2,6,6-tetramethyl-4-piperidinyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-)
Piperidinyl) sebacate, bis (2,2,6,6-tetramethyl-4-piperidinyl) terephthalate, bis (1,2,2,6,6-pentamethyl-4-piperidinyl) di (tridecyl) -1,2 , 3,4-butanetetracarboxylate, bis (2,2,6,6-tetramethyl-4-piperidinyl) di (tridecyl) -1,
2,3,4-butanetetracarboxylate, tris (2,2,6,6-tetramethyl-4-piperidine) phosphite, tris (2,2,6,6-tetramethyl-
4-piperidinyl) benzene-1,3,5-tricarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidinyl) -1,2,3,4-butanetetracarboxylate, tetrakis ( 2,2,6,6
-Tetramethyl-4-piperidinyl) -1,2,3,4
-Butanetetracarboxylate, dimethyl succinate
1- (2-hydroxyethyl) -4-hydroxy-2,
2,6,6-tetramethylpiperidine polycondensate, poly [
{6- (1,1,3,3-tetramethylbutyl) imino-1,3,5-triazine-2,4-diyl} (2
2,6,6-tetramethyl-4-piperidinyl) imino {hexamethylene} (2,2,6,6-tetramethyl-4-piperidinyl) imino}], 2,2,6,6-tetramethylpiperidi Nyl-4-benzoate, 4-benzyloxy-2,2,6,6-tetramethylpiperidine, 1,3,8-triaza-7,7,9,9-tetramethyl-2,4-dioxo-spiro [ 4,5] decane, tri- (4-acetoxy-2,2,6,6-tetramethylpiperidine) -amine, 1,2,3,4-tetra (4-
Carbonyloxy-2,2,6,6-tetramethylpiperidine) butane, 4- (phenylcarbamoyloxy)
-2,2,6,6-tetramethylpiperidine, (2,
2,6,6-tetramethylpiperidine) -4-spiro-
2 '-(6', 6'-dimethylpiperidine) -4'-spiro-5 "-hydantoin, 4- (p-toluenesulfonyloxy) -2,2,6,6-tetramethylpiperidine, 1,3, 8-Triaza-7,7,9,9-tetramethyl-3-n-octyl-spiro [4,5] decane-
2,4-dione, 4-stearoyloxy-2,2,
6,6-tetramethylpiperidine, 2- (3,5-di-
Bis (1,2,2,6,6-pentamethyl-tert-butyl-4-hydroxybenzyl) -2-n-butylmalonate
And hindered amine light stabilizers (HALS) such as 4-piperidinyl).

The amount of the light stabilizer is usually 0.01 to 10 parts by weight per 100 parts by weight of the resin component in the base film. Examples of the lubricant include saturated fatty acid amides such as lauric acid amide and stearic acid amide, and unsaturated fatty acid amides such as erucic acid amide and oleic acid amide. Among them, erucamide is preferred.

The amount of the lubricant is usually 0.01 to 10 parts by weight per 100 parts by weight of the resin component in the base film.
Urethane resin beads as anti-blocking agents,
Organic powders such as polycarbonate resin beads, pigments such as carbon black, calcium carbonate, barium sulfate,
Examples include inorganic powders such as silica, silica alumina, clay, talc, and titanium oxide.

The addition amount of the antiblocking agent is usually 0.01 to 1 per 100 parts by weight of the resin component in the base film.
0 parts by weight. The substrate film of the present invention may be a single layer or a multilayer, but is particularly preferably a laminated film having an inner layer, an intermediate layer, and an outer layer, and the intermediate layer contains 5 to 20% by weight of titanium oxide, and The thickness of the intermediate layer is preferably 50% or more of the total thickness of the laminated film.

The base film may be manufactured by using a general method for forming a polyolefin resin film such as a T-die extrusion molding method, an inflation molding method and a calendar molding method. As a method of manufacturing a laminated film having an inner layer, an intermediate layer, and an outer layer, a method of laminating each formed film using a laminator or a method of pressing and laminating at the same time as film forming can be used. It is particularly preferable to form a laminated film simultaneously with molding because the number of steps can be reduced.

The thickness of the base film varies depending on the application, but is usually 30 to 500 μm, preferably 50 to 300 μm.
m. In order to satisfy the initial and long-term adhesion to various inks, the substrate film of the present invention is preferably subjected to an easy adhesion treatment on the surface of the film. Examples of the easy adhesion treatment include known methods such as corona discharge treatment, plasma treatment, ozone treatment, and flame treatment. The treatment conditions are the composition of the polyolefin resin film and the wetting index (JIS K6).
768) must be appropriately selected in consideration of the attenuation rate.
What is necessary is just to adjust so that the wetting index of the easily adhesively treated surface of the polyolefin resin film at the time of the primer treatment is at least 370 μN.

The polyolefin resin laminated film of the present invention has a primer layer containing a polyurethane resin mainly composed of a polycarbonate polyurethane resin formed on at least one surface of a substrate film. Among them, the primer layer is preferably made of a polyurethane resin containing the polycarbonate polyurethane resin as a main component. Further, the ratio of the polycarbonate polyurethane resin is preferably 55 to 100% by weight, and particularly preferably 70 to 100% by weight in the polyurethane resin.

The polycarbonate polyurethane resin is a polymer of a polycarbonate diol and an aliphatic and / or alicyclic diisocyanate and has a hydroxyl group at a molecular terminal and has a weight average molecular weight of 15,000 to 150,
Preferably, the main component is a polycarbonate polyurethane (for example, a lacquer type). The polycarbonate polyurethane is preferably 50 to 100% by weight of the polycarbonate polyurethane resin,
In particular, it is preferably from 70 to 100% by weight.

If the weight average molecular weight of the polycarbonate polyurethane is less than 15,000, an excessive amount of a cross-linking agent is required to improve the drying property. As a result, the degree of cross-linking of the polycarbonate polyurethane becomes too high and a flexible cured film is formed. It tends to be difficult to obtain, and the blocking property of the primer layer in the roll state, the UV ink adhesion property, and the curved surface following property tend to be inferior.

On the other hand, when the weight average molecular weight of the polycarbonate polyurethane exceeds 150,000, the solution viscosity at the time of primer coating becomes high, workability and drying property are deteriorated, and excess solvent remains and the frequency of generation of bubbles is high. This is not preferable because it causes a decrease in adhesion to a film serving as a substrate. The primer layer has a tensile modulus of 300 MPa
Or less, and more preferably 295 MPa or less. The value of the tensile modulus of the primer layer in the present invention is determined by forming a primer layer on a base film to form a polyolefin resin laminated film of the present invention, and then subjecting the film to room temperature 23 ° C. and 50% relative humidity. After storage for one month under the conditions described above, measured by the method described in Examples.

The polycarbonate diol is represented by the following general formula (1).

[0036]

Embedded image HO — [— R—O—COO—] _n —R—OH (1) (R is an aliphatic or alicyclic substituent) The polycarbonate diol is, for example, an alkylene carbonate, It is obtained by reacting one or more compounds selected from the group consisting of diaryl carbonates and dialkyl carbonates with diols and / or polyether polyols.

Examples of the alkylene carbonate include ethylene carbonate, 1,2-propylene carbonate, 1,2-butylene carbonate and the like. Examples of diaryl carbonates include diphenyl carbonate, phenyl-naphthyl carbonate, dinaphthyl carbonate, 4-methyldiphenyl carbonate,
-Ethyldiphenyl carbonate, 4-propyldiphenylcarbonate, 4,4'-dimethyl-diphenylcarbonate, 4,4'-diethyl-diphenylcarbonate, 4,4'-dipropyl-diphenylcarbonate and the like.

Examples of dialkyl carbonate include dimethyl carbonate, diethyl carbonate, di-n-
Propyl carbonate, diisopropyl carbonate,
Examples thereof include di-n-butyl carbonate, diisobutyl carbonate, di-t-butyl carbonate, di-n-amyl carbonate, diisoamyl carbonate, and the like.

Examples of co-reactants for these carbonates include diols such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, and 1,4-butanediol. , 2-methyl-1,3-propanediol, neopentyl glycol, 2-methyl-pentanediol, 3
-Methyl-pentanediol, 2,2,4-trimethyl-1,6-hexanediol, 2,3,5-trimethylpentanediol and the like.

Examples of polyether polyols include, for example, polytetramethylene glycol obtained by ring-opening polymerization of tetrahydrofuran, and alkylene oxide adducts of diols. Examples of diols used herein include, for example, ethylene glycol, 1,
2-propanediol, 1,3-propanediol,
1,3-butanediol, 1,4-butanediol, isomeric pentanediols, isomeric hexanediols or octanediols such as 2-ethyl-1,3-hexanediol, 1,2-bis (hydroxymethyl) −
Cyclohexanone, 1,3-bis (hydroxymethyl)
-Cyclohexanone, 1,4-bis (hydroxymethyl) -cyclohexanone, trimethylolpropane, glycerin and the like. Examples of the alkylene oxide include ethylene oxide, propylene oxide, 1,2-butylene oxide, and 1,3-butylene. Examples thereof include butylene oxide, 2,3-butylene oxide, tetrahydrofuran, styrene oxide, and epichlorohydrin. These can be used in combination of two or more.

The above-mentioned diols and polyether polyols may be used alone or in combination of two or more. Any of these can be reacted with one or more compounds selected from the above-described alkylene carbonate, diaryl carbonate, and dialkyl carbonate by a known method to form a polycarbonate diol.

The polycarbonate diol has a weight average molecular weight of 500 to 4,000, preferably 1,000 to 3,000.
If less than 500, chipping resistance is reduced,
If it exceeds 4,000, phenomena such as shrinkage and undulation on the appearance of the coating film occur, which is not preferable. Next, as the diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate,
Examples thereof include aliphatic and alicyclic diisocyanates such as hydrogenated tolylene diisocyanate and xylene diisocyanate.

The polycarbonate polyurethane is prepared by reacting a polycarbonate diol with a diisocyanate compound in a molar ratio of polycarbonate diol: diisocyanate compound = 1: 1 to 1: 5.
It can be manufactured by a known method. As such a method, known methods such as a method of producing a high-molecular-weight polyurethane using a crosslinking agent or a chain extender after pre-polymerization in advance, or a method of producing a high-molecular-weight polyurethane by reacting all the components in one step are used. Method.

Regardless of the production method, the molecular structure of the polycarbonate polyurethane is preferably a structure mainly composed of a linear structure for the purpose of forming a primer layer having rubber elasticity. The primer containing the polycarbonate polyurethane resin used in the present invention can be used as a one-pack type coating agent without adding a crosslinking agent. Cross-linking agent (curing agent)
Can also be used as a mixture.

The crosslinking agent to be mixed is obtained by addition polymerization of at least one of aliphatic, alicyclic and aromatic diisocyanates with ethylene glycol, propylene glycol, hexanetriol, trimethylolpropane trimethacrylate and the like. Adducts and isocyanurate polymers obtained by polymerizing aliphatic, alicyclic or aromatic diisocyanates and the like are mentioned.

The mixing ratio of the main agent / crosslinking agent is usually 5 to 40 parts by weight, preferably 10 to 30 parts by weight of the crosslinking agent based on 100 parts by weight of the polycarbonate polyurethane resin as the main agent. Usually, these main agents or the main agent and the crosslinking agent are used by dissolving in a solvent, and further adjusted to an appropriate concentration by using a diluting solvent or the like, and the base film or the base film of the base film is rolled or gravure rolled. A primer layer is formed by coating and drying on the easily bonded surface.

The dry film thickness of the obtained primer layer is usually about 0.3 to 3 μm. Further, in the polyolefin resin laminated film of the present invention, an organic or inorganic powder may be added to the primer layer for the purpose of preventing the state of a roll and blocking in a printing step and improving the transferability of ink. Examples of the organic powder include urethane resin beads, polycarbonate resin beads, and pigments such as carbon black.Examples of the inorganic powder include calcium carbonate, barium sulfate, silica, silica alumina, clay,
Pigments such as talc and titanium oxide are exemplified.

Among them, it is particularly preferable to use silica powder having an average particle diameter of 0.1 to 5 μm. The amount of the organic and / or inorganic powder to be added is preferably 1 to 100 parts by weight based on 100 parts by weight of the polycarbonate polyurethane resin, and is preferably used in consideration of the desired transparency, surface gloss and non-blocking property. I just need.

For example, in the case of silica powder, if the addition amount exceeds 20 parts by weight, choking and fine cracks in the primer layer are liable to occur after the weather resistance test, which is not preferable because it causes poor adhesion to the printing ink. When the polyolefin-based resin laminated film of the present invention is applied to a transparent use, the amount of the silica powder in the primer layer may be controlled so as not to adversely affect the transparency. Usually, the addition amount of the silica powder is more preferably 1 to 20 parts by weight.

In addition, in the present invention, a known powdery and / or liquid ultraviolet absorber and a light stabilizer such as a hindered amine light stabilizer are added to the primer layer for the purpose of imparting long-term outdoor weather resistance. Can be. These are preferably liquid. As the ultraviolet absorber and the light stabilizer, those mentioned in the description of the base film can be used. The addition ratio of the ultraviolet absorber and the light stabilizer is about 1/1 to 2/1 (weight ratio), and 1 to 70 parts by weight can be added to 100 parts by weight of the polycarbonate polyurethane resin.

If necessary, an antistatic agent having a quaternary ammonium base can be added to the primer layer in an amount of 0.5 to 5.0 parts by weight based on 100 parts by weight of the polycarbonate polyurethane resin. If the addition amount is less than 0.5 parts by weight, the antistatic effect is low, and there is a possibility that a blocking trouble in a conveyance step before printing, a foreign substance adhesion in a printing step, and the like may occur. On the other hand, when the amount exceeds 5.0 parts by weight, the non-transferability of the ink is deteriorated and the ink adhesion is impaired. Examples of the antistatic agent having a quaternary ammonium base include those having 1 to 2 carbon atoms.
0, dimethyl or diethyl sulfate such as alkyldimethylamine and alkyldiethylamine, and those having a hydroxyl group instead of hydrogen in the alkyl group are particularly preferable.

After printing on the surface of the polyolefin resin laminated film of the present invention on the primer layer side and, if necessary, corona discharge treatment or anchor coating on the surface opposite to the surface, the adhesive layer is formed. By providing, a label or a sticker is obtained. The type of the adhesive is not particularly limited, for example, natural rubber, synthetic rubber,
Acrylic, urethane, vinyl ether, silicone, amide, styrene adhesive, styrene elastomer, olefin elastomer, acid-modified olefin resin graft-modified with ethylenically unsaturated carboxylic acid and its anhydride, etc. An adhesive is suitably used,
The form may be any of a solution type, an emulsion type, a hot melt type and the like. In the pressure-sensitive adhesive layer, for example, α-pinene or β
-Terpene resins such as pinene polymer, diterpene polymer, α-pinene / phenol copolymer, hydrocarbon resins such as aliphatic and aromatic, aliphatic / aromatic copolymers, and other rosin resins And a suitable tackifier such as coumarone-indene resin, (alkyl) phenol resin and xylene resin. Further, various additives such as a softening agent such as a liquid polymer and a paraffin-based oil, a filler, a pigment, a colorant, an antioxidant, a stabilizer, and an ultraviolet absorber can be added according to the intended use.

An additional layer may be provided between the polyolefin resin laminated film of the present invention and the pressure-sensitive adhesive layer, if necessary.

[0054]

EXAMPLES The embodiments of the present invention will be described below in detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist. <Evaluation method> (1) Crosslinking rate of primer layer The laminated film made of polyolefin resin (not corona-treated) prepared in Examples or Comparative Examples was used as a base film, and a 10 μm thick primer layer was formed thereon. Then, a test piece was punched out into a circle having a diameter of 28 mm.
Next, a diluting solvent (toluene / ethyl acetate = 45/55)
The molded article was immersed in the solution at room temperature of 25 ° C. for 3 days, and the dry gel weight of the insoluble portion relative to the original molded article weight (weight of the primer layer before immersion) was measured and expressed as a percentage. (2) Weight average molecular weight of polyurethane Showa Denko Co., Ltd., using tetrahydrofuran (THF) as a solvent, using an HLC8020 type gel permeation chromatography (GPC) apparatus manufactured by Tosoh Corporation.
The column was developed using KF806L.

The obtained results were expressed as a weight average molecular weight (Mw) based on a polystyrene standard sample. (3) Tensile modulus The tensile modulus of the base film was measured according to JIS K7127. Measurement samples were sampled after film formation and corona treatment, and stored for one day at room temperature of 23 ° C. and 50% relative humidity.
Each specimen was stored (aged) for 3 days in a warm room at 0 ° C. and collected as test specimens.

However, the dumbbell was No. 1, and the pulling speed was 50 m.
m / min. For the test piece for measuring the tensile modulus of the primer layer film, a non-corona-treated substrate film was prepared, a primer was applied thereon, and a primer layer having a thickness of 10 μm after drying was prepared. After storing for one month under the conditions of room temperature 23 ° C. and 50% relative humidity, the substrate film was peeled off, and the tensile modulus of the primer layer itself was measured in the same manner. (4) Initial adhesion to substrate film After the surface of the test piece (substrate film / primer layer) on the primer layer side and the adhesive surface of Cellotape (registered trademark) are adhered using a roller, 90 ° peeling and 180 ° peeling are performed. The state of adhesion between the primer layer and the base film at this time was visually judged.

The peeling was performed manually, and was performed at an instantaneous high speed. ：: No peeling was observed in all cases. △: The peeling of the primer layer was slight but there was × .: The peeling of the primer layer was more than half. (5) Chargeability The primer layer side was regarded as the surface side and JIS L 1094 was used.
According to Method B, one of the test pieces (base film / primer layer)
The friction band voltage value after one minute was measured. In Comparative Example 1, the frictional charged voltage value of the surface of the substrate film one minute after was measured. (6) Slipperiness The primer layer surface (base film surface in Comparative Example 1) and thickness 2 of the test piece (base film / primer layer)
The quality of slipperiness was determined by a method in which the back surface of a release paper (liner) of 00 μm was overlapped and rubbed by hand.

：: Good slipperiness Δ: Slightly poor ×: Poor slipperiness and immobile (7) Blocking resistance A test piece (base film / primer layer, base film in Comparative Example 1) of 1 in a rolled state Monthly room temperature (35
C), the molded product was rewound and the blocking state was evaluated.

The evaluation results were ranked as follows. ：: Rewinding (peeling) was possible without blocking △: Blocking during peeling ×: Difficult to peel (8) Presence or absence of curl and warpage Acrylic adhesive was coated on a 200 μm thick liner, dried and tested A laminate (a base film / primer layer, the base film in Comparative Example 1) on the side opposite to the primer layer (corona treated) and the pressure-sensitive adhesive surface of the liner were bonded to a 40 cm square size. After being cut and left on a flat surface for one week, the state of curl and warpage was visually determined.

：: There is no problem in practical use Δ: There is curl and warpage of about 5 mm ×: There are curl and warp to be practically problematic. (9) UV ink suitability A commercially available UV ink (Toyo Ink (Toyo Ink) was used on the primer layer (on the base film surface in Comparative Example 1) of the test piece (base film / primer layer, base film in Comparative Example 1). Offset printing (dry coating amount: 2 g / m ² ) using FD-O manufactured by KK, and then UV irradiation with a UV irradiator (1.5 kW high-pressure mercury lamp manufactured by Eye Graphic Co., Ltd.) to cure. Then, a printed film was formed. For the obtained printed film, the ink transfer rate when using a polyvinyl chloride resin film as the base film is 100%.
The transfer rate of the ink of each test piece to the test piece was visually determined, the adhesion to cellophane tape was evaluated by the method described in (4), and the adhesion between the primer layer and the UV printing film was evaluated.

：: None peeled off Δ: Slight peeling of the printed film was present X: Half or more peeled of the printed film (10) Cutability Test piece (base film / primer layer, base material in Comparative Example 1) The film was punched out with a circular blade having a diameter of 6 mm, and the state was observed.

Good: Cut uniformly along a circular line, and the cut surface is clean. Δ: Most of the cut was performed, but a cut part extended in a whisker-like shape was partially observed. X: A part remains without being cut. (11) Weather resistance A test piece (base film / primer layer) having a size of 5 cm × 11 cm was set so that light was irradiated to the primer layer side, and a sunshine weatherometer manufactured by Suga Test Instruments Co., Ltd. was used. After exposure for 2,000 hours at (condition: black panel temperature: 63 ° C., rainfall: 12 minutes / 60 minutes), the appearance change (discoloration and cracks) of the test piece and the adhesion state between the substrate film and the primer layer were visually evaluated. .

[0063] Appearance change ○: good appearance △: Some changes Yes ×: remarkable change in appearance there contact state ○: Both None peeling △: × There but slight peeling of the primer layer: Peeling of more than half a primer layer located Example 1-4 <Preparation of base film and easy adhesion treatment> A homopropylene polymer having a melting point of 165 ° C and a melt flow rate of 2.4 (g / 10 minutes), a melting point of 165 ° C and a melt flow rate of 15.0.
(G / 10 min) homopropylene polymer and melting point 140
Using a polypropylene resin composition obtained by mixing a random propylene copolymer having a melt flow rate of 7.0 (g / 10 minutes) with a random propylene copolymer at a ratio shown in Table 2, using a multilayer extrusion molding machine manufactured by Mitsubishi Heavy Industries, Ltd. , A laminated film having the same composition as each layer having a thickness of 100 μm (layer thickness ratio: inner layer / intermediate layer / outer layer = 1/8)
/ 1).

Next, both sides of the laminated film were subjected to corona treatment to obtain a double-sided corona-treated base film. The wetting index on both sides of the obtained base film was 450 μN.
Table 2 shows the results of measuring the tensile modulus. <Primer treatment of base film> Polyhexamethylene polycarbonate diol and isophorone diisocyanate are mixed at a molar ratio of 1: 1 and urethanized and polymerized. Using a diisocyanate trimer as a crosslinking agent, a primer coating solution was prepared (as described in Table 1 below).

Next, one surface of the substrate film (the inner layer side)
After applying the primer coating solution to the corona-treated surface of the above using a 175 mesh gravure roll, it was continuously heated in a hot air drier at 80 ° C. for 10 seconds, and was naturally cooled in the line, and was obtained. Winding tension of polyolefin resin laminated film (base film / primer layer) 10k
Under a condition of g / full width, the film was wound in a roll of 1000 m. In addition, the result of measuring the weight of the primer layer after drying was 0.6 g / m ² . The thickness of the primer layer was 0.6 μm.

Next, various evaluations were performed using the polyolefin resin laminated film and the like. Table 2 shows the results. Example 5 < Preparation of white base film and primer treatment> Example 3
Titanium oxide pigment 1
A laminated film having a composition containing 3 parts by weight was prepared.

Next, both sides of the film were subjected to corona treatment to obtain a double-sided corona-treated base film. The wetting index of the corona-treated surface of the obtained base film was 470 μN. Table 2 shows the results of measuring the tensile modulus. Next, on the corona-treated surface on one side (the inner layer side) of the base film,
The same primer treatment as in Examples 1 to 4 was performed.

Various evaluations were carried out using the obtained polyolefin resin laminated film (base film / primer layer). Table 2 shows the results. Comparative Example 1 Various evaluations were performed in the same manner as in Examples 1 to 5, except that the double-sided corona-treated base film obtained in Example 3 was used without any primer treatment.

Comparative Example 2 Melting point 140 ° C., melt flow rate 7.0 (g / 10
Min) random propylene copolymer 75 parts by weight, melting point 1
Examples 1 to 5 were prepared using a composition obtained by mixing 25 parts by weight of a low-crystalline propylene homopolymer having a melt flow rate of 2.5 (g / 10 minutes) and a heat of crystal fusion of 90 J / g at 60 ° C.
By the same extrusion molding as described above, a laminated film having the same composition of each layer having a thickness of 100 μm (layer thickness: inner layer / intermediate layer / outer layer = 1/8)
/ 1).

Next, both sides of the laminated film were subjected to corona treatment to obtain a double-sided corona-treated base film. The wetting index on both sides of the obtained base film was 450 μN. Table 2 shows the results of measuring the tensile modulus. Next, the same primer treatment as in Examples 1 to 4 was performed on the corona-treated surface on one surface (the inner layer side) of the base film.

Various evaluations were carried out using the obtained polyolefin resin laminated film (base film / primer layer). Table 2 shows the results.

[0072]

[Table 1]

[0073]

[Table 2]

[0074]

The polyolefin resin film of the present invention can be handled in the form of a roll similar to the polyvinyl chloride resin film, and further has good adhesion to various inks, especially ultraviolet curing inks. Non-curl,
Excellent performance such as long-term weather resistance, and especially in automatic cutter work with a flat blade or rotary blade,
It is suitable for use as a base material film for markings such as stickers and labels since troubles of uncut defects do not occur when cutting or half-cutting into various shapes.

 ────────────────────────────────────────────────── ─── Continuing on the front page F term (reference) 4F100 AA01B AA01C AA21D AK03A AK07A AK07D AK51B AK51C AL03A AL05A AL05D BA02 BA03 BA06 BA10B BA10C BA15A BA16A BA25B BA25C CA23B CA23C CA23D DE01B DE01Y00K

Claims (9)

[Claims] 1. A tensile modulus (JIS K 7127) of 6
A primer layer having a thickness of 0.3 to 3 μm containing a polyurethane resin containing a polycarbonate polyurethane resin as a main component is laminated on at least one surface of a polyolefin resin film having a thickness of 00 to 1200 MPa and a thickness of 30 to 500 μm. Characterized laminated film made of polyolefin resin. 2. The polypropylene resin laminated film according to claim 1, wherein the polyolefin resin film is a laminated film composed of a homopropylene polymer and a random propylene copolymer. 3. A laminated film having a polyolefin resin film having an inner layer, an intermediate layer and an outer layer, wherein the inner layer comprises 25 to 75% by weight of a homopropylene polymer and 75 to 25% by weight of a random propylene copolymer. The laminated film made of a polypropylene-based resin according to claim 1 or 2, comprising: 4. The polyolefin resin film is a laminated film having an inner layer, an intermediate layer and an outer layer, wherein the intermediate layer contains 5 to 20% by weight of titanium oxide and has a thickness of the entire laminated film. The polyolefin-based resin laminated film according to any one of claims 1 to 3, which is 50% or more of the thickness. 5. The polycarbonate polyurethane resin,
A polymer of a polycarbonate diol and an aliphatic and / or alicyclic diisocyanate, having a hydroxyl group at a molecular terminal and having a weight average molecular weight of 15,000 to 150,000.
The laminated film made of a polyolefin-based resin according to any one of claims 1 to 4, comprising a polycarbonate polyurethane of 0 as a main component. 6. A primer layer formed by reacting a polycarbonate polyurethane resin with at least one of (a) an adduct of an aliphatic, alicyclic or aromatic diisocyanate or (b) an isocyanurate polymer. ,
And a tensile modulus of 300 MPa or less.
The laminated film made of a polyolefin resin according to any one of the above. 7. The primer layer has an average particle size of 0.1 to 5
The laminated film made of a polyolefin-based resin according to any one of claims 1 to 6, further comprising a μm inorganic powder. 8. The polyolefin resin laminated film according to claim 1, wherein the polyolefin resin film is an aged film. 9. A display substrate comprising the polyolefin resin laminate film according to claim 1. Description: