JP2002096412A - Printing film material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a film material for ink jet printing which uses recycled polyester resins, contains fabric materials, has strong mechanical strengths and is inexpensive. SOLUTION: An ink receiving layer is formed at least on one side of a fiber base cloth containing 50 wt.% or more of recycled polyester fibers. A weight ratio of the ink receiving layer to the total weight is controlled to a range of 5-25%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a film material for printing which is excellent in printability, in particular, printability by an ink jet printer, and is suitable for applications such as indoor / outdoor signboards, banners, curtains, wall materials, and interior decoration materials. It is.

[0002]

2. Description of the Related Art Polyester resins represented by polyethylene terephthalate have excellent mechanical properties, heat resistance, and moldability, and are widely used as raw materials for molded articles such as textiles, films, and bottles for drinking water. It is used for various purposes, and its production volume is enormous. These products are generally disposed of or landfilled or incinerated after use, but recently, efforts have been made to recycle resources for the purpose of reducing adverse effects on the environment.

Under these circumstances, polyethylene terephthalate bottles for drinking water (so-called PET bottles) have a large production volume and a separate collection system. It is attracting attention as a material that is being recycled. However, although the recycled polyester resin made from these has the advantage of low cost, it is not used as the raw material of the original drinking water bottle with a large production volume due to safety and health problems, and its use is carpet and some Since it is limited to textile raw materials for apparel, further expansion of its use is required for the purpose of promoting the reuse of resources.

[0004] In recent years, ink jet printers have attracted attention as means for producing indoor / outdoor signboards, banners, wall coverings, interior decorations, and the like. Wide format printers having a printing width of more than 1 m have emerged, and furthermore, remarkable progress has made it possible to obtain output quality approaching that of silver halide photography. As a recording medium used in an ink jet printer,
Various printing sheets (or printing film materials) such as paper, plastic films, and fabrics have been provided. On these surfaces, for example, a method using polyvinylpyrrolidone and polyvinyl butyral as in JP-A-57-102391, or a method using ultrafine anhydrous silica and a cationic polymer as in JP-A-2-188287. A special surface treatment layer called an ink receiving layer is formed by a method or the like. This ink receiving layer quickly absorbs ink droplets ejected from the printer, thereby obtaining good printability.

[0005] Such printing sheets are often made of paper or plastic film as a base material in applications where they are attached to walls or panels, such as decorative materials.
In applications such as banners and outdoor signboards, they may be fluttered by the wind or fluttered or stretched under tension, so they are likely to be folded and wrinkled. A film material for printing on a fabric base made of polyester fiber or the like having excellent degree characteristics is selected. However, printing materials using a fabric substrate include:
There is a problem that the cost is very high as compared with a printing sheet made of paper or a plastic film substrate.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a film material for printing including a fabric base material which has a low production cost while expanding the use of fibers produced from recycled polyester resin. Things.

[0007]

The printing film material of the present invention comprises:
A composite comprising a fiber base fabric and a printing ink receiving layer formed on at least one surface thereof, wherein the weight ratio of the ink receiving layer to the total weight of the composite is 5 to 25%, and 5% of the total weight of the composite
It is characterized by containing 0% or more of recycled polyester fiber.

[0008]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The fiber base fabric used in the printing membrane material of the present invention is a fabric made of polyester (such as polyethylene terephthalate) fiber, or a used polyester resin bottle, a polyester resin packaging material, and a polyester resin. A recycled polyester fiber (hereinafter, referred to as a recycled polyester fiber) recycled using flakes and / or pellets of waste generated from a waste route in a product manufacturing process; The weight ratio of the recycled polyester fiber in the cloth is at least 50%, preferably at least 70%. If the weight ratio of the recycled polyester fiber is less than 50%, sufficient cost merit cannot be obtained, and it is not preferable from the viewpoint of resource reuse, and therefore, the object of the present invention cannot be achieved.

[0009] The fibers in the fiber base fabric may be in any shape, such as spun short fiber yarn, long fiber yarn, split yarn, and tape yarn. Further, the base fabric structure may be any of a woven fabric, a knitted fabric, a nonwoven fabric or a composite thereof. There is no particular limitation on the knitting structure of the base fabric, but, for example, coarse knitted woven fabric composed of yarns including at least a warp and a weft arranged in parallel with a gap between yarns,
And non-coarse knitted fabrics (knitted fabrics in which substantially no gap is formed between yarns). The basis weight of coarse fabric is 30-7
00 g / m ² , and the open area ratio of the coarse knitted fabric is 10 to 10 with respect to the entire surface area of the coarse knitted fabric.
It is preferably about 95%. When the fiber base fabric is a non-coarse knitted fabric, its structure, basis weight, thickness, etc. are not limited, but depending on the purpose of use, knitted fabrics such as plain weave, twill weave, circular knit, weft knit, and warp knit. And the basis weight is preferably about 50 to 1000 g / m ² .

There is no particular limitation on the strength of the base cloth used in the film agent of the present invention. For example, when the base material is used for an expanded film material such as a large area tent or an internally illuminated signboard, the ink receiving layer The tensile strength after formation is 392N / 3cm (40kgf
/ 3 cm) or more. For the purpose of imparting water resistance and water absorption prevention properties, these fiber base fabrics may be previously prepared using, for example, a wax emulsion, a wax emulsion containing a resin binder, an emulsion of a silicone-based compound, or a solution of these. The above may be subjected to a water-repellent pretreatment by spraying or dipping.

The printing film material of the present invention has a printing ink receiving layer formed by appropriately combining a pigment, a binder, a cationic polymer and the like. Pigments that can be used in the ink receiving layer include calcium carbonate, magnesium carbonate, kaolin, talc, calcium sulfate, barium sulfate, titanium oxide, zinc oxide, zinc sulfate, zinc carbonate, satin white, aluminum silicate, diatomaceous earth, and zeolite. , Inorganic fine particles such as sepiolite, calcium silicate, magnesium silicate, silica, aluminum hydroxide, alumina, lithopone, or styrene plastic pigment, acrylic plastic pigment, microcapsules, urea resin pigment, melamine resin pigment, cellulose powder, collagen Organic fine particles such as powder and silk protein powder can be used.

These pigments may be used alone or as a mixture. In particular, it is preferable to use silica or calcium carbonate. As the silica, a synthetic amorphous silica produced by a wet precipitation method or a gel method is preferably used. The calcium carbonate may be either heavy calcium carbonate or light calcium carbonate.
When these pigments are added to the ink receiving layer, the ink absorbency is improved, and in addition, the blocking of the ink receiving layer can be suppressed. When a pigment having a large oil absorption is used, the ink absorbency is further improved, which is more preferable. Although there is no particular limitation on the particle size of the pigment used, it is preferable to use a pigment not exceeding 20 μm. If the particle size exceeds 20 μm, the coating strength of the ink receiving layer may be reduced and the smoothness may be insufficient.

[0013] Binders that can be used in the ink receiving layer include starches such as oxidized starch and etherified starch, cellulosics such as carboxymethylcellulose and hydroxyethylcellulose, and natural or semi-synthetic water-soluble compounds such as casein, gelatin and soy protein. Polymers: polyvinyl alcohol and its derivatives, polyethylene oxide, acrylic acid, maleic anhydride,
Synthetic water-soluble polymers such as polyacrylamide, polyvinylpyrrolidone, and polyamine; acrylate, polyamide, polyurethane, polyester,
Synthetic polymers such as polyvinyl butyral, epoxy and polyolefin; styrene-butadiene copolymer,
Conjugated diene polymer latexes such as methyl methacrylate-butadiene copolymer; acrylic polymer latexes such as acrylic acid ester and methacrylic acid ester polymer or copolymer; vinyl such as ethylene-vinyl acetate copolymer Polymer latexes; and functional group-modified polymers obtained by imparting a functional group such as a cationic group, a silanol group, or a silyl group to these various polymers can be used. These binders may be used alone or as a mixture. Among the above binder polymers, those obtained by using an ethylene-vinyl acetate copolymer or a urethane-based resin in combination with a water-soluble resin such as polyvinyl alcohol or polyvinylpyrrolidone are preferred.

As the cationic polymer used in the ink receiving layer, a polymer or copolymer containing a primary, secondary and tertiary amino group and a quaternary ammonium group as the cationic group can be used. . Examples thereof include polyethyleneimine salts, dimethylamine epihalohydrin condensates, polyvinylamine salts, polyallylamine salts, polydiallylamine salts, salts of polyalkylenepolyamines, polydiallyldimethylammonium salts, and salts of polydiallylamine-acrylamide copolymers. . In particular, dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate,
Cationic monomers having a tertiary amino group such as N, N-dimethylaminoethyl (meth) acrylamide and N, N-dimethylaminopropyl (meth) acrylamide are polymerized alone or copolymerized with other copolymerizable monomers. A polymer obtained by reacting a diol, a triol, a diamine or a triamine compound having a tertiary amino group with a polyol compound and a diisocyanate compound to neutralize the urethane polymer with an acid, or Cationic polymers quaternized with an agent are preferred. Examples of the acid used at this time include organic acids such as formic acid, acetic acid, propionic acid, butyric acid, lactic acid, and citric acid, and inorganic acids such as hydrochloric acid, phosphoric acid, phosphorous acid, and nitric acid. Examples of the quaternizing agent include ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin,
Use of epoxy compounds such as epipromohydrin, or sulfates such as dimethyl sulfate, diethyl sulfate, and methyl p-toluenesulfonate, or alkyl halides such as methyl chloride, ethyl chloride, benzyl chloride, methyl bromide, and ethyl bromide. Can be.

The amounts of the pigment, binder and cationic polymer in the ink receiving layer of the printing film material of the present invention are as follows:
Based on 100 parts by weight of the binder, 10 to 200 parts by weight of the pigment and 30 parts by weight or less of the cationic polymer, and the mixing ratio thereof depends on the type of the ink to be used (for example, an aqueous dye ink or a solvent-based pigment ink). Is adjusted appropriately. Further, a curing agent may be added to the ink receiving layer for the purpose of increasing the film strength of the ink receiving layer. Examples of the curing agent include isocyanate-based, carbodiimide-based, epoxy-based, melamine-based, oxazoline-based, and zirconium-based curing agents, and are appropriately selected according to the type of binder used in the ink receiving layer. Surfactants, water repellents, fungicides, antibacterials, ultraviolet absorbers, light stabilizers, antioxidants, flame retardants, fluorescent brighteners, colorants, dispersants, thickeners in the ink receiving layer An additive known in the art, such as an agent, may be used in combination. Further, the ink receiving layer may be formed by laminating two or more ink receiving layers having different compositions.

The amount of the ink receiving layer attached to the printing film material of the present invention is 5 to 25% of the total weight of the fiber-based fabric ink receiving layer composite. If the attached amount is less than 5%, the ink absorbency becomes insufficient, so that the value of use as a film material for printing is lost. If it exceeds 25%, the ink is absorbed too deeply by the ink receiving layer, and the color developability is reduced, and in addition, it is disadvantageous in terms of cost.

In the printing film material of the present invention, an adhesive layer can be provided if necessary for the purpose of improving the adhesion between the ink receiving layer and the fiber base fabric. Adhesives that can be used for forming the adhesive layer include melamine, phenol, epoxy, polyester, polyethyleneimine, polyisocyanate, oxazoline, polyurethane, acrylic, polyamide, and ethylene-acetic acid. Vinyl copolymer adhesives, etc.,
It is appropriately selected according to the type of the binder used for the ink receiving layer.

In the printing film material of the present invention, a method for forming an ink receiving layer on a fiber base fabric includes a blade coater, an air knife coater, a knife coater, a roll coater, a curtain coater, a bar coater, a gravure coater, and a comma coater. Etc. are available. Alternatively, a dip-nip method in which a base cloth is impregnated with a coating liquid and then squeezed with a mangle roll may be used.

The ink jet printing ink will be described as a typical example of the printing ink used in the printing film material of the present invention. The ink jet printing ink may be any of a water-based ink, an oil-based ink, and a solvent-based ink. Good.
The aqueous ink referred to here is one containing water and a water-soluble organic solvent as main components as a dispersion solvent of a dye or a pigment. Water-soluble organic solvents include diethylene glycol,
Polyhydric alcohols such as polyethylene glycol and glycerin, polyalkylene oxides, N-methyl-2-
Wetting agents for aqueous inks such as pyrrolidone, N-ethyl-2-pyrrolidone, pyrrolidones such as N-vinylpyrrolidone, and ethylene glycol monomethyl ether;
And penetrants for aqueous inks such as glycol ethers such as diethylene glycol monomethyl ether. The amount of the water-soluble organic solvent to be added to water is preferably in the range of 5 to 60% based on the total weight of the aqueous ink. In addition, various additives such as a pH adjuster, a surfactant, an oxygen scavenger, a conductivity-imparting agent, an aqueous polymer dispersant, a chelating agent, an antifoaming agent and an antiseptic / antifungal agent are added to the aqueous ink composition as required. May be added.

The oil-based ink is an ink mainly containing gas oil, naphtha, or a non-water-soluble organic solvent having a boiling point of 150 ° C. or higher as a pigment dispersion solvent.
The solvent-based ink is an ink mainly containing an organic solvent having a boiling point of 150 ° C. or lower, such as cyclohexane, acetone, methyl ethyl ketone, or a carboxylic acid ester, as a pigment dispersion solvent. The composition of the oil-based ink and the solvent-based ink includes colorants such as dyes (oil-soluble dyes), carbon black, and organic pigments, and phenol resins, acrylic resins, maleic resins, rosin resins, and epoxy resins as binder resins. A thermoplastic resin such as a resin and a butyral resin is used, and if necessary, additives such as a surfactant, an antioxidant, an ultraviolet absorber, a conductivity imparting agent, and an antiseptic / antifungal agent may be added.

Examples of the dye used as a colorant for the ink-jet ink include known dyes such as natural dyes and synthetic dyes, for example, nitroso, nitro, azo, stilbene, diphenylmethane, triarylmethane, quinoline, and the like. Examples include methine, polymethine, thiazole, indamine, indophenol, azine, oxazine, thiazine, aminoketone, oxyketone, anthraquinone, indigoid, and phthalocyanine dyes.

On the other hand, examples of the pigment include known pigments such as organic pigments and inorganic pigments such as azo, phthalocyanine, quinacridone, anthraquinone, dioxazine, indico, benzidine, thioindico, perinone, Examples include isoindolinone-based, titanium oxide, cadmium-based, iron oxide-based, and carbon black-based pigments.

The printing film material of the present invention is not limited to ink-jet printing, but can be gravure-printed, screen-printed, or offset-printed using a printing ink such as an aqueous ink or an oil-based ink. As these printing inks, known printing inks composed of pigments, binders, and auxiliaries can be used. As the aqueous ink, a colorant component of an organic pigment, an inorganic pigment, a binder resin component such as a water-soluble resin, a colloidal dispersion, an emulsion, and a latex, a plasticizer, a film softener such as a softener, ammonia, Water-soluble agents such as water-soluble amines, and other additives such as friction resistance improvers, pigment dispersants, anti-separation agents, defoamers, thickeners, anti-settling agents, leveling agents, matting agents, etc. In addition, those obtained from a drying property adjusting agent such as water, alcohols, and glycols can be used.

As the organic pigments and inorganic pigments, conventionally known pigments such as azo, phthalocyanine, quinacridone, anthraquinone, dioxazine, indico, benzidine, thioindico, perinone, perylene, Examples include pigments of isoindolinone type, titanium oxide, cadmium type, iron oxide type, carbon black type and the like. As the pigment used in the production of these aqueous printing inks, the above-mentioned organic pigments and raw pigments composed of powder or press cake of inorganic pigments may be used, but the organic pigments and inorganic pigments may be used. Is an aqueous dispersion of a pigment in which water is dispersed using a nonionic or anionic surfactant as a dispersant, an easily water-dispersible pigment obtained by applying a surface treatment coat of a pigment with a hydrophilic resin, or a pigment and a resin. It is particularly preferable to use a processed pigment composed of colored chips that have been formed into pieces and chips by using the present roll in terms of workability, color development stability, and hue stability.

Examples of the water-soluble resin include natural products such as starch, dextrin and alginates, natural product derivatives such as hydroxyethyl cellulose and carboxymethyl cellulose, polyvinyl alcohol, polyvinyl amine, polyvinyl methyl ether, polyacrylamide, polyethylene oxide, and the like. Examples include synthetic resins such as sodium polyacrylate and dimethylaminoethyl methacrylate. These water-soluble resins can be used together as an auxiliary mainly for the purpose of adjusting the viscosity and fluidity of the ink, and dispersing and fixing the pigment. As the colloidal dispersion, for example, a shellac resin, a styrenated shellac resin, a styrene-maleic acid copolymer resin, a rosin-maleic acid resin, an acrylate or a methacrylate obtained by copolymerization with an unsaturated carboxylic acid. Carboxyl group-containing alkali-soluble acrylic copolymer resin and the like. Among them, a shellac resin can be used by dissolving in a water-alcohol mixed system and aqueous ammonia, and a styrene-maleic acid copolymer resin has an acid value of Approximately 170-350, softening temperature of 130-170 ° C can be water-soluble in the presence of ammonia and water-soluble amines (monoethanolamine, dimethylethanolamine, morpholine, etc.), or can be converted to alcohol, glycol ether, etc. Can be used after being dissolved, and ink film is possible Unsaturated fatty acids such as oleic acid, is the addition of polyethylene glycol and its derivatives preferred as agents. The carboxyl group-containing alkali-soluble acrylic copolymer resin has an acid value of 150 to 200 and a softening temperature of 100.
〜150 ° C. can be used in the presence of ammonia and a water-soluble amine, or can be used after being solubilized in alcohol, glycol ether, or the like. DBP, DOP, DOA, DBS , DOS
It is preferable to add a plasticizer commonly used in the field of soft PVC. As the emulsion, for example, acrylic resin, vinyl acetate resin, styrene resin, emulsion polymerization resin such as vinyl chloride resin,
Examples include emulsifying resins such as polyurethane resins, polyester resins, alkyd resins, epoxy ester resins, and rosin ester resins. Examples of the latex include styrene-butadiene-based resin, acrylonitrile-butadiene-based resin, methyl methacrylate-butadiene-based resin, polychloroprene, polyisoprene, and vinylidene chloride-based resin. Among them, as the resin binder of the aqueous printing ink, an acrylic resin emulsion can be preferably used, and in particular, an emulsion polymerization of a monomer selected from one or more of acrylic acid, methacrylic acid, acrylate, methacrylate and the like. Acrylic resin emulsion obtained and other monomers copolymerizable with these monomers, for example, styrene, vinyl acetate, acrylonitrile, N-methylol acrylamide, acrylic resin obtained by emulsion copolymerization with glycidyl methacrylate and the like Copolymer emulsions and the like can be preferably used. In order to improve the fluidity, leveling property, and gloss of the ink, an appropriate amount of the above-mentioned colloidal dispersion can be blended and used in combination with these acrylic copolymer resin emulsions. As plasticizers for softening ink films, DBP, DO
In addition to plasticizers widely used in the field of soft PVC such as P, DOA, DBS, and DOS, butyl carbitol, triethyl citrate, p-toluenesulfonamide, and tall oil fatty acid can be used.

As the oil-based ink, a colorant component of an organic pigment or an inorganic pigment, a binder resin component, a plasticizer,
Softeners and other softening agents for coatings, and other improvers for friction resistance,
Those composed of additive components such as a pigment dispersant, an anti-separation agent, an antifoaming agent, a thickener, an anti-settling agent, a leveling agent, a matting agent and a solvent component, or a water component can be used. As the organic pigment and the inorganic pigment, conventionally known pigments, for example, insoluble azo, soluble azo, copper phthalocyanine, quinacridone, anthraquinone, dioxazine, indigo, benzidine, thioindico, perinone, Examples of organic pigments such as perylene-based, isotondrinone-based, and polyazo-based pigments and inorganic pigments include titanium oxide, calcium carbonate, barium sulfate, cadmium-based, iron oxide-based, and carbon black-based pigments.

As the binder resin component, polyurethane resin, polyester resin, polyamide resin (condensate of dimer acid and diamine), acrylic resin, vinyl acetate resin, ethylene-vinyl acetate copolymer resin, vinyl chloride -Vinyl acetate copolymer resin, polyvinyl butyral resin, chlorinated polypropylene resin (chlorination degree 2
5 to 65% by weight), nitrocellulose, cellulose esters, cellulose ethers, cured rosin (metal salt with abietic acid), dimerized rosin, rosin ester, rosin-modified maleic resin, rosin-modified fumaric resin, rosin-modified Phenolic resin, ketone resin, terpene resin,
Cyclic rubber, chlorinated rubber and the like can be mentioned, and those using these resins in combination can be used.

Examples of the solvent used for the oil-based ink include n
Hydrocarbon solvents such as -hexane, n-heptane, cyclohexane, toluene and xylene; ester solvents such as methyl acetate, ethyl acetate and isopropyl acetate; acetone, methyl ethyl ketone and methyl isobutyl ketone;
Examples thereof include ketone solvents such as cyclohexanone, alcohol solvents such as methanol, ethanol, and isopropyl alcohol, and polyhydric alcohol derivative solvents such as methyl cellosolve and ethyl cellosolve. These solvents can be used in combination.

[0029]

The present invention is further described by the following examples. The test items used for evaluating the performance of the printing film material of the present invention are as follows.

[0030] 1. An ink-on-demand type ink-jet printer (Pentel Corporation model: PRP-2) in which a piezo-type head is mounted on a test printing film material on which an ink- jet printable ink receiving layer is formed.
2; water-based ink, manufactured by Pentel Co., Ltd., trademark: Dyna
jetII: oil-based ink, solvent-based ink), and filled with an ink for an inkjet printer having the composition shown in Table 1 for printing. At this time, printability with an aqueous ink, printability with an oil-based ink, and printability with a solvent ink were performed. Was independently evaluated. The output resolution in printing is 360d
Under the control of pi, a landscape photograph image was drawn, and the ink absorbency and the ink coloring property were evaluated. <Ink Absorbability> Printing was performed using the above-described inkjet printer, and the drying speed of the ink was evaluated by touching with a finger. Those dried within 30 seconds are indicated by “◎”, those dried within 1 minute are indicated by “○”, those dried within 2 minutes are indicated by “△”, and those dried over 2 minutes are indicated by “×” did. <Coloring property> The print density of the image printed by the above-mentioned ink jet printer was evaluated on a three-point scale of "very dark", "dark", and "light".
Indicated by “O” and “X”.

[0031]

[Table 1]

[0032]

[Table 2]

[0033]

[Table 3]

[0034] 2. A water-based ink (trademark: Tent Art (black), made by Turner Color) and an oil-based ink (trademark: Sericol PPE (911 Ink), manufactured by Teikoku Ink Manufacturing Co., Ltd.) Using a 225 mesh screen, a stripe pattern (alternate continuous pattern of a 5 mm-width linear printing portion and a 5 mm-width non-printing portion) was printed for each of the samples, and the transfer state of the ink was observed. "○" indicates that the ink transfer state is uniform, "X" indicates that the ink transfer state is not uniform
And

[0035] 3. Anti-fold wrinkle, anti-breaking length 30 cm, horizontal 20 cm wide test piece of printing film material with metal eyelets punched into the four corners and stretched and fixed to the film material support through a rope Was exposed outdoors and the state after one month was observed. Those having no wrinkles or tears were marked with "O", and those having broken wrinkles or tears were marked with "x".

Example 1 A non-coarse plain woven fabric consisting of 100% recycled polyester resin spun yarn having the following weaving structure was used as a fiber base fabric. This non-mesh fabric has a weight of 200 g /
At m ² , the tensile strength in the warp direction was 1230 N / 3 cm. (Polyester non-coarse plain fabric) 295 dtex × (20 English count) / 2 × 295 dtex × (20 English count) / 2） ５８ 58 x 49 (book / 25.4mm)

A coating liquid for an ink receiving layer having the following composition was prepared. (Coating liquid for ink receiving layer) Polyvinyl alcohol 100 parts by weight (trademark: PVA117, manufactured by Kuraray, saponification degree: 99%) Amorphous synthetic silica 80 parts by weight (trademark: Fine Seal X-30, precipitated silica, average) Secondary particle diameter: 3.2 μm, manufactured by Tokuyama) 50 parts by weight of diallyldimethylammonium chloride polymer (14 parts by weight in terms of solids) (trademark: PAS-H-5L, manufactured by Nitto Boss, solids: 28% by weight) 600 parts by weight of ion-exchanged water The above-mentioned coating liquid for an ink receiving layer is applied to one surface of the fiber base fabric by a knife coater, and dried at 140 ° C. for 2 minutes to form an ink receiving layer adhesion layer of 30 g / m ^2. Was prepared. The weight ratio of the ink receiving layer is 30 / (200
+30) × 100 = 13%. Table 4 shows the test results of the obtained film material for printing.

Example 2 In the same manner as in Example 1, a film material for printing was produced. However, instead of the diallyldimethylammonium chloride polymer, the diallyldimethylammonium chloride / acrylamide copolymer (trademark: PAS-J-) was used as the cationic polymer.
81, manufactured by Nitto Bo, solid content: 25% by weight) was added in an amount of 14 parts by weight in terms of nonvolatile components. Table 4 shows the test results of the obtained film material for printing.

Example 3 In the same manner as in Example 1, a film material for printing was produced. However, instead of the diallyldimethylammonium chloride polymer, 14 parts by weight of a polyethylenepolyamine-based compound (trade name: IJC-2, manufactured by Nikka Chemical Co., Ltd., solid content: 70% by weight) in terms of nonvolatile content was added as the cationic polymer. . Table 4 shows the test results of the obtained film material for printing.

Example 4 A film material for printing was produced in the same manner as in Example 1. However, instead of the diallyldimethylammonium chloride polymer, a copolymer of vinylpyrrolidone and methacrylamidopropyltrimethylammonium salt (trade name: GAFQUAT HS-100, manufactured by ISP, solid content: 20% by weight) is used as the cationic polymer. 14 parts by weight in terms of minutes were added. Table 4 shows the test results of the obtained film material for printing.

Example 5 A film material for printing was produced in the same manner as in Example 1. However, as the cationic polymer, dimethylaminoethyl methacrylate quaternary ammonium salt (trademark: PCQ-1, manufactured by Senka, solid content: 20% by weight) was used instead of the diallyldimethylammonium chloride polymer in an amount of 14 parts by weight in terms of nonvolatile content. Was added. Table 4 shows the test results of the obtained film material for printing.

Example 6 A printing film material was produced in the same manner as in Example 1. However, the blending amount of polyvinyl alcohol used as a binder is 1
00 parts by weight to 20 parts by weight, and an ethylene-vinyl acetate copolymer latex (trade name: Sumikaflex 75)
2. Sumitomo Chemical Co., Ltd., vinyl acetate content: 90% by weight,
(Solid content: 50% by weight) was added in an amount of 80 parts by weight in terms of nonvolatile content. Table 4 shows the test results of the obtained film material for printing.

Example 7 A printing film material was produced in the same manner as in Example 1. However, instead of polyvinyl alcohol, 100 parts by weight of a urethane-based emulsion (trade name: IJR-7, manufactured by Nikka Chemical Co., Ltd., solid content: 40% by weight) was added in terms of nonvolatile matter. The amount of ion-exchanged water was changed from 600 parts by weight to 200 parts by weight. Table 4 shows the test results of the obtained film material for printing.

Example 8 In the same manner as in Example 1, a film material for printing was produced. However, the silica used as the pigment was changed to one having an average secondary particle diameter of 8 μm (trade name: Mizukasil P-78D, gel method silica, manufactured by Mizusawa Chemical Industry). Table 4 shows the test results of the obtained film material for printing.

Example 9 In the same manner as in Example 1, a film material for printing was produced. However, instead of silica, 20 parts by weight of colloidal silica having an average particle diameter of 45 nm (trade name: Snowtex 20L, manufactured by Nissan Chemical Industries, solid content: 20% by weight) was added as a pigment. Table 4 shows the test results of the obtained film material for printing.

Example 10 A printing film material was produced in the same manner as in Example 1. However, an alumina sol in which alumina hydrate having a pseudo-boehmite structure is formed instead of silica as a pigment (trade name: alumina sol 520, manufactured by Nissan Chemical Industries, solid content: 2
1% by weight) was added in an amount of 40 parts by weight in terms of solid content. Table 4 shows the test results of the obtained film material for printing.

Example 11 A printing film material was produced in the same manner as in Example 1. However, silica used as a pigment was replaced with acrylic porous fine particles (trademark: Matsumoto Microsphere, average particle size:
3 μm, manufactured by Matsumoto Yushi). Table 4 shows the test results of the obtained film material for printing.

Example 12 In the same manner as in Example 1, a film material for printing was produced. However, 5 parts by weight of a melamine resin (trade name: Sumireze Resin 613, manufactured by Sumitomo Chemical Co., Ltd., solid content: 80) as a cross-linking agent was added to the ink receiving layer coating liquid. Table 4 shows the test results of the obtained film material for printing.

Example 13 In the same manner as in Example 1, a film material for printing was produced. However, the composition of the ink receiving layer coating liquid was changed to the following composition. Table 4 shows the test results of the obtained film material for printing. (Coating liquid for ink receiving layer) 100 parts by weight of polyvinylpyrrolidone (trademark: K-90, manufactured by ISP) 50 parts by weight of diallyldimethylammonium chloride polymer (14 parts by weight in terms of solid content) (trademark: PAS-H- 5L, manufactured by Nitto Bo, solid content: 28% by weight)

Example 14 In the same manner as in Example 1, a film material for printing was produced. However, the adhesion amount of the ink receiving layer was set to 50 g / m ² . The weight ratio was 50 / (200 + 50) × 100 = 20%. Table 4 shows the test results of the obtained film material for printing.

Comparative Example 1 A film material for printing was produced in the same manner as in Example 1. However, a non-coarse plain woven fabric made of 100% virgin polyester short fiber spun yarn (the woven structure is the same as in Example 1)
Changed to

Comparative Example 2 In the same manner as in Example 1, a film material for printing was produced. However, the adhesion amount of the ink receiving layer was set to 80 g / m ² . The weight ratio was 80 / (200 + 80) × 100 = 28.6%. Table 4 shows the test results of the obtained film material for printing.

Comparative Example 3 In the same manner as in Example 1, a film material for printing was produced. However, the adhesion amount of the ink receiving layer was 6 g / m ² . Its weight ratio was 6 / (200 + 6) × 100 = 2.9%. Table 4 shows the test results of the obtained film material for printing.

Comparative Example 4 A printing film material was prepared in the same manner as in Example 1. However, a recycled polyester resin film (thickness: 100 μm, weight: 140 g / m ² ) was used in place of the fiber base cloth, and a printing film material having an ink receiving layer adhesion amount of 30 g / m ² was produced by a bar coater. Table 4 shows the test results of the obtained film material for printing.

[0055]

[Table 4]

As is clear from Table 4, the printing film material of the present invention was excellent in printability with respect to an ink jet printer, not only small in environmental load, but also good in anti-fold wrinkling property and anti-breaking property. . The screen printability was also good.

[0057]

Industrial Applicability The printing film material of the present invention is excellent in printability, anti-folding property and tear resistance while being inexpensive, so that it can be used as a printing film material for indoor and outdoor signs, banners, curtains,
It can be suitably used for applications such as wall covering materials and interior decoration materials. Also, since a large amount of recycled polyester fiber is used, P
It is suitable for use as a polyester resin that is regenerated by recycling ET bolts, and has an unprecedented advantage that the environmental load can be reduced from the viewpoint of resource reuse.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) D06P 3/52 D06P 3/56 3/56 5/00 DBC 5/00 DBC 104 104 111A 111 B41J 3/04 101Y F-term (reference) 2C056 EA13 FB03 FC06 2H086 BA01 BA15 BA22 4F100 AK21 AK41A AR00B BA02 CC00 DG11A DG12 EH462 EJ862 GB08 HB31B JD14B JL16A 4H057 AA01 BA81 DA01 CA02 BA03 DA06 CA06 AB03

Claims (1)

[Claims] 1. A composite comprising a fiber base fabric and a printing ink receiving layer formed on at least one surface thereof, wherein the weight ratio of the ink receiving layer to the total weight of the composite is 5 to 25%. And the fibrous base fabric contains 50% or more of recycled polyester fiber by total weight of the composite.