JP2000344907A - Printing film - Google Patents

Abstract

(57) [Problem] To provide a printing film excellent in weather resistance, storage property and low-temperature impact resistance. SOLUTION: It is made of a vinyl chloride resin containing an elastomer component, has no stickiness or change in physical properties due to blooming of a plasticizer, has excellent weather resistance and storage properties, and can be used outdoors. Very little surface contamination, beautiful print surface can be maintained for a long time, and furthermore, the use of a specific elastomer makes low-temperature impact resistance even better, and is suitable for use in winter construction and outdoor use. Printing film.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a printing film which does not need to contain a plasticizer and has excellent weather resistance and storage stability.

[0002]

2. Description of the Related Art Conventionally, signs, figures, symbols, patterns, patterns, and the like for advertisement and guidance display of goods are displayed on signboards and bulletin boards of stations by photoengraving or silk-screen printing. However, this method has disadvantages that it takes a lot of production days and is expensive. Therefore, recently, a method of performing full color printing of characters, figures, photographs, and CG images input on a personal computer on a film using an ink jet printer has become widespread.

As a printing film, for example, Japanese Patent Application Laid-Open No. 63-302042 discloses a method in which an ink absorbing layer is provided on a soft vinyl chloride resin film containing 30 parts by weight of a plasticizer, and a pattern is formed on the surface by an ink jet printer. And the like, after performing desired printing such as this, the printing film is heat-bonded to a homogenous style raw material to produce a vinyl floor tile.

As such a printing film, a vinyl chloride resin is widely used. However, in order to improve weather resistance, it is necessary to add titanium oxide, calcium carbonate, an ultraviolet absorber and the like. However, when these additives are added,
Since the elastic modulus of the film increases and becomes too hard, and the film is liable to bend or crack, a plasticizer is added in most cases to prevent this and provide appropriate elasticity. However, since the plasticizer causes blooming that protrudes over the film surface with time, there are problems that the film surface becomes sticky and that it is difficult to maintain stable physical properties over a long period of time.

In order to solve the above problems, for example, Japanese Patent Application Laid-Open No. 9-31279 discloses an average molecular weight of 1,000 to 1,000.
A method for preventing the volatilization of the plasticizer from the vinyl chloride film using an aliphatic dicarboxylic acid polyester plasticizer of 4000 is disclosed. However, since the plasticizer is used, the volatilization of the plasticizer is eliminated. Can not do, use conditions,
It has been difficult to maintain the initial performance depending on the period of use. Despite the above-mentioned problems, plasticizers have been used exclusively because the development of new materials is very difficult, and so far plasticizers have been eliminated from vinyl chloride films for printing. I couldn't do that.

[0006] Further, by providing an adhesive layer on the surface opposite to the printing surface of the printing film, the film may be attached to a wall or a floor, but the attaching surface is not always horizontal. , Curved surfaces or two surfaces having an angle. At that time, if the low-temperature characteristics of the printing film were poor, there was a problem that the film might break or bend particularly during construction in winter.

Conventionally, low-temperature characteristics are controlled by the amount of plasticizer added. To increase low-temperature characteristics, it is necessary to reduce the amount of plasticizer. On the other hand, to reduce the amount of volatilization, the amount of plasticizer is reduced. Has to be reduced.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems of the prior art, and to provide a printing film which does not require the addition of a plasticizer and has excellent weather resistance and storage stability. . Another object of the present invention is to provide a printing film having excellent low-temperature impact resistance.

[0009]

[Means for Solving the Problems]

[0010] The printing film of the present invention is a film used exclusively for printing, and during storage, during printing, and during handling before and after the printing, the sheets to be superimposed due to stickiness such as stickiness of the surface thereof may be used. It does not adhere to each other, the printed coating does not peel off, and on the contrary it has a moderate flexibility and flexibility that does not become hard and bends or cracks, especially in beautiful inkjet printers It is a printing film that has a printability that enables printing with high finish and efficiency, and that has excellent weather resistance with little change in physical properties even for long-term outdoor use. In addition, it can be diverted to other film applications such as packaging and cushioning for printing purposes, as in the case of conventional printing films.

[0011] The printing film of the present invention comprises a vinyl chloride resin containing an elastomer component. The vinyl chloride resin containing the elastomer component is a graft product obtained by graft copolymerizing a vinyl monomer containing vinyl chloride as a main component in the elastomer component, a blend of the elastomer component and the vinyl chloride polymer,
Alternatively, it is preferably one of a blend of an elastomer component and the graft. In the above graft, two or more grafts having different elastomer components may be used in combination.

[0012] The elastomer used in the present invention is not particularly limited as long as it is a polymer material having flexibility at ordinary temperature. Examples of preferred elastomers include ethylene-vinyl acetate copolymer (EVA), ethylene- (meth) acrylate copolymer (EA), acrylonitrile-butadiene copolymer (NBR), chlorinated polyethylene (CPE), (Meth) acrylic ester copolymer (AC), methyl methacrylate-styrene-butadiene copolymer (MBS), chlorosulfonated polyethylene (CSPE), polyurethane (PU) and the like. These elastomers may be used alone or in combination of two or more.

The EVA is, for example, a vinyl acetate content of 10 to 80% by weight and a melt flow rate (MFR) value of 0.5 measured according to JIS K 6760.
To 300 and the like.

As the EA, for example, the type of the acrylate is ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, etc., the content of the acrylate is 10 to 80% by weight, and the MFR value is 0.1%.
1 to 100 and the like.

As the above-mentioned NBR, for example, an acrylonitrile content of 20 to 50% by weight, Mooney viscosity (ML)
(1 + 4: 100 ° C.) from 10 to 200.

Examples of the CPE include those having a chlorine content of 20 to 55% by weight and an MFR value of 0.1 to 100.

The AC is, for example, an acrylic acid ester, which is a glass transition temperature (Tg) of a homopolymer.
Having a high Tg such as methyl methacrylate; a polymer mainly composed of monomers such as ethyl acrylate, n-propyl acrylate, butyl acrylate, hexyl acrylate and 2-ethylhexyl acrylate. Is a multilayer structure obtained by copolymerization or multi-stage polymerization; and a polymer obtained by using a difunctional or higher functional monomer and having a crosslinked structure. The average particle diameter of the AC is not particularly limited, and is preferably 0.01 to 5 μm.

Examples of the MBS include those having a butadiene component of 50 to 90% by weight, a methyl methacrylate component of 5 to 45% by weight, and a styrene component of 5 to 45% by weight. The average particle size of the MBS is not particularly limited, and is preferably 0.01 to 5 μm.

The above-mentioned CSPE has, for example, a chlorine content of 20 to 50% by weight and a sulfur content of 0.5 to 2.0%.
Weight%, Mooney viscosity (ML1 + 4: 100 ° C) is 10
To 200 and the like.

As the PU, for example, a linear polymer obtained by reacting a functional active hydrogen compound such as a polyol with an isocyanate compound of the whole reaction system or a compound having a partially cross-linked structure can be mentioned. Caprolactone type,
Adipate type, ether type and the like can be mentioned.

Of the above elastomers, 100 parts by weight of an acrylic monomer component containing 50% by weight or more of an alkyl (meth) acrylate monomer having a glass transition temperature of a homopolymer of -140 to -20 ° C, and a polyfunctional monomer component 0 Particularly preferred is an elastomer which is a crosslinked acrylic copolymer obtained by copolymerizing 0.01 to 30 parts by weight. If the glass transition temperature is lower than -140 ° C, it is not suitable as a polymer used industrially, and if it exceeds -20 ° C, it is difficult to impart sufficient flexibility to the obtained film.

When the content of the alkyl (meth) acrylate monomer in the acrylic monomer component is 50,
If the amount is less than 10% by weight, it is difficult to impart sufficient flexibility to the obtained film. Preferably 80 to 100% by weight
It is. When the polyfunctional acrylic monomer is less than 0.01 part by weight or exceeds 30 parts by weight based on 100 parts by weight of the acrylic monomer component, the crosslinked acrylic copolymer does not function as an elastomer, and It is difficult to impart sufficient flexibility to the resulting film. Preferably, it is 0.1 to 10 parts by weight.

As the alkyl (meth) acrylate monomer, the homopolymer has a glass transition temperature of -140 to
The temperature is not particularly limited as long as it is −20 ° C., for example, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl (meth) Acrylate, isooctyl acrylate, n-nonyl (meth) acrylate, isononyl acrylate, n-decyl (meth) acrylate, lauryl (meth) acrylate and the like can be mentioned. These may be used alone or 2
More than one species may be used in combination.

The polyfunctional monomer component is not particularly limited as long as it can be copolymerized with the alkyl (meth) acrylate monomer. For example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, 6-hexanediol di (meth) acrylate, trimethylolpropane di (meth)
Polyfunctional acrylates such as acrylate and trimethylolpropane tri (meth) acrylate; polyfunctional allyl compounds such as diallyl phthalate, diallyl maleate and triallyl isocyanurate; and unsaturated compounds such as butadiene. These may be used alone or in combination of two or more.

The crosslinked acrylic copolymer is, for example,
It can be obtained by an emulsion polymerization method, a suspension polymerization method, a dispersion polymerization method, or the like. Among them, the emulsion polymerization method is suitably used because the control of the resin particle size is easy. The emulsion polymerization method can be performed by a conventionally known method. For example, an emulsifying dispersant, a polymerization initiator, a pH adjuster, an antioxidant, and the like may be added as needed.

The emulsifying and dispersing agent is not particularly limited.
For example, anionic surfactants, nonionic surfactants, partially saponified polyvinyl alcohol, cellulose dispersants, gelatin and the like can be mentioned. Examples of the anionic surfactant include polyoxyethylene nonyl ether sulfate and the like. These may be used alone or in combination of two or more.

The polymerization initiator is not particularly limited.
Examples include water-soluble initiators such as ammonium persulfate, potassium persulfate, and hydrogen peroxide; organic peroxides such as benzoyl peroxide and lauroyl peroxide; and azo-based initiators such as azobisisobutyronitrile. . These may be used alone or in combination of two or more.

The specific method of the emulsion polymerization method is not particularly limited, and examples thereof include a batch polymerization method, a monomer dropping method,
Emulsion dropping method and the like can be mentioned.

In the batch polymerization method, pure water, an emulsifier / dispersant, a polymerization initiator, and a mixed monomer (the acrylic monomer component and the polyfunctional monomer component) are packaged in a jacketed polymerization reactor. This is a method in which the mixture is added, stirred under a nitrogen stream pressurized and sufficiently emulsified, and then the inside of the reactor is heated with a jacket to start the reaction.

In the monomer dropping method, pure water, an emulsifying dispersant, and a polymerization initiator are charged into a jacketed polymerization reactor, and the temperature of the reactor is increased under a nitrogen stream. Component and polyfunctional monomer component) are added dropwise in a fixed amount to start a polymerization reaction.

In the emulsion dropping method, a mixed monomer (the acrylic monomer component and the polyfunctional monomer component), an emulsifying dispersant, and pure water are stirred to prepare an emulsifying monomer in advance, followed by a polymerization reaction with a jacket. This is a method in which pure water and a polymerization initiator are placed in a vessel, and the temperature inside the reactor is raised under a nitrogen stream, and then the emulsified monomer is dropped in a predetermined amount to start a polymerization reaction.

The form and structure of the crosslinked acrylic copolymer are not particularly limited. For example, a core-shell structure in which the surface layer of the resin particles and the internal monomer composition and the crosslinked structure are different is preferable. According to this structure, the stability of the resin particles and the strength performance of the molded article can be improved.

Examples of the method for forming the core-shell structure include a method in which a polymerization initiator is added to an emulsified monomer prepared from a mixed monomer, pure water, and an emulsifier, which constitutes the core, and the core is graft-copolymerized. No.

In the resin particles thus obtained, the shell part three-dimensionally covers the surface of the core part, and the copolymer forming the shell part and the copolymer forming the core part Partially covalently bond, and the shell forms a three-dimensional crosslinked structure. In the above method, the graft copolymerization of the shell may be continuously performed in the same polymerization step as the polymerization of the core.

The monomer having vinyl chloride as the main component used in the present invention is vinyl chloride or a mixture of vinyl monomers copolymerizable with vinyl chloride, and the vinyl chloride polymer is defined as a single polymer of vinyl chloride. It is a copolymer of vinyl chloride and a vinyl monomer having vinyl chloride as a main component and copolymerizable with vinyl chloride.

The above-mentioned monomers copolymerizable with vinyl chloride are not particularly restricted but include, for example, α-olefins such as ethylene, propylene and butylene; vinyl esters such as vinyl acetate and vinyl propionate; ethyl vinyl ether and butyl vinyl ether Vinyl ethers such as
Acrylic esters such as methyl acrylate, butyl acrylate, and hydroxyethyl acrylate; methacrylic esters such as methyl methacrylate, butyl methacrylate, and hydroxyethyl methacrylate; aromatic vinyls such as styrene and α-methyl styrene; Vinyl halides such as vinylidene chloride and vinylidene chloride; and N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide. These may be used alone or in combination of two or more.

The amount of the vinyl monomer copolymerizable with the vinyl chloride monomer varies depending on the type and reactivity of the vinyl monomer, but is not more than 20% by weight based on the total amount of vinyl chloride and the vinyl monomer. Preferably it is. If it exceeds 20% by weight, the properties inherent in the vinyl chloride resin may be lost.

The degree of polymerization of the vinyl chloride polymer is 40
0 to 2500 is preferred. If the degree of polymerization is less than 400, the durability will be poor. If the degree of polymerization exceeds 2500, the melt viscosity of the resin will be high and the moldability will be poor. More preferably, it is 500 to 1600.

The amount of the elastomer component in the vinyl chloride resin used in the present invention is preferably from 10 to 50% by weight. When the amount of the elastomer is less than 10% by weight, the obtained printing film lacks flexibility, and is likely to bend, crack, or the like, resulting in poor handling. 50% by weight
If it exceeds, sufficient strength cannot be obtained, and a problem may occur in the workability of the obtained printing film.

The graft copolymerization of the above elastomer with a vinyl monomer mainly composed of vinyl chloride is not particularly limited, and can be carried out by a conventionally known method, for example, a suspension polymerization method, an emulsion polymerization method, a solution polymerization method and the like. Is mentioned. Among them, the suspension polymerization method is suitably used. In the suspension polymerization method, a dispersant, a polymerization initiator and the like are used.

The dispersant is not particularly restricted but includes, for example, methylcellulose, ethylcellulose, hydroxypropylmethylcellulose, polyvinyl alcohol and partially saponified products thereof, gelatin, polyvinylpyrrolidone,
Starch, maleic anhydride-styrene copolymer, and the like. These may be used alone or in combination of two or more.

The polymerization initiator is not particularly limited.
For example, organic peroxides such as lauroyl peroxide, t-butyl peroxypivalate, diisopropyl peroxy dicarbonate, dioctyl peroxy dicarbonate, t-butyl peroxy neodecanoate, α-cumyl peroxy neodecanoate, etc. Class; 2,2-
Azobisisobutyronitrile, 2,2-azobis-2,
An azo compound such as 4-dimethylvaleronitrile and the like can be mentioned. These may be used alone or in combination of two or more. Also, if necessary, a pH adjuster,
An antioxidant and the like may be added.

As the above suspension polymerization method, for example, the following method is used. After charging a pure water, a dispersant, a polymerization initiator, and an elastomer into a polymerization vessel with a temperature controller and a stirrer, and removing air from the polymerization vessel by a vacuum pump,
Vinyl chloride is introduced into the polymerization vessel. After the elastomer is dispersed or dissolved in vinyl chloride, the temperature is raised to initiate polymerization at a desired polymerization temperature. After completion of the reaction, the remaining monomer is discharged out of the polymerization vessel to obtain a slurry. After dehydration with a dehydrator, drying is performed to obtain a vinyl chloride resin.

In the above-mentioned vinyl chloride resin, if necessary, compounding agents such as stabilizers, stabilizing aids, lubricants, processing aids, ultraviolet absorbers, light stabilizers, antioxidants and fillers are added. May be done.

The stabilizer is not particularly restricted but includes, for example, dimethyltin mercapto, dibutyltin mercapto, dioctyltin mercapto, dibutyltin malate, dibutyltin maleate polymer, dioctyltin malate, dioctyltin maleate polymer, dibutyltin laurate , Organic tin stabilizers such as dibutyltin laurate polymer; lead white, basic tin sulfite, dibasic lead sulfite, tribasic lead sulfite,
Lead-based stabilizers such as dibasic lead phosphite, silica gel coprecipitated lead silicate, lead stearate, lead benzoate, dibasic lead stearate, lead naphthenate; calcium stearate, barium stearate, zinc stearate Metal soaps such as;
Calcium-zinc stabilizer, barium-zinc stabilizer,
Barium-cadmium stabilizer, hydrotalcite,
Zeolite and the like can be mentioned. These may be used alone or in combination of two or more.

The stabilizing aid is not particularly limited.
For example, epoxidized soybean oil, epoxidized linseed oil, epoxidized tetrahydrophthalate, epoxidized polybutadiene, phosphate ester and the like can be mentioned. These may be used alone or in combination of two or more.

The lubricant is not particularly restricted but includes, for example, montanic acid wax, paraffin wax, polyethylene wax, stearic acid, stearyl alcohol, butyl stearate and the like. These may be used alone or in combination of two or more.

The processing aid is not particularly limited, and examples thereof include (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylate.
Acrylate homopolymer; copolymer of two or more monomers selected from the above (meth) acrylate homopolymers; copolymer of (meth) acrylate and vinyl monomers such as styrene, vinyltoluene, and acrylonitrile And the like. These may be used alone or in combination of two or more.

The ultraviolet absorber is not particularly limited, and examples thereof include salicylate-based, benzophenone-based, benzotriazole-based, and cyanoacrylate-based ultraviolet absorbers. These may be used alone or in combination of two or more.

The light stabilizer is not particularly restricted but includes, for example, hindered amine light stabilizers.

The antioxidant is not particularly limited.
For example, phenolic antioxidants and the like can be mentioned.

The filler is not particularly restricted but includes, for example, silica, diatomaceous earth, alumina, zinc oxide, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, ferrites, calcium hydroxide, water Magnesium oxide, aluminum hydroxide, basic magnesium carbonate, calcium carbonate, magnesium carbonate, zinc carbonate, barium carbonate, dawsonite, hydrotalcite, calcium sulfate, barium sulfate, gypsum fiber, calcium silicate, talc, clay, mica, montmorillonite , Bentonite, activated clay, sepiolite, imogolite, sericite, glass fiber, glass beads, silica balun, aluminum nitride, boron nitride, silicon nitride, carbon black, graphite, carbon fiber, carbon balun, charcoal powder Various metal powders, potassium titanate, magnesium sulfate (MOS), titanate zirconium lead, aluminum borate, molybdenum sulfide, silicon carbide, stainless steel fiber, zinc borate, various magnetic powder,
Slag fibers, fly ash, dewatered sludge, and the like are included. These may be used alone or in combination of two or more.

The printing film of the present invention preferably contains a pigment. The pigment is added to the vinyl chloride resin for the purpose of improving weather resistance, print clarity, mechanical properties, and the like. The amount of the pigment added is preferably 3 to 100 parts by weight, more preferably 5 to 50 parts by weight, and particularly preferably 7 to 25 parts by weight based on 100 parts by weight of the vinyl chloride resin.

The above-mentioned pigment is not particularly limited because it is appropriately selected according to the intended use. Examples thereof include azo-based pigments, phthalocyanine-based pigments, and the like.
Organic pigments such as sullen and dye lakes; inorganic pigments such as oxides, molybdenum chromates, sulfides / selenides, and ferrocyanides; titanium oxide, titania, titanium white, zinc white, zinc oxide, Zinc white, zinc sulfide, lithopone,
White pigments such as lead white, antimony white and zirconium oxide;
Barium sulfate, barite powder, calcium carbonate, white carbon, silica, alumina white, diatomaceous earth, iron oxide, tin oxide, antimony oxide, ferrites, calcium hydroxide, magnesium hydroxide, aluminum hydroxide,
Basic magnesium carbonate, magnesium carbonate, zinc carbonate, barium carbonate, dawsonite, hydrotalcite, calcium sulfate, gypsum fiber, calcium silicate, kaolin, talc, clay, mica, montmorillonite, bentonite, activated clay, sepiolite, imogolite,
Sericite, silica-based balun, aluminum nitride, boron nitride, silicon nitride, carbon black, graphite, carbon balun, charcoal powder, potassium titanate, magnesium sulfate, lead zirconia titanate, aluminum borate, molybdenum sulfide, silicon carbide, boric acid Extenders such as zinc, fly ash, and dehydrated sludge; Among the above pigments, titanium oxide, barium sulfate, calcium carbonate, talc and the like are preferably used from the viewpoints of weather resistance, print clarity and the like. These may be used alone or 2
More than one species may be used in combination.

The order and method of mixing the above-mentioned various compounding agents with the above-mentioned vinyl chloride resin are not particularly limited, and any method can be adopted, and may be a method by hot blending or a method by cold blending.

As a method for molding the above-mentioned vinyl chloride resin as the printing film of the present invention, it is general to produce it by a calendering method. The vinyl chloride resin and the above-mentioned various compounding agents are mixed by heating with a ribbon type blender, a Henschel type mixer, etc., kneaded with a blend master with a Banbury mixer, etc., tempered with a roll, and then charged on a calender roll, and charged at 140 to 180 ° C. Rolled sheeting at a temperature of, and formed through a cooling and winding process.

In addition, as an extrusion method, 150 to 200 ° C.
And a method of extrusion molding from a T die, a coat hanger die, or the like.

In the printing film of the present invention, the thickness of the film is preferably 50 to 300 μm. 50 thickness
If it is less than μm, sufficient strength as a film cannot be obtained, and if it exceeds 300 μm, the film becomes too hard and has poor flexibility, and the workability when attaching the printing film to a wall deteriorates.

The above printing film preferably has a total absorbed energy of 8 J or more in a multiaxial impact test at 0 ° C. The multi-axial impact test is based on JIS K 708
5 was measured in accordance with the multiaxial impact test method for carbon fiber reinforced plastics described in 5, and the measurement results are shown by the load-displacement line shown in FIG. 1, and the total absorbed energy is the load shown in FIG. -Represented by the total area enclosed by the breakthrough in the displacement diagram. When the total absorbed energy absorption is less than 8 J, cracks and cracks are easily formed, particularly in winter, when a printing film attached to a wall, a bulletin board, or the like is impacted by any flying object or impact. I will.

Further, when the printing film is left in a constant temperature bath at 70 ° C. for 24 hours, the weight change before and after the standing is preferably less than 5%. Here, the weight change rate is represented by equation (1).

[0061]

(Equation 1)

If the rate of change in weight exceeds 5%, the initial performance of the film changes, and not only cannot stable performance be exhibited over a long period of time, but also wrinkles occur on the film surface,
Significantly impairs the print design.

The printing film of the present invention is preferably applied to an ink jet printer and printed. The inkjet printer is not particularly limited, and a commercially available inkjet printer is used. For example, JP-A-9-2
There is a charge deflection type ink jet printer as disclosed in JP-A-07499.

The method for printing on the above-mentioned printing film by an ink jet printer is not particularly limited.
A conventionally known inkjet recording method can be adopted. For example, there are a deflection method, a cavity method, a thermojet method, a bubble jet method, a thermal ink jet method, a slit jet method, a spark jet method, and a charge deflection type ink jet method. According to various operating principles, these ink droplets fly ink droplets and attach them to a printing film or an ink receiving layer of a printing film described later to record characters, figures, patterns, patterns, and the like. It is.

As the ink used in the ink jet printer, an oil-based ink comprising an oil-soluble dye solution is preferably used. The oil-soluble dye is not particularly limited as long as it can be applied to a vinyl chloride resin.Examples include a naphthol dye, an azo dye, a metal complex dye, an anthraquinone dye, a quinoimine dye, an indigo dye, a cyanine dye, and quinoline. Dyes, nitro dyes, nitroso dyes, benzoquinone dyes, carbonium dyes, naphthoquinone dyes, naphthalimide dyes, phthalocyanine dyes, veniline dyes and the like can be mentioned. The solvent for dissolving the oil-soluble dye is not particularly limited as long as it has a property that enables ink to be ejected by an ink jet printer, for example, isoparaffins, ethers,
An organic solvent such as a plasticizer can be used.

The printing film of the present invention preferably has an ink receiving layer provided on at least one side of the printing film. The ink receiving layer is laminated so that oil-based, semi-oil-based or aqueous ink is well adsorbed, and a transferred image of characters, figures, symbols, patterns, patterns, and the like is formed on the receiving layer. Further, a transparent protective layer may be provided thereon as required. Further, on the surface opposite to the receiving layer, an adhesive is laminated as necessary, and further,
A releasable protective layer may be provided to protect the pressure-sensitive adhesive layer until the printing sheet is attached to the target attaching location.

The receiving layer is not particularly limited as long as it is suitably used for a printing film made of a vinyl chloride resin, and examples thereof include JP-A-10-147066 and JP-A-8-324106. And an ink receiving layer excellent in ink absorbency, printability, ink drying property, etc. The thickness of the ink receiving layer is 1
Generally, it is about 0 to 50 μm.

The pressure-sensitive adhesive is not particularly limited as long as it is suitably used for a vinyl chloride resin film.
For example, an acrylic adhesive, an SBR adhesive, a polyurethane adhesive, a chloroprene adhesive, a butyl rubber adhesive, or the like can be used.

The ink receiving layer and the pressure-sensitive adhesive layer are formed by a roll coater, a reverse roll coater, a knife coater,
Comma coater, blade coater, bar coater, gravure coater, curtain coater, applicator,
It can be formed by applying a required thickness using a die coater, an edge coater or the like.

The printing film provided with the bright ink receiving layer is an ink jet printer using a water-soluble dye and at least water or a medium mainly composed of water, for example, an aqueous ink containing water, an organic solvent and a dispersant. It is preferably applied to

The water-soluble dye is not particularly limited, and includes direct dyes, acid dyes, basic dyes, reactive dyes and disperse dyes. The water-soluble organic solvent is not particularly limited, and polyhydric alcohols such as ethylene glycol, diethylene glycol, and propylene glycol, monoethanolamine, diethanolamine, N,
Examples thereof include alkanolamines such as N-dimethylethanolamine and morpholine, and glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol dimethyl ether. The dispersant is not particularly limited, and examples thereof include an anionic activator, a nonionic activator, an amphoteric activator, and a polymer activator. A binder and various additives may be added to the aqueous ink as needed.

(Function) The printing film of the present invention is made of a vinyl chloride resin containing an elastomer component, and has a suitable tensile strength and stiffness without adding a plasticizer. No plasticizer is added, so there is no stickiness or change in physical properties due to the blooming of the plasticizer over time, and it has excellent weather resistance and storage properties. Contamination is extremely small, and a beautiful printed surface can be maintained for a long time. Furthermore,
By using the specific elastomer, the low-temperature impact resistance is further improved, and it is more suitably used for winter construction and outdoor use.

[0073]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. Example 1 Polyvinyl chloride resin (manufactured by Tokuyama Sekisui Industry Co., Ltd., polyvinyl chloride,
Trade name "TS-1000R", degree of polymerization 1000, 70% by weight in the table below, abbreviated as ST-PVC), elastomer (Kaneace FM-
21 ", the average particle diameter after dispersion is 0.1 to 1 μm, and in Table 1,
A processing aid (manufactured by Mitsubishi Rayon Co., Ltd.) was added to 100 parts by weight of a vinyl chloride resin composition comprising 30% by weight of AC.
1 part by weight of trade name “P-501A”), 4 parts by weight of barium-zinc-based stabilizer (trade name “AC-168” manufactured by Asahi Denka Co., Ltd.), calcium stearate (trade name “S” manufactured by Sakai Chemical Co., Ltd.)
C-100 ") 1 part by weight, 1 part by weight of an internal lubricant (trade name" G-60 "manufactured by Henkel Japan Co., Ltd.), 20 parts by weight of titanium oxide (trade name" RTC-30 "manufactured by Tyoxide Corporation), and benzophenone 0.5 parts by weight of a UV-absorbent (BASF, trade name "Uvinul M40")
The mixture was mixed with a 100 liter super mixer (trade name, manufactured by Kawada Industries Co., Ltd.), and a printing film having a thickness of 120 μm was prepared by a calendar molding method. The printing films obtained were evaluated as described below. Table 1 shows the results.

Examples 2 to 8 Printing films were prepared in the same manner as in Example 1 except that the elastomers shown in Table 1 were used instead of the elastomers of Example 1. About the obtained printing film,
The following evaluation was performed. Table 1 shows the results.

Example 9 Instead of the vinyl chloride resin of Example 1, a vinyl chloride resin shown in Table 1 (vinyl chloride-ethylene copolymer manufactured by Tokuyama Sekisui Kogyo Co., Ltd., trade name "VE-T", polymerized A printing film was prepared in the same manner as in Example 1 except that the temperature was 1000 and the ethylene content was 8% by weight. The printing films obtained were evaluated as described below. Table 1 shows the results.
Shown in

[0076]

[Table 1]

Example 10 [Preparation of vinyl chloride graft polymerized elastomer]
7.5 kg of pure water was placed in a 15-liter reactor equipped with a stirrer and a jacket for temperature adjustment, and E was used in Example 2.
VA 1.49 kg, partially saponified polyvinyl alcohol as a dispersant (Kuraray Co., Ltd., trade name "Kuraray Povar L-
8 ", 300 g of a 3% by weight aqueous solution, and as a polymerization initiator, t
1 g each of -butylperoxydecanoate and α-cumylperoxydecanoate were added, and the air in the reactor was discharged by a vacuum pump, and then the vinyl chloride monomer was stirred.
8 kg was added, and the reactor was heated to 64 ° C. to start the graft polymerization reaction.

When the pressure in the reactor dropped to a pressure of 5.6 kgf / cm 2, it was confirmed that the conversion of the vinyl chloride monomer had reached 80% by weight, and the reaction was stopped.
After the termination of the reaction, unreacted vinyl chloride monomer was removed, and the polymer was dehydrated and dried to prepare an elastomer (60% by weight of vinyl chloride component) on which vinyl chloride was graft-polymerized.

In the same manner as in Example 1, 100 parts by weight of a vinyl chloride resin composition comprising 75% by weight of the obtained vinyl chloride-grafted elastomer and 25% by weight of the vinyl chloride resin used in Example 1 was processed. The following additives were added, and a printing film having a thickness of 120 μm was prepared by a calendar molding method. About the obtained printing film,
The following evaluation was performed. Table 2 shows the results.

Examples 11 to 17 The elastomers shown in Table 2 (same as the elastomers used in Examples 1 to 8) were used instead of the elastomer of Example 10 in preparing the vinyl chloride-grafted elastomer. Except for this, a printing film was produced in the same manner as in Example 10. The printing film obtained was evaluated as described below. The results are shown in Table 2.

[0081]

[Table 2]

Examples 18 to 25 Vinyl chloride resins obtained by adding the vinyl chloride graft-polymerized elastomers used in Examples 10 to 13 and the elastomers used in Examples 1 to 8 in the proportions and proportions shown in Table 3. To 100 parts by weight of the composition, the following additives were added in the same manner as in Example 1, and a printing film having a thickness of 120 μm was produced by a calender molding method. The printing films obtained were evaluated as described below. Table 3 shows the results.

[0083]

[Table 3]

Examples 26 to 29 The vinyl chloride graft-polymerized elastomers used in Examples 10 to 13 and the vinyl chloride graft-polymerized elastomers used in Examples 14 to 17 were blended in the proportions and proportions shown in Table 4. Added vinyl chloride resin composition 100
To the parts by weight, the following additives were added in the same manner as in Example 1 to produce a printing film having a thickness of 120 μm by a calender molding method. The following evaluation was performed about the obtained film for printing sheets. Table 4 shows the results.

Examples 30 to 33 Elastomers obtained by graft polymerization of vinyl chloride used in Examples 10 to 13, elastomers obtained by graft polymerization of vinyl chloride used in Examples 14 to 17 and Examples 1, 2 and
To 100 parts by weight of the vinyl chloride resin composition in which the elastomers used in Nos. 5 and 6 were added in the proportions and proportions shown in Table 4, the following additives as processing aids were added in the same manner as in Example 1, and calender molding was performed. A printing film having a thickness of 120 μm was produced by the method. About the obtained printing film,
The following evaluation was performed. Table 4 shows the results.

[0086]

[Table 4]

Examples 34 to 37 Vinyl chloride graft-polymerized elastomers used in Examples 10 to 13, vinyl chloride graft-polymerized elastomers used in Examples 14 to 17, Examples 1, 2, 5 and 6 To 100 parts by weight of the vinyl chloride resin composition obtained by adding the elastomer used and the vinyl chloride resin used in Example 1 at the compounding ratio and the compounding ratio shown in Table 5, the addition of the processing aid and the same as in Example 1 The agent was added, and a printing film having a thickness of 120 μm was prepared by a calendar molding method. The printing films obtained were evaluated as described below. Table 5 shows the results.

[0088]

[Table 5]

Example 38 [Preparation of Acrylic Copolymer (Emulsion Polymerization)] 4 kg of pure water was placed in a 10 liter reactor equipped with a stirrer and a reflux condenser.
24 g of ammonium persulfate (10% by weight aqueous solution) was added as a polymerization initiator, the inside of the vessel was replaced with nitrogen, and the temperature in the reactor was raised to 75 ° C. with stirring. 1.5 kg of pure water, 50 g of Hytenol N-08 (Daiichi Kogyo Seiyaku Co., Ltd.) as an emulsifier
(10% by weight aqueous solution), n-
Butyl acrylate (nBA, glass transition temperature Tg-5)
(4 ° C.) An emulsified monomer liquid prepared from 2.4 kg of 2.4 kg and 10 g of trimethylolpropane triacrylate (TMPA) as a polyfunctional monomer was dropped at a constant dropping rate into the reactor after the temperature was raised. Dropping of all emulsified monomer liquids was completed in 3.0 hours, and thereafter, stirring was continued for 1 hour, and then polymerization was terminated to obtain an acrylic copolymer latex having a solid content of 30% by weight. .

[Preparation of Vinyl Chloride Resin (Graft Copolymerization)] Then, 7.5 kg of pure water, 1.42 kg of the above acrylic copolymer latex (acryl copolymer) were placed in a 15 liter polymerization vessel equipped with a stirrer and a jacket. (Solid weight 0.43 kg), partially saponified polyvinyl alcohol (Kuraray Co., Ltd., Kuraray Povar L-8) as a dispersant
A 300% by weight aqueous solution, 1 g of t-butylperoxydecanoate as a polymerization initiator, and 1 g of α-cumylperoxydecanoate were added, and the air in the reactor was discharged by a vacuum pump. 0.8 kg was added. The temperature of the reactor was raised to 64 ° C. to initiate polymerization.

When the pressure in the polymerization vessel dropped to a pressure of 5.6 kgf / cm 2, it was confirmed that the conversion of the vinyl chloride monomer had reached 80%, and the reaction was stopped. Thereafter, the unreacted vinyl chloride monomer was removed, and further dehydration drying was performed to obtain a vinyl chloride resin.

[Preparation of Printing Film] In order to prepare a printing film, a printing film having a thickness of 120 μm was prepared in the same manner as in Example 1 using the above-mentioned vinyl chloride resin. The printing films obtained were evaluated as described below. Table 6 shows the results.

Example 39 The procedure of Example 38 was repeated, except that the graft polymerization was carried out so that the content of the acrylic polymer in the vinyl chloride resin was 40% by weight.
Was prepared. The printing films obtained were evaluated as described below. Table 6 shows the results.

Examples 40 to 47 A printing film having a thickness of 120 μm was prepared in the same manner as in Example 38 except that the type of the grafted elastomer was changed as shown in Table 6. The printing films obtained were evaluated as described below. Table 6 shows the results.

[0095]

[Table 6]

Examples 48 to 54 Example 3 except that the constituents of the grafted crosslinked acrylic copolymer or the contents thereof were changed as shown in Table 7.
In the same manner as in No. 8, a printing film having a thickness of 120 μm was produced. The printing films obtained were evaluated as described below. Table 7 shows the results.

[0097]

[Table 7]

Example 55 The ink receiving layer coating liquid containing polyacrylate as a main component was coated on the printing film obtained in Example 38 by a roll coater so that the dry coating amount was 6 g / m 2. , Dried and finally calendered to obtain a printing film. Both calender moldability and coatability were good. In order to evaluate the printability of the obtained film with an aqueous ink, a solid cyan image was printed on the receptor layer using a thermal inkjet type inkjet printer. The printability was good.

The abbreviations of the elastomers used in Tables 1 to 6 represent the following elastomers, respectively. AC: (meth) acrylic ester copolymer “KANEACE FM-21” (average particle diameter after dispersion of 0.1 to 1 μm,
AC1: Acrylic copolymer shown in Example 38 EVA1: Ethylene-vinyl acetate copolymer “Evaflex 45LX” (vinyl acetate content 45% by weight, MFR
EVA2: ethylene-vinyl acetate copolymer “Ultracene 634” (vinyl acetate content 26% by weight, MFR4,
EA: Ethylene-acrylate copolymer “Evaflex EEA A-709” (MFR25, manufactured by Du Pont-Mitsui Chemicals) NBR: Acrylonitrile-butadiene copolymer “JS
RPN30A ”(acrylonitrile content 35% by weight, ML1 + 4: 100 ° C. = 42, manufactured by Nippon Synthetic Rubber Co., Ltd.) CPE: chlorinated polyethylene“ Eraslen 351A ”
(Chlorine content 35% by weight, MFR2, manufactured by Showa Denko KK) MBS: Methyl methacrylate-butadiene-styrene copolymer “BTA-751” (average particle size after dispersion of 0.1 to 0.1)
CSPE: Chlorsulfonated polyethylene “Hypylon 40” (chlorine content 35% by weight, sulfur content 1.1)
(% By weight, ML1 + 4: 100 ° C. = 30, manufactured by Tosoh Corporation) PU: Polyurethane “Pandex 500E” (caprolactone-based, manufactured by Dainippon Ink Co., Ltd.).

Comparative Examples 1 to 3 As shown in Table 8, a predetermined amount of a plasticizer (dibutyl phthalate) was added to 100 parts by weight of the vinyl chloride resin used in Example 1. Using a vinyl chloride-based resin composition to which the following additives were added, a printing film having a thickness of 120 μm was produced by a calender molding method. The printing films obtained were evaluated as described below. Table 8 shows the results.

[0101]

[Table 8]

[Evaluation Methods] The surface properties and weather resistance, low-temperature impact resistance, weight change rate, and printability of the printing film having a thickness of 120 μm were evaluated as follows. (Surface properties) According to JIS K 6722, length 90
The two obtained films having a width of 60 mm and a width of 60 mm were faced to each other, and were sandwiched between two smooth glass plates having a length of 60 mm and a width of 60 mm each along with one side of the width of the test piece. A weight of 60 mm in length and width on the bottom surface and a weight of 3 kg was placed on this, left in an air oven at 50 ° C. for 24 hours, and then taken out. Then remove the weight and let cool at room temperature for 1 hour.
When the test pieces were gently peeled off, the degree of stickiness on the surface was evaluated in the following three grades by a sensory test by touching the surface of the obtained molded article. ○: almost no stickiness △; slight stickiness ×: clear stickiness This is caused when the film is kept unused for printing or when it is stored after printing. The evaluation was performed to evaluate the possibility of adhesion and peeling of the printed surface, and was evaluated as storage stability.

(Weather Resistance) A 15 mm × 25 mm test piece cut out from the obtained film was used. A super UV tester (manufactured by Iwasaki Electric Co., Ltd.) was used for the weather resistance test.
The test piece was irradiated with a black panel at a temperature of 53 ± 2 ° C. with an ultraviolet illuminance of 70 mW / cm 2 for 3 cycles of 12 hours of ultraviolet irradiation, 8 hours of rest, and 4 hours of condensation.
The tensile properties of the test piece before and after the test by the above-mentioned super UV tester were measured according to JIS K 6745, and the tensile strength after the test was 95 to 105% of the tensile strength before the test as the mechanical strength of the molded product. It was judged that there was sufficient weather resistance if there was. This is to evaluate how much the strength has changed from the initial material design due to the blooming of the plasticizer after the weather resistance test.

(Low-temperature impact resistance) test was conducted according to JIS K7
The test was performed in accordance with the multiaxial impact test method for carbon fiber reinforced plastic described in No. 085. HTM-
1 (manufactured by Shimadzu Corporation) was used. However, since the measurement sample was a film, the thickness of the film was 120 μm. The measurement temperature was set to 0 ° C. in order to evaluate the material properties at a low temperature. The impact speed was 3.0 m / s. The striker diameter used was 12.7 mm. The total absorbed energy obtained in this test indicates the entire enclosed area (shaded area) up to the maximum displacement at the time of penetration failure in the load-displacement diagram shown in FIG.

(Rate of change in weight) A test piece of 50 mm × 50 mm cut out from the obtained film was used. Preliminarily measure the weight of this test piece to four decimal places (initial weight)
The sample was left for 24 hours in a 70 ° C. air oven. After the standing, the weight of the test piece was measured, and the rate of weight change with respect to the initial weight was measured.

(Printability) In order to confirm the printability of the obtained film with oil-based ink, a solid cyan image was printed on each print film using an on-demand inkjet printer. These printed films were placed in an atmosphere of 60 ° C. and 90% RH for 3 hours.
After standing for 0 days, the degree of change of the image was evaluated as follows: ：: Normally, no blurring in the image, good image quality,
Δ: Three-stage sensory test: Normally, blurring was slightly observed in the image, and the image quality was slightly insufficient. ×: Normally, blurring was observed in the image, and the image quality was insufficient. The printability was evaluated by:

[0107]

The printing film of the present invention is made of a vinyl chloride resin containing an elastomer component, has no stickiness or change in physical properties due to blooming of a plasticizer, and has weather resistance, storage properties and printability. It can maintain stable performance for a long period of time even outdoors, and can be suitably used in applications exposed to the outdoors. In addition, the use of a specific elastomer further improves low-temperature impact resistance, and is suitable for winter construction.

[Brief description of the drawings]

FIG. 1 is a diagram showing a load-displacement line in a multiaxial impact test at 0 ° C., which is measured according to a multiaxial impact test method for carbon fiber reinforced plastic described in JIS K 7085.

 ──────────────────────────────────────────────────続 き Continuing on the front page F term (reference) 2H086 BA15 BA19 BA33 BA53 BA56 4F071 AA12 AA13 AA15X AA24 AA24X AA28X AA77 AA78 AA86 AE09 AH19 BC01 BC10 BC12 4J002 AC072 BB062 BB072 BB242 BB272 BD041 BG272

Claims (12)

[Claims] 1. A printing film comprising a vinyl chloride resin containing an elastomer component. 2. The content of the elastomer component is 10 to 10.
The printing film according to claim 1, wherein the content is 50% by weight. 3. A graft obtained by graft copolymerizing a vinyl monomer containing vinyl chloride as a main component with an elastomer component, a blend of an elastomer component and a vinyl chloride polymer, or an elastomer component. The printing film according to claim 1, wherein the printing film is any one of a blend of the polymer and the graft. 4. An elastomer comprising an ethylene-vinyl acetate copolymer, an ethylene- (meth) acrylate copolymer, an acrylonitrile-butadiene copolymer, a chlorinated polyethylene, a (meth) acrylate copolymer, The methyl methacrylate-styrene-butadiene copolymer, chlorosulfonated polyethylene, and at least one elastomer selected from the group consisting of polyurethane polymers, according to any one of claims 1 to 3, The printing film according to the above. 5. An elastomer comprising 100 parts by weight of an acrylic monomer component containing 50% by weight or more of an alkyl (meth) acrylate monomer having a glass transition temperature of a homopolymer of -140 to -20 ° C. and a polyfunctional monomer component 0 .0
The printing film according to any one of claims 1 to 4, which is a crosslinked acrylic copolymer obtained by copolymerizing 1 to 30 parts by weight. 6. The printing film according to claim 1, comprising a vinyl chloride resin and a pigment. 7. The thickness is 50 to 300 μm, and
Total absorption energy is 8J in multiaxial impact test at 0 ℃
The printing film according to claim 1, wherein: 8. The printing method according to claim 1, wherein a weight change rate before and after the standing is less than 5% when left in a constant temperature bath at 70 ° C. for 24 hours. For film. 9. The printing film according to claim 1, wherein the printing means is an ink jet printer. 10. The printing film according to claim 9, wherein the ink used in the inkjet printer is an oil-based ink comprising an oil-soluble dye solution. 11. A printing film according to claim 1, wherein an ink receiving layer is provided on at least one side of the printing film, and the printing means is an ink jet printer. 12. The printing film according to claim 11, wherein the ink used in the ink jet printer is an aqueous ink comprising a water-soluble dye and a medium mainly composed of water.