JP4633710B2 - Laminated film - Google Patents

Description

The present invention relates to a printing film, an overlaminating film, and a laminated film.

Conventionally, polyvinyl chloride films (PVC films) have been mainly used as indoor wall covering materials such as films and sheets for interior wallpaper. For the design of such a film, the surface of the monochromatic film or base printing film colored by adding a pigment in the polyvinyl chloride compound is given a design such as wood grain by gravure printing, etc. A means for laminating a clear film on the surface is widely used. Furthermore, in order to ensure the workability of the film on the wall, there are many film products that have a structure in which an adhesive layer and a separator layer are laminated on the back of the design film, and are used as high-grade wall covering films in buildings, stores, etc. Has been.

Recently, due to the diversification of design requirements, there is a growing demand for the use of individual designs output on demand as wall covering films. The film production using is increasing. As ink jet printers, water-based inks and solvent-based ink types are used. However, there is a high demand for applying designs with solvent-based inks from the viewpoint of production speed and durability. When a solvent-based ink is used, a PVC film is generally often used because the ink can be fixed by swelling the film layer itself with a solvent.

However, when a design is imparted to a PVC film using a solvent-based ink, the ink often bleeds or the color developability (color density) varies depending on the composition of the film. Specifically, in a blended system in which a large amount of a low molecular weight plasticizer (for example, DOP) is added, the plasticizer bleeds on the film surface over time, so that the bleed plasticity when contacting with solvent-based ink during printing. The fixing function on the film surface may be impaired due to mixing of the agent and the ink.

As a result, problems such as slow drying of the ink, bleeding of the ink, poor workability, and poor appearance may occur. Further, when the solvent is absorbed into the PVC film, the oily component migrates into the pressure-sensitive adhesive layer, so that the cohesive force of the pressure-sensitive adhesive layer is weakened and the pressure-sensitive adhesive properties are sometimes lowered. On the other hand, when the added amount of the plasticizer is too small, the swelling with the solvent-based ink is insufficient, so that the fixing of the ink may be poor.

Also, when affixing a design film to a substrate, it is often applied while rubbing the surface with a squeegee. At this time, an overlaminate film is laminated in order to prevent scratches, peeling, etc. on the printed surface. It is widely done. Further, by protecting with such an overlaminate film, it is possible to provide functions such as prevention from contamination such as dust and dust, and prevention (protection) of scratches due to scratches, etc. in actual use after construction.

When laminating an overlaminate film on the surface printed using the solvent-based ink described above, the solvent component permeates into the film through the adhesive layer of the overlaminate film, so the overlaminate film needs to have solvent resistance. . For this reason, when a large amount of oily components such as plasticizers are added, the film layer is extremely softened when the solvent is absorbed, and a large amount of oily components penetrate into the interface between the pressure-sensitive adhesive layer and the PVC film, causing the pressure-sensitive adhesive to aggregate. The force was weakened, and the physical properties of the adhesive were sometimes lowered.

Furthermore, when used for interior use, it is necessary to obtain non-combustibility certification from the Ministry of Land, Infrastructure, Transport and Tourism in the layered structure after the print overlaminating process [Article 68-26 of Building Standard Law, Paragraph 5 Performance evaluation according to regulations; issued by the Japan Building Research Institute * Fireproof and fireproof performance test / evaluation work method document 4.10 Nonflammability performance test / evaluation method (Performance evaluation according to Article 68-26, Paragraph 5 of the Building Standards Act) ]]. For this reason, it is also required to have such characteristics.

Patent Documents 1 and 2 describe the use of a polyvinyl chloride resin material and a plastic material as a material for a print medium for interior materials. Patent Documents 3 to 5 describe using a vinyl chloride resin as a material for a printing sheet. Patent Documents 6 to 7 describe interior sheets. However, in these documents, detailed examination is not performed on the relationship between the average degree of polymerization of polyvinyl chloride and the number average molecular weight of the plasticizer.
JP 2001-79974 A JP 2001-150660 A Japanese Patent Laid-Open No. 10-309764 Japanese Patent Laid-Open No. 11-43869 JP 2003-48378 A JP 2003-53868 A JP 2004-230883 A

In view of the current situation, the present invention is a printing film excellent in printability and adhesive physical properties, an overlaminating film excellent in adhesive physical properties used by being stuck on the printing surface of the printing film on which printing has been performed, And it aims at providing the laminated | multilayer film which was excellent also in nonflammability.

The present invention has a polyvinyl chloride film (A1) and an adhesive layer (A2), and the polyvinyl chloride film (A1) has 100 mass of polyvinyl chloride resin (2) having an average degree of polymerization of 700 to 1200. It is obtained using a resin composition (2) in which 15 to 35 parts by mass of a plasticizer (2) having a number average molecular weight of 380 to 2000 is blended with respect to parts, and printing is performed using a solvent-based ink. A film for printing;
It has a polyvinyl chloride film (B1) and an adhesive layer (B2), and the polyvinyl chloride film (B1) is based on 100 parts by mass of the polyvinyl chloride resin (3) having an average degree of polymerization of 700 to 1300. Overlaminate film obtained by using resin composition (3) containing 15 to 40 parts by mass of plasticizer (3) having a number average molecular weight of 380 to 3000
And
The polyvinyl chloride film (A1) has a thickness of 40 to 100 μm,
The pressure-sensitive adhesive layer (A2) has a thickness of 20 to 60 μm,
The polyvinyl chloride film (B1) has a thickness of 40 to 160 μm,
The pressure-sensitive adhesive layer (B2) has a thickness of 20 to 60 μm,
The total thickness is 240 μm or less,
The overlaminating film was laminated on the printing surface of the printing film,
Used for indoor wall coverings
It is the laminated film characterized by this.

In the laminated film, the plasticizer (2) preferably has a molecular weight of 390 to 435, more preferably 390 to 419. The plasticizer (2) is preferably a phthalic acid diester.
In the laminated film, the printing method is preferably a solvent-based inkjet printing method.
In the laminated film, the pressure-sensitive adhesive layer (A2) and the pressure-sensitive adhesive layer (B2) preferably contain an acrylic pressure-sensitive adhesive.
The laminated film preferably further has a separator layer (A3) on the pressure-sensitive adhesive layer (A2) side.
In the laminated film, the overlaminate film preferably has a total light transmittance of 80% or more in accordance with JIS K 7105.
Hereinafter, the present invention will be described in detail.

The printing film of the present invention comprises a resin composition (1) containing a specific amount of a polyvinyl chloride resin (1) having an average degree of polymerization of 1000 to 1400 and a polyester plasticizer (1) having a number average molecular weight of 1000 to 3000, or Polyvinyl chloride film (A1) obtained from a resin composition (2) containing a specific amount of a polyvinyl chloride resin (2) having an average degree of polymerization of 700 to 1200 and a plasticizer (2) having a number average molecular weight of 380 to 2000 Is to use. Thereby, the outstanding printability and the adhesive physical property can be obtained.

That is, at the time of printing, bleeding of the plasticizer is prevented and the film is sufficiently swollen by the solvent-based ink, so that excellent ink fixability can be obtained. Therefore, good drying property and color developability (color density) of the ink can be obtained, and deterioration of workability due to ink bleeding or the like can be prevented.

Furthermore, since the shift of the solvent in the solvent-based ink to the pressure-sensitive adhesive layer can be suppressed, it is possible to prevent a decrease in the pressure-sensitive adhesive properties. For this reason, it is possible to prevent the occurrence of adhesive residue on the base material to be attached, or to suppress the shrinkage of the film over time after being attached to the base material, thereby preventing the occurrence of a frame phenomenon.

The printing film of the present invention has a polyvinyl chloride film (A1) obtained by using the resin composition (1) or (2).
The resin composition (1) contains a polyvinyl chloride resin (1) having an average degree of polymerization of 1000 to 1400. By being within the above range, excellent printability and adhesive properties can be obtained. If it exceeds 1400, the calendar processability may be deteriorated. It is preferable that it is 1000-1300.

In this specification, the average degree of polymerization of a polyvinyl chloride resin means the average degree of polymerization measured based on JIS K-6721 "Test method of vinyl chloride resin".
Examples of the polyvinyl chloride resin (1) include vinyl chloride homopolymers and copolymers of vinyl chloride and other monomers copolymerizable therewith.
Examples of the other copolymerizable monomers include vinyl esters such as vinyl acetate and vinyl propionate, olefins such as ethylene, propylene, and styrene, methyl acrylate, ethyl acrylate, and methyl methacrylate. ) Acrylic acid esters, maleic acid diesters such as dibutyl maleate and diethyl maleate, fumaric acid diesters such as dibutyl fumarate and diethyl fumarate, vinyl cyanide such as acrylonitrile and methacrylonitrile, vinylidene chloride and vinyl bromide Examples thereof include vinyl ethers such as vinyl halide, methyl vinyl ether, and ethyl vinyl ether. These may be used alone or in combination of two or more.

The content of the other copolymerizable monomer in the copolymer is usually 50% by weight or less, preferably 10% by weight or less. If it exceeds 50% by weight, the bending resistance of the laminate may be reduced. Among the vinyl chloride resins, a vinyl chloride homopolymer is preferable because excellent printability and adhesive properties can be obtained.

As the above-mentioned polyvinyl chloride resin (1), ethylene vinyl acetate (EVA), styrene-ethylene-butylene-styrene (SEBS), styrene, which are elastic bodies, from the viewpoint of excellent physical properties of the polymer and bending resistance of the laminate. -What added isoprene-styrene (SIS), methyl methacrylate-butylene-styrene (MBS), a chlorinated polyethylene, etc. is preferable.

The resin composition (1) contains a polyester plasticizer (1) having a number average molecular weight of 1000 to 3000. By being within the above range, excellent printability and adhesive properties can be obtained. If it exceeds 3000, the plasticizer becomes difficult to be absorbed by the polyvinyl chloride resin, and the plasticizer plate-out occurs during calendering. It is preferable that it is 2500-3000.

In this specification, the number average molecular weight of a plasticizer is a measured value in terms of polystyrene by GPC (gel permeation chromatograph) measurement.
The GPC measurement method is performed according to a standard method. A dilute tetrahydrofuran solution of a plasticizer to be measured was prepared and measured using a GPC measuring device “HLC-8220GPC” manufactured by Tosoh Corporation under a flow rate condition of 0.6 ml / min. As the column, “KF606M” and “KF603” manufactured by Showa Denko KK were used.

The polyester plasticizer (1) can be used without particular limitation as long as it is compatible with the polyvinyl chloride resin (1). For example, polyethylene glycol diester of phthalic acid, Polyalkylene glycol diesters such as polypropylene glycol diester and polyethylene glycol polypropylene glycol diester, and polyalkylene glycol diesters such as polyethylene glycol diester of aliphatic dibasic acids such as adipic acid and sebacic acid, polypropylene glycol diester, polyethylene glycol polypropylene glycol diester, etc. It is preferable to use it. Especially, it is preferable to use the polyalkylene glycol diester of an aliphatic dibasic acid, and it is especially preferable to use the polyalkylene glycol diester of adipic acid from the point from which the outstanding printability and adhesive physical property are acquired. These plasticizers may be used alone or in combination of two or more.

In the resin composition (1), the content of the polyester plasticizer (1) is 20 to 40 parts by mass with respect to 100 parts by mass of the polyvinyl chloride resin (1). If it is less than 20 parts by mass, the average polymerization degree of the polyvinyl chloride resin (1) is high and the amount of the plasticizer is too small, so that the solvent-based ink is insufficiently swollen and into the polyvinyl chloride film (A1). The ink permeability of the ink is poor, and the drying property of the ink is poor. This phenomenon is because the solvent-based ink is not absorbed in the film, so that the ink is accumulated on the film surface, and it takes time to dry, and the solvent component in the ink volatilizes on the film surface. Inadequate adhesive strength.

On the other hand, when it exceeds 40 parts by mass, the plasticizer in the film bleeds on the surface over time, and when the solvent-based ink comes into contact, the oil component on the surface and the ink are mixed, and the ink hardly penetrates into the film layer. Become. In this state, since the ink and the liquid component are mixed, the ink absorptivity into the film layer is deteriorated, and the adhesive force between the ink and the film surface is weakened. Further, since the amount of the oily component present differs depending on the location on the film surface, the color developability of the ink varies, resulting in uneven density. Further, regarding the physical properties of the adhesive, the cohesive force decreases due to the transfer of the oily component and the solvent component to the adhesive layer, and the adhesive strength decreases. In addition, due to the decrease in cohesive strength of the pressure-sensitive adhesive layer and the inclusion of oily components between the pressure-sensitive adhesive layer and the film layer, the glue is transferred to the base material side when the film once attached to the base material is peeled off (residue remaining) ) Trouble occurs. Further, the cohesive force decreases, so that the adhesive strength is reduced, and the film is peeled off after being attached to the base material, and the shrinkage of the polyvinyl chloride film (A1) cannot be suppressed. It is preferable that it is 25-35 mass parts.

The resin composition (2) contains a polyvinyl chloride resin (2) having an average degree of polymerization of 700 to 1200. By being within the above range, excellent printability and adhesive properties can be obtained. If the molecular weight is less than 700, the molecular weight becomes small and the solvent swells excessively. It is preferable that it is 800-1000.

As said polyvinyl chloride resin (2), the thing similar to the polyvinyl chloride resin (1) mentioned above can be mentioned. Among these, a vinyl chloride homopolymer is preferable from the viewpoint that excellent printability and adhesive properties can be obtained.

The resin composition (2) contains a plasticizer (2) having a number average molecular weight of 380 to 2,000. By being within the above range, excellent printability and adhesive properties can be obtained. If it is less than 380, bleeding from the film occurs. If it exceeds 2000, plate-out occurs.

The plasticizer (2) can be used without particular limitation as long as it is compatible with the polyvinyl chloride resin (2). For example, the above-mentioned polyester plasticizer (1) and The same can be mentioned. Further, phthalic acid dioctyl (di-2-ethylhexyl phthalate (DOP)), dibutyl phthalate, phthalic acid diester such as dinonyl phthalate, dioctyl adipate, aliphatic dibasic acid diesters such as dioctyl sebacate, tricresyl Phosphate triesters such as phosphates and trioctyl phosphates, epoxy plasticizers such as epoxidized soybean oil and epoxy resins, and the like can also be used. Especially, it is preferable to use the polyalkylene glycol diester of an aliphatic dibasic acid, and it is especially preferable to use the polyalkylene glycol diester of adipic acid from the point from which the outstanding printability and adhesive physical property are acquired. It is also preferable to use DOP. These plasticizers may be used alone or in combination of two or more.

In the resin composition (2), the content of the plasticizer (2) is 15 to 35 parts by mass with respect to 100 parts by mass of the polyvinyl chloride resin (2). If it is less than 15 parts by mass, the drying property of the ink may be deteriorated. If it exceeds 35 parts by mass, the ink absorptivity into the film layer and the adhesive force between the ink and the film surface may be reduced. In addition, density unevenness may occur, adhesive strength may decrease, and adhesive residue may occur. It is preferable that it is 25-35 mass parts.

The resin compositions (1) and (2) preferably contain a stabilizer. Examples of the stabilizer include metal soaps such as fatty acid calcium, fatty acid zinc, and fatty acid barium, and hydrotalcite. Examples of the fatty acid component of the metal soap include calcium laurate, calcium stearate, calcium ricinoleate, zinc laurate, zinc ricinoleate, zinc stearate, barium laurate, barium stearate, and barium ricinoleate. it can. In addition, as the stabilizer, epoxy stabilizer, barium stabilizer, calcium stabilizer, tin stabilizer, zinc stabilizer; calcium-zinc (Ca-Zn), barium-zinc (Ba) Composite stabilizers such as —Zn-based ”can also be used.

In the resin compositions (1) and (2), a colorant generally used for a polyvinyl chloride resin can be blended, if necessary, within a range not impairing the effects of the present invention.
Examples of the colorant include titanium oxide, zinc oxide, carbon black, nigrosine dye, aniline blue, carlo oil blue, chrome yellow, ultramarine blue, dupont oil red, quinoline yellow, methylene blue chloride, phthalocyanine blue, and malachite green oxa. Rate, mixtures thereof, and the like. A colored film is obtained by using the colorant.

In the resin compositions (1) and (2), lubricants, modifiers, fillers, dilutions generally used for polyvinyl chloride resins are used as necessary, as long as the effects of the present invention are not impaired. You may add additives, such as an agent and a foaming agent.

The polyvinyl chloride film (A1) preferably has a thickness of 40 to 180 μm. If it is less than 40 μm, printability and tensile properties may be deteriorated. If it exceeds 180 μm, the flexibility and nonflammability of the film may be reduced. More preferably, it is 50-100 micrometers.

The polyvinyl chloride film (A1) can be produced by calendar molding, extrusion molding, injection molding or the like. Of these, those obtained by calendar molding are preferred. The resin compositions (1) and (2) are excellent in calendar workability, and can prevent the occurrence of problems such as plate-out and splayed irregularities during the calendar process. Examples of the calendar format used for the calendar molding include an inverted L shape, a Z shape, an upright two shape, an L shape, and an inclined three shape.

The printing film has an adhesive layer (A2). Thereby, it becomes possible to affix a film on an indoor wall suitably. The pressure-sensitive adhesive layer (A2) is provided on one side of the polyvinyl chloride film (A1).

The pressure-sensitive adhesive layer (A2) can be formed by using a conventionally known pressure-sensitive adhesive. For example, the pressure-sensitive adhesive layer (A2) can be formed by using an acrylic pressure-sensitive adhesive or a rubber pressure-sensitive adhesive.

The acrylic pressure-sensitive adhesive is composed of an acrylic polymer, and examples of the acrylic polymer include a homopolymer of (meth) acrylic acid alkyl ester or a copolymer thereof. it can. As alkyl in the said (meth) acrylic-acid alkylester, C4-C12 linear or branched alkyl is preferable.

Examples of the rubber adhesive include polyisobutylene / polybutene, styrene / diene / styrene block copolymer, styrene / butadiene, nitrile, chloroprene, vinylpyridine, polyisobutylene, butyl, isoprene, A rubber-based pressure-sensitive adhesive made of isobutylene or the like can be mentioned. Among the above-mentioned pressure-sensitive adhesives, it is preferable to use an acrylic pressure-sensitive adhesive.

The thickness of the pressure-sensitive adhesive layer (A2) is preferably 20 to 60 μm. If it is less than 20 μm, the cohesive force is insufficient, so that the target adhesive force may not be achieved. If it exceeds 60 μm, not only the adhesive strength becomes too high, but also the cohesive failure of the pressure-sensitive adhesive layer may occur when it is peeled off from the substrate. In addition, there is a risk that wrinkles will occur during re-stretching. More preferably, it is 20-40 micrometers.

The printing film having the pressure-sensitive adhesive layer (A2) preferably further has a separator layer (A3). The separator layer (A3) protects the pressure-sensitive adhesive layer (A2) until the film is attached, and is peeled off at the time of attachment. In this case, examples of the printing film include those obtained by laminating a polyvinyl chloride film (A1), an adhesive layer (A2), and a separator layer (A3) in this order.

Examples of the separator layer (A3) include high-density base paper such as glassine paper, clay-coated paper, craft paper, or high-quality paper, casein, dextrin, starch, carboxymethylcellulose, methylcellulose, ethylcellulose, hydroxyethylcellulose, polyvinyl alcohol, Mainly composed of natural or synthetic resin such as styrene-butadiene copolymer, methyl methacrylate-butadiene copolymer, ethylene-vinyl chloride copolymer, ethylene-vinyl acetate copolymer, acrylate ester copolymer, and pigment. Sheets provided with a sealing layer; Laminated paper obtained by laminating polyethylene or the like on kraft paper or high-quality paper; Water, solvent-type or useless-type silicone resin or fluorine resin, etc. on sheets such as polypropylene Usually 0.05 by dry mass 3 g / m ² after coating, thermosetting, may be used such as those formed with the separator layer by electron radiation curing and the like. Especially, the film etc., such as a polypropylene processed with the silicone resin, can be used suitably from an environmental viewpoint.
The pressure-sensitive adhesive layer (A2) and separator layer (A3) can be formed by a conventionally known coating method or the like.

The printing film of the present invention is printed using a solvent-based ink. Printing is performed on the polyvinyl chloride film (A1) surface of the printing film.
The solvent-based ink was obtained by dissolving a colorant and other components (for example, resin used for the purpose of improving the dispersibility of the pigment, preventing clogging of the head, adjusting the viscosity, etc.) in an organic solvent. Is.

Examples of the colorant used in the solvent-based ink include quinacridone, anthraquinone, perylene, perinone, diketopyrrolopyrrole, isoindolinone, condensed azo, benzimidazolone, monoazo, Organic pigments such as insoluble azo, naphthol, flavanthrone, anthrapyrimidine, quinophthalone, pyranthrone, pyrazolone, thioindigo, anthanthrone, dioxazine, phthalocyanine, indanthrone; nickel dioxin yellow, Examples thereof include metal complexes such as copper azomethine yellow, metal oxides such as titanium oxide, iron oxide and zinc oxide, metal salts such as barium sulfate and calcium carbonate, and inorganic pigments such as carbon black.

Organic solvents used in the above solvent-based inks are alcohols such as ethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, and dipropylene glycol; ethylene glycol mono (methyl) to prevent head drying and clogging. , Ethyl, butyl, phenyl, benzyl, ethylhexyl) ether, ethers such as ethylene glycol di (methyl, ethyl, butyl) ether; diethylene glycol di (methyl, ethyl, butyl) ether acetate, propylene glycol mono (methyl, ethyl, butyl) ) Ether acetate, dipropylene glycol mono (methyl, ethyl) ether acetate, tripropylene glycol monomethyl ether acetate, 2- (methoxy, ethoxy, butoxy) It can be mentioned ketones such as cyclohexanone; chill acetate, 2-ethylhexyl acetate, dimethyl phthalate, diethyl phthalate, esters such as butyl lactate. Especially, since the outstanding printability and adhesive physical property are acquired, it can apply suitably for the printing using the solvent-type ink containing an ester-type organic solvent.

The printing film of the present invention can be suitably applied to a solvent-based inkjet printing method. In this case, excellent printability and adhesive properties can be obtained. The solvent-based ink jet printing method is a printing method in which fine solvent-based ink is ejected from a nozzle of a head.

The printing film of the present invention is used for indoor wall coverings. In this case, the (separator layer (A3)) is peeled off as necessary, and the pressure-sensitive adhesive layer (A2) is attached to the wall and used as wallpaper or the like.

The overlaminating film of the present invention is used by being stuck on the printing surface of the above-described printing film on which printing has been performed. That is, when printing is performed on the polyvinyl chloride film (A1) of the printing film by a printing method such as a solvent-based inkjet printing method, the adhesive for the overlaminating film is formed on the printed surface (printing surface). The layer (B2) is pasted and laminated for use. The overlaminating film of the present invention is a film that is surface-protected by laminating on the printing film.

The overlaminate film is a polychlorinated resin obtained from a resin composition (3) in which a specific amount of a polyvinyl chloride resin (3) having an average degree of polymerization of 700 to 1300 and a plasticizer (3) having a number average molecular weight of 380 to 3000 are blended. A vinyl film (B1) is used. Thereby, the outstanding adhesive physical property can be obtained.

That is, since the solvent in the solvent-based ink can be prevented from penetrating into the overlaminating film through the pressure-sensitive adhesive layer (B2) of the overlaminating film, it is possible to prevent the deterioration of the adhesive physical properties. For this reason, generation | occurrence | production of the adhesive residue in the printing film to stick can be prevented, or the shrinkage | contraction of an overlaminating film can be suppressed with time after sticking to a printing film, and generation | occurrence | production of a frame phenomenon can be prevented.

The overlaminating film of the present invention has a polyvinyl chloride film (B1) obtained by using the resin composition (3).
The resin composition (3) contains a polyvinyl chloride resin (3) having an average degree of polymerization of 700 to 1300. By being within the above range, excellent adhesive properties can be obtained. If it is less than 700, the same problem as when the average degree of polymerization of the polyvinyl chloride resin (2) is less than 700 occurs. It is preferable that it is 800-1100.

As said polyvinyl chloride resin (3), the thing similar to the polyvinyl chloride resin (1) mentioned above can be mentioned. Among these, a vinyl chloride homopolymer is preferable from the viewpoint that excellent adhesive properties can be obtained.

The resin composition (3) contains a plasticizer (3) having a number average molecular weight of 380 to 3000. By being within the above range, excellent printability and adhesive properties can be obtained. When it is less than 380, when it exceeds 3000, the same problem as when the number average molecular weight of the plasticizer (2) is less than 380 and exceeds 2000 occurs.

The plasticizer (3) can be used without particular limitation as long as it is compatible with the polyvinyl chloride resin (3). For example, the plasticizer (3) is the same as the plasticizer (2) described above. Things can be mentioned. Especially, it is preferable to use the polyalkylene glycol diester of an aliphatic dibasic acid, and it is especially preferable to use the polyalkylene glycol diester of adipic acid from the point from which the outstanding adhesive physical property is obtained. It is also preferable to use DOP. These plasticizers may be used alone or in combination of two or more.

In the resin composition (3), the content of the plasticizer (3) is 15 to 40 parts by mass with respect to 100 parts by mass of the polyvinyl chloride resin (3). When the content is in the above range, after overlaminating, remarkable softening due to penetration of the solvent into the film and reduction in cohesive force of the adhesive layer (B2) (decrease in adhesive strength) can be suppressed. When the amount is less than 15 parts by mass, the film can be softened and the adhesive properties can be maintained well, but the workability is low due to creases remaining at the time of bonding to the base material and poor followability to the curved surface shape. May be worse. If the amount exceeds 40 parts by mass, the film may be softened and the cohesive strength of the pressure-sensitive adhesive layer may be reduced (decrease in the adhesive strength) after overlaminating.

The resin composition (3) preferably contains the same stabilizer as the resin compositions (1) and (2) described above. In addition, the resin composition (3) may contain additives such as the above-described colorants, lubricants, modifiers, fillers, diluents, foaming agents and the like as long as they do not impair the effects of the present invention. May be added.

The polyvinyl chloride film (B1) preferably has a thickness of 40 to 160 μm. If it is less than 40 μm, the tensile properties may deteriorate. If it exceeds 160 μm, the flexibility and nonflammability of the film may be reduced. More preferably, it is 50-100 micrometers.

The polyvinyl chloride film (B1) can be produced by the same method as the polyvinyl chloride film (A1) described above. Especially, it is preferable that it is what is obtained by the said calendar molding. The resin composition (3) is excellent in calendar workability and can prevent the occurrence of problems such as plate-out and cascading irregularities during calendar processing.

The overlaminate film has a pressure-sensitive adhesive layer (B2). Thereby, it becomes possible to affix the overlaminating film on the said printing film suitably. The pressure-sensitive adhesive layer (B2) is provided on one side of the polyvinyl chloride film (B1).

The pressure-sensitive adhesive layer (B2) can be formed by using a conventionally known pressure-sensitive adhesive. For example, the pressure-sensitive adhesive layer (B2) can be formed by using the above-mentioned acrylic pressure-sensitive adhesive or rubber pressure-sensitive adhesive. it can. Especially, it is preferable to use an acrylic adhesive.

The thickness of the pressure-sensitive adhesive layer (B2) is preferably 20 to 60 μm. If it is less than 20 μm, the cohesive force is insufficient, so that the target adhesive force may not be achieved. If it exceeds 60 μm, not only the adhesive strength becomes too high, but also the cohesive failure of the pressure-sensitive adhesive layer may occur when it is peeled off from the substrate. Moreover, there exists a possibility that cost may become high. More preferably, it is 20-40 micrometers.

The overlaminating film having the pressure-sensitive adhesive layer (B2) preferably further has a separator layer (B3). The separator layer (B3) protects the pressure-sensitive adhesive layer (B2) until the film is pasted, and is peeled off when pasting. In this case, examples of the overlaminate film include a laminate of a polyvinyl chloride film (B1), an adhesive layer (B2), and a separator layer (B3) in this order.

As said separator layer (B3), the thing similar to the separator layer (A3) mentioned above can be used, for example. Especially, the film etc., such as a polypropylene processed with the silicone resin, can be used suitably from an environmental viewpoint.
The pressure-sensitive adhesive layer (B2) and separator layer (B3) can be formed by a conventionally known coating method or the like.

The overlaminate film preferably has a total light transmittance of 80% or more in accordance with JIS K 7105. When it has such a characteristic, the design of the printing film already printed can fully be visually recognized. If it is less than 80%, the designability may be impaired. More preferably, it is 90% or more. By setting the amount of the pigment component added to the polyvinyl chloride resin (3) to 0.5 parts by mass or less, a total light transmittance of 80% or more can be obtained. The total light transmittance is a value measured using an overlaminate film composed of the polyvinyl chloride film (B1) and the pressure-sensitive adhesive layer (B2).

The laminated film of the present invention is obtained by laminating the above-described overlaminating film on the printing surface of the above-described printing film on which printing has been performed. Therefore, since the laminated film is excellent in printability and adhesive properties, it can be suitably used as an indoor wall covering material (wallpaper or the like). The laminated film can be produced by sticking and laminating the pressure-sensitive adhesive layer (B2) of the overlaminating film on the printing surface of the printed printing film by a known method. Examples of the laminated film include those obtained by laminating the polyvinyl chloride film (B1), the adhesive layer (B2), the polyvinyl chloride film (A1), and the adhesive layer (A2) in this order. .

The laminated film preferably has a total thickness of 240 μm or less. Thereby, since the component which a film burns can be reduced, favorable nonflammability can be obtained and the satisfactory result can be obtained in a fire-proof performance test. The total thickness is the thickness of the entire laminated film, and is a laminate of the polyvinyl chloride film (B1), the pressure-sensitive adhesive layer (B2), the polyvinyl chloride-based film (A1), and the pressure-sensitive adhesive layer (A2). In some cases, it is the total thickness of (A1), (A2), (B1) and (B2). The total thickness is more preferably 200 μm or less.

Hereinafter, examples of the printing film, overlaminating film, and laminated film of the present invention will be described with reference to FIGS.
FIG. 1 is a schematic view of a printing film in which a polyvinyl chloride film 1, an adhesive layer 2, and a separator layer 3 are laminated in this order. FIG. 2 is a schematic view of an overlaminating film in which a polyvinyl chloride film 4, an adhesive layer 5 and a separator layer 6 are laminated in this order. Since the printing film and the overlaminating film have the above-described configuration, the printing film is excellent in printability and adhesiveness, and the overlaminating film is excellent in adhesiveness. FIG. 3 is a schematic view of a laminated film in which a polyvinyl chloride film 4, an adhesive layer 5, a film 7 printed on the polyvinyl chloride film 1 and an adhesive layer 2 are laminated in this order. This indicates a film in which the pressure-sensitive adhesive layer (B2) side of the overlaminating film is laminated on the print surface of the printed printing film, and the pressure-sensitive adhesive layer 2 can be used by sticking it to a substrate such as a wall. it can.

Since the printing film of the present invention has the polyvinyl chloride film (A1) obtained from the resin composition (1) or (2) and the pressure-sensitive adhesive layer (A2), printability and adhesion Excellent physical properties. Moreover, since the film for overlaminating of this invention has a polyvinyl chloride film (B1) obtained from the said resin composition (3), and an adhesive layer (B2), it is excellent in adhesive physical property. Yes. In addition, the resin compositions (1), (2), and (3) are excellent in calendar workability, and prevent the occurrence of problems such as plate-out and scalloped irregularities during calendar processing. Can do. Furthermore, since the laminated film of the present invention is obtained by laminating the overlaminating film on the printed surface of the printed film, printing properties and adhesive properties are excellent.

EXAMPLES Hereinafter, although an Example is hung up and demonstrated in more detail, this invention is not limited only to these Examples. In the examples, “parts” and “%” mean “parts by mass” and “% by mass” unless otherwise specified.

Examples 1-10 and Comparative Examples 1-9
By the following methods, a printing film, an overlaminating film, and a laminated film were produced and evaluated.
The commercially available polyester plasticizer used is as follows.
Polyester plasticizer (adipic acid type) number average molecular weight 1200; “PN-7230” (Asahi Denka Kogyo Co., Ltd.)
Polyester plasticizer (adipic acid type) number average molecular weight 1900; “PN-280” (Asahi Denka Kogyo Co., Ltd.)
Polyester plasticizer (adipic acid type) number average molecular weight 2600; "PN-7535" (Asahi Denka Kogyo Co., Ltd.)
Polyester plasticizer (adipic acid type) number average molecular weight 3000; “PN-350” (Asahi Denka Kogyo Co., Ltd.)

[Preparation of printing film with adhesive]
A PVC compound was prepared with the composition shown in Table 1, stirred for 15 minutes with a blender, and then sheeted with a reverse L-shaped calendar roll. The thickness and specifications are shown in Tables 2 and 3.
The pressure-sensitive adhesive layer was formed on a silicon-treated surface of a paper separator (“SLK • 80WK” manufactured by Sumika Kogyo Co., Ltd.) with an acrylic pressure-sensitive adhesive solution (100 parts by weight of “SK Dyne 1506” manufactured by Soken Chemical Co., Ltd.). 3 parts by mass of the mixed solution) was applied with a comma bar coater, the solvent was dried in a drying furnace, a 20 μm pressure-sensitive adhesive layer was formed, the PVC film was bonded, and the pressure-sensitive adhesive was applied to the PVC film side. The layer was transferred and wound with a paper separator attached. Unnecessary portions of both ears were slit at both ears to obtain a printing film as a 20 m roll.

[Evaluation of printing film]
(1) Solid printing with an ink ejection amount of 100 to 400% was performed with a printable solvent-based ink jet printer (“IP-6500” manufactured by Seiko Instruments Inc., ester lactate (lactic acid) solvent ink). Ink absorbability, drying property, and color developability were evaluated by the following methods. These evaluations were performed on samples immediately after film sheeting and on samples left in a gear oven at 60 ° C. for 7 days for evaluation of aging acceleration.
(Ink absorption)
○: Ink does not bleed.
X: Ink blots.
(Drying)
○: After 20 minutes of printing, the back separator surface is brought into contact with the printed portion and pressed from above, so that ink does not adhere to the separator surface.
X: Ink is attached.
(Color development)
○: The ink density is uniform and uniform.
X: Ink density unevenness.

(2) Physical properties of adhesive (initial adhesive strength)
Conforms to JIS Z0237. A solid printed film with an ink ejection amount of 200% is pasted on an aluminum substrate and left for 24 hours in an environment of 23 ± 2 ° C. and 60% RH, and then a tensile test (23 ± 2 ° C., tensile speed 300 mm / min) Thus, the adhesive strength and the adhesive remaining state on the substrate were visually evaluated.
Target level: Adhesive strength of 10 N / 25 mm or more ○: No adhesive residue on the base material is generated.
X: Adhesive residue on the substrate is generated.
(Adhesive strength over time)
Conforms to JIS Z0237. The film with pressure-sensitive adhesive is left in a gear oven at 60 ° C for 7 days, and after taking out, printing is performed with a solvent-based ink jet printer with an ink ejection amount of 200%, and the film is attached to an aluminum plate, 23 ± 2 ° C, 60% RH After being allowed to stand for 24 hours in this environment, the adhesive strength and the state of adhesive remaining on the substrate were visually evaluated by a tensile test (23 ± 2 ° C., tensile speed 300 mm / min).
Target level: Adhesive strength 8 N / 25 mm or more ○: No adhesive residue on the substrate.
X: Adhesive residue on the substrate is generated.

(3) Calendar processability Regarding the calendar processability during the production of the printing film, two items of plate-out and film smoothness were evaluated according to the following criteria.
i) Plate-out o: Plate-out to calendar roll did not occur.
X: Plate out to calendar roll occurred.
ii) Film smoothness ◯: The surface state is uniform and smooth.
X: There are irregularities on the surface due to shading and insufficient temperature.

[Production of overlaminate film]
A PVC compound was prepared with the composition shown in Table 1, stirred for 15 minutes with a blender, and then sheeted with a reverse L-shaped calendar roll. The thickness and specifications are shown in Tables 2 and 3.
The pressure-sensitive adhesive layer is formed on the silicon-treated surface of a paper separator (Sumika Kogyo Co., Ltd. “SLK / 80WK”) with an acrylic pressure-sensitive adhesive solution (“SK Dyne 1570” manufactured by Soken Chemical Co., Ltd.) in 100 parts by mass. -45E "(mixed solution with 1.33 parts by mass added) was applied with a comma bar coater, and after drying the solvent in a drying furnace, a 20 μm pressure-sensitive adhesive layer was formed, and a PVC film was bonded together. The pressure-sensitive adhesive layer was transferred to the film side and wound up with a paper separator attached. Unnecessary portions of both ears were slit at both ears to obtain a film for overlaminate as a roll of 20 m.

[Evaluation of overlaminate film]
(1) Total light transmittance Based on JISK7105, the total light transmittance (%) of the film for overlaminates which consists of a PVC film and an adhesive layer was measured.
(2) Physical properties of adhesive (adhesive strength)
Conforms to JIS Z0237. After laminating an overlaminating film on the surface of a solid-printed film with an ink jetting amount of 200% and leaving it in an environment of 23 ± 2 ° C. and 60% RH for 24 hours, the printed surface and the overlaminating film adhesive layer The adhesion between the layers is evaluated by a tensile test (23 ± 2 ° C., tensile speed 300 mm / min).
Target level: Adhesive strength 15 N / 25 mm or more.
(3) Calendar processability The calendar processability at the time of production of the overlaminating film was evaluated according to the same criteria as the above-mentioned printing film.

[Production of laminated film (overlaminating film / printing film)]
The obtained film for overlaminating and the film for printing were laminated at room temperature using a laminator to obtain a laminated film.

[Evaluation of laminated film]
(Non Flammable)
Issued by Japan Architectural Comprehensive Testing Laboratory Fireproof and fireproof performance test / evaluation work method manual 4.10 In the evaluation by the nonflammability performance test / evaluation method, the following i), ii) and iii) were evaluated.
i) The total calorific value for 20 minutes after the start of heating is 8 MJ / m ² or less.
ii) 20 minutes after the start of heating, there should be no cracks or holes penetrating to the back side, which is harmful to fire prevention.
○: There are no cracks and holes penetrating to the back surface.
X: There are cracks and holes penetrating to the back surface.
iii) 20 minutes after the start of heating, the maximum heat generation rate should continue for 10 seconds or more and not exceed 200 KW / m ² .
A: The maximum heat generation rate does not exceed 200 KW / m ² continuously for 10 seconds or more.
X: The maximum heat generation rate continuously exceeds 200 KW / m ² for 10 seconds or more.

[Workability]
(Folded wrinkle mold)
The paper separator of the printing film cut into 200 mm square is peeled off and attached to a galvanized steel sheet, and the film is peeled off from the substrate immediately after. At this time, whether or not the folded mold remained in the film layer was visually evaluated.
○: No bent mold remains.
X: A folded mold remains.
(Curved surface processing)
A 200 mm square laminated film was affixed to a plastic substrate having a height of 5 mm, a length of 100 mm square, and a cubic curved surface with a corner portion 50R, and the suitability along the corner portion was visually evaluated.
○: Floating at the corner, no wrinkles, etc., and evenly adhered to the substrate.
×: Floating at the corner, wrinkled, etc.

From Tables 2 and 3, the printing films obtained in the examples had excellent printability and adhesive properties, and the overlaminate films had excellent adhesive properties and total light transmittance. Moreover, it had the outstanding calendar workability at the time of film preparation. Furthermore, the laminated films obtained in the examples were excellent in nonflammability and workability. On the other hand, those obtained in Comparative Examples were not obtained with all these characteristics being good.

In the printing film, overlaminating film, and laminated film of the present invention, the overlaminating film can be suitably used as an indoor wall covering material (wallpaper or the like).

It is an example of the schematic of the film for printing of this invention. It is an example of the schematic of the film for overlaminating of this invention. It is an example of the schematic of the laminated | multilayer film of this invention.

Explanation of symbols

1, 4 Polyvinyl chloride film 2, 5 Adhesive layer 3, 6 Separator layer 7 Film printed on polyvinyl chloride film 1

Claims (8)

It has a polyvinyl chloride film (A1) and an adhesive layer (A2), and the polyvinyl chloride film (A1) is based on 100 parts by mass of the polyvinyl chloride resin (2) having an average degree of polymerization of 700 to 1200. A printing film obtained by using a resin composition (2) containing 15 to 35 parts by mass of a plasticizer (2) having a number average molecular weight of 380 to 2000, and printed using a solvent-based ink; ,
It has a polyvinyl chloride film (B1) and an adhesive layer (B2), and the polyvinyl chloride film (B1) is based on 100 parts by mass of the polyvinyl chloride resin (3) having an average degree of polymerization of 700 to 1300. An overlaminating film which is obtained using a resin composition (3) containing 15 to 40 parts by mass of a plasticizer (3) having a number average molecular weight of 380 to 3000,
The polyvinyl chloride film (A1) has a thickness of 40 to 100 μm,
The pressure-sensitive adhesive layer (A2) has a thickness of 20 to 60 μm,
The polyvinyl chloride film (B1) has a thickness of 40 to 160 μm,
The pressure-sensitive adhesive layer (B2) has a thickness of 20 to 60 μm,
The total thickness is 240 μm or less,
Laminating the overlaminating film on the printing surface of the printing film,
A laminated film characterized by being used for indoor wall coverings. The laminated film according to claim 1 , wherein the plasticizer (2) has a molecular weight of 390 to 435. The laminated film according to claim 1 , wherein the plasticizer (2) has a molecular weight of 390 to 419. The laminated film according to any one of claims 1 to 3, wherein the plasticizer (2) is a phthalic acid diester. The laminated film according to any one of claims 1 to 4, wherein the printing method is a solvent-based inkjet printing method. The laminated film according to any one of claims 1 to 5, wherein the pressure-sensitive adhesive layer (A2) and the pressure-sensitive adhesive layer (B2) contain an acrylic pressure-sensitive adhesive. The laminated film according to any one of claims 1 to 6, further comprising a separator layer (A3) on the pressure-sensitive adhesive layer (A2) side. The laminated film according to any one of claims 1 to 7, wherein the overlaminate film has a total light transmittance of 80% or more based on JIS K 7105.

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