JP4396501B2 - Biodegradable printed film material - Google Patents

Description

  The present invention relates to a biodegradable printing film material that is preferably printed by inkjet and used for pops, posters, and large banners, has high printability and flexibility, and is disposed of after disposal in the soil. The present invention relates to a biodegradable printing film material suitably used as a printing substrate that is biodegradable and is friendly to the global environment.

Inkjet printing is a method of printing ink on a printing substrate as a fine jet stream. There is also recent technological innovation, and the image / image quality and printing speed comparable to silver halide photographs are improved, and printing on the surface of a CD-ROM or the like is possible. Applications are expanding rapidly and are becoming the standard for printing methods. As a printing substrate used for inkjet printing, paper such as natural paper or synthetic paper, a resin film made of polyvinyl chloride or polyester, and a nonwoven fabric made of polypropylene fiber or polyester fiber (Patent Document 1) are known. ing. A printing substrate other than paper has a low ability to adsorb ink to the printing substrate itself, so that it is difficult to produce a clear image quality. Therefore, a printing base material on which an ink receiving layer using a cationic resin or an inorganic material is formed is also known. Such a printing substrate has a short period of use and is discarded, and those made of wood such as paper have an adverse effect on the global environment, such as deforestation. In particular, printing substrates using polyvinyl chloride and synthetic resin products have the problem of waste as industrial waste, and in particular, polyvinyl chloride products generate any harmful gases during incineration. It is not configured with consideration for the global environment. Further, the quaternary ammonium salt type cationic resin generally used as an ink receiving layer is not biodegradable, and the ink receiving layer does not decompose even if it is attached to a biodegradable sheet. It was insufficient as a biodegradable printing substrate.
JP 2003-96687 A

  An object of the present invention is to provide a biodegradable printed film material that is biodegradable and has excellent recording characteristics and flexibility in view of the background of the prior art.

The present invention employs the following means in order to solve such problems. That is, the biodegradable printed film material of the present invention is an ink comprising a biodegradable resin composition containing an inorganic substance and a water-absorbing resin having an average particle size of 10 to 50 μm on at least one side of a fiber fabric having biodegradability. A biodegradable printed film material comprising a receiving layer laminated thereon.
According to a preferred aspect of the biodegradable printed film material of the present invention, the inorganic substance is silica, and the silica is contained in an amount of 20 to 80% by weight based on the biodegradable resin. In the product, the water-absorbing resin is contained in an amount of 20 to 70% by weight based on the biodegradable resin, and the biodegradable plasticizer is contained in an amount of 10 to 50% by weight based on the biodegradable resin.

According to the preferable aspect of the biodegradable printed film material of the present invention, the amount of the biodegradable resin composition attached to the fiber fabric is 20 to 100 g / m ² .
According to a preferred aspect of the biodegradable printed film material of the present invention, the fiber constituting the fiber fabric contains 0.1 to 5 wt% of fatty acid amide, and the fiber constituting the fiber fabric. The total carboxyl terminal concentration is 10 equivalent / t or less.
According to a preferred embodiment of the biodegradable printed film material of the present invention, the fiber fabric is composed of polylactic acid fibers to which a polycarbodiimide compound is added, and the b value as an index of color tone is 7 or less.
According to a preferred aspect of the biodegradable printed film material of the present invention, the fiber fabric or the biodegradable printed film material is calendered.
According to a preferred embodiment of the biodegradable printed film material of the present invention, the biodegradable printed film material of the present invention is suitably used as a substrate for ink jet printing.

  According to the present invention, a biodegradable printed film material having biodegradability and excellent in high recording characteristics and flexibility can be obtained. By using this biodegradable printed film material, because it is biodegradable, it does not cause environmental impact during disposal, and because it has flexibility, it can be installed in structures of any shape, such as banners and posters The printing base material suitable for the advertising medium is obtained.

  The present inventors have intensively studied a biodegradable printed film material that has biodegradability, high recording characteristics and flexibility, and is composed of a biodegradable resin on at least one side of a fiber fabric having biodegradability. When an inorganic material and a water-absorbing resin were added to the biodegradable resin as a base material for ink-jet printing having a laminated film, it was found that the problem was unexpectedly solved at once.

  The material constituting the biodegradable fiber fabric used in the present invention includes natural fibers such as cotton and hemp, natural products such as natural leather and wood, and “Green Plastic” (Biodegradable Plastics Study Group). , Registered trademark), and the like. Among these materials, polylactic acid that can be landfilled and decomposed in soil and further compostable is preferable.

The fiber made of polylactic acid is polymerized using plant-derived lactic acid as a raw material to form a polylactic acid resin, and then fiberized. In the fiber state, the melting point is around 170 ° C., and the water is heated to about 120 ° C. Since it also withstands, it can be made into a textile fabric such as a woven fabric and can be subjected to various treatments. Polylactic acid fibers are biodegradable and are reduced to water and carbon dioxide through hydrolysis and microbial degradation in soil and water, increasing the burden on the global environment. A life cycle can be formed without any problems. The specific gravity of the polylactic acid fiber is 1.2 to 1.3, which is lighter than the polyester fiber, and is advantageous in terms of reducing the weight of the fiber fabric as the base fabric. The tensile strength of the polylactic acid fiber is about 5000 N / cm ² and has a sufficient strength. Polylactic acid fibers are made into fibers by melt spinning, but the strength of polylactic acid fibers is 400 mN / dtex, which is relatively strong as a fiber. The melting point is 175 ° C., which is relatively low, but there is no problem as a printing base fabric. The moisture absorption is 0.5%, exhibits hydrophobicity, and is suitable for use as an outdoor advertising medium.

  As the type of fiber fabric, at least one selected from woven fabrics, knitted fabrics and non-woven fabrics can be preferably used, but among these, those having a smoother surface than improved strength, dimensional stability and recording characteristics. A woven fabric is preferably used because it is good. Examples of the texture of the woven fabric include plain weave, twill weave, satin weave, honeycomb, leopard weave, oblique weave, double texture, pile texture, entangled texture and woven texture, and plain weave is preferred for the above reasons. The weaving means of the woven fabric may be any type such as an air jet, a water jet, and a rapier.

  The composition of the biodegradable printing film material suitable for the substrate for ink jet printing of the present invention is such that an ink receiving layer that absorbs ink discharged from the ink jet printer is installed on the printing surface side, and the biodegradable printing film material In order to maintain the mechanical characteristics, a fiber fabric is provided under the ink receiving layer. The ink receiving layer needs to absorb ink quickly, touch the hand after printing, do not transfer even when pressed against paper, and express vivid colors by absorbing ink appropriately. In addition, when used as a biodegradable printed film material, characteristics such as strength, durability and flexibility are required.

  Since it has biodegradability, it is necessary to use a biodegradable resin as the ink receiving layer. In general, a quaternary ammonium salt type cation resin is used as an ink receiving agent. However, since this quaternary ammonium salt type cation resin does not have biodegradability, the quaternary ammonium salt type cation resin is laminated as an ink receiving layer. When the printing substrate is discarded and buried in the soil, the ink receiving layer remains as dust, and as a result, the environmental load is not reduced. The biodegradable resin is not particularly limited as long as it has biodegradability. For example, vinyl acetate, chemically synthesized aliphatic polyester resin and polylactic acid are used, and these resins are mixed. Can also be used.

  The biodegradable printed film material of the present invention needs to contain an inorganic substance and a water-absorbing resin in the biodegradable resin. The reason is to develop high recording characteristics, and the required characteristics include ink absorption speed, absorption amount, bleeding prevention, ink back-through prevention, recording density and image sharpness. Since these inks for ink jet printing are mostly composed of water-based inks, these performances can be expressed by absorbing water and retaining ink components (dyes and pigments).

  Examples of inorganic substances used in the present invention include alumina, ceramics, zinc oxide, calcium carbonate, iron oxide, talc, and aluminum oxide in addition to metal oxides such as titanium oxide and silica. Porous silica, which has excellent water absorption performance and can retain ink components, is preferred and used.

  Porous silica can retain ink components in its pores, and can prevent bleeding. In addition, porous silica has many pores and a large surface area, and can contain a large amount of moisture. Therefore, the absorption rate and the amount of absorption can be improved.

For porous, there is an index called simple BET method (one-point BET method), there is a method of calculating from the adsorption amount of nitrogen gas, in the present invention, the specific surface area is preferably 100 [m ² / g] or more, For example, porous silica having a specific surface area of about 300 [m ² / g] can be used.
Further, in order to improve the absorption rate and the absorption amount, it is necessary to add a water-absorbing resin in the biodegradable resin. The water-absorbing resin has a lower ink component retention performance than silica and the like, but has a significantly superior absorption speed and absorption amount, and therefore does not adhere to other objects after printing. The water-absorbing resin is not particularly limited as long as it has a water-absorbing performance, but it is not limited to acrylic acid polymer partial sodium salt cross-linked product, acrylic acid / sodium acrylate copolymer, and modified alkylene oxide. Among them, an acrylic acid polymer partial sodium salt cross-linked product is preferably used as one having particularly good performance.

In the present invention, the water absorption is preferably one that can absorb 10 times or more water weight with respect to 1 g of the water absorbent resin .

Silica preferable as an inorganic substance is preferably contained in the biodegradable resin composition in an amount of 20 to 80 % by weight based on the biodegradable resin. In order to improve the above-mentioned printability, it is necessary to add an inorganic substance such as silica. However, if the addition amount is less than 20% by weight, the absorption performance is inferior, and if it exceeds 80 % by weight, cracks are generated. Since the quality deteriorates and the biodegradable resin as the binder resin cannot retain the silica, the silica falls off, and the dropped silica causes problems such as nozzle clogging, so the added amount is 20 to 80 % by weight. Is an appropriate amount, and a more preferable addition amount is 30 to 50% by weight.
Moreover, the average particle diameter (laser method) of silica is preferably 1 to 6 μm, and more preferably 1.5 to 4.0 μm. If the particle diameter is too small, the recording area tends to be inferior because the surface area is small and the amount of absorption decreases. On the other hand, if the particle size is too large, the particles are likely to aggregate and cracks may be generated, resulting in poor surface quality, which may cause silica to fall off.

Moreover, it is preferable that 20-70 weight% of water absorbing resin is contained with respect to biodegradable resin in a biodegradable resin composition. If the addition amount is less than 20 % by weight, both the absorption speed and the absorption amount are inferior, resulting in poor recording characteristics. If the addition amount is more than 70 % by weight, the water absorbent resin swells when it absorbs water, so that the surface quality is low. If it is deteriorated and pressed, water may be released and reattachment may occur. Moreover, it is preferable that the average particle diameter of a water absorbing resin is 10-50 micrometers. If the average particle size is smaller than 10 μm, the amount of absorption decreases and the recording characteristics may deteriorate. Further, since it is difficult to make a water-absorbing resin having a finer particle diameter, it is preferably 10 μm or more. Further, the average particle diameter of normally water-absorbent resin often or more of 350 .mu.m, as the average particle size is above a 50μm greater, a tendency that the surface quality deteriorates to swell by water absorption.

The amount of the biodegradable resin composition attached to the fiber fabric is preferably ²⁰ to 100 g / m ² . When the adhesion amount is less than 20 g / m ^2, the absolute amount of silica or water-absorbing resin is decreased, and the recording characteristics may be deteriorated. In addition, since the amount of the biodegradable resin as the binder resin is reduced, the silica and the water-absorbing resin cannot be retained, and the dropping may occur. In addition, when the adhesion amount exceeds 100 g / m ^2, the amount of the biodegradable resin increases and becomes hard as a texture, or becomes stiff and unusable for applications such as a hanging curtain. Since the resin does not follow the flexibility, problems such as peeling may occur.

More preferably, when measured based on the hydrostatic pressure method in the water resistance test method A (low pressure method) specified in JIS L 1092 5.1 (1998), the biodegradable resin is 1000 mmH ₂ O or more. adhesion amount of the composition is preferably ^{40g / m 2 ~80g / m 2} .
As a method of laminating the ink receiving layer comprising the biodegradable resin composition on the fiber fabric, the biodegradable resin composition is applied by a coating method or a dipping method, and preferably dried at a temperature range of 100 to 130 ° C. A solidification method is preferred. A commonly used processing method can be adopted as the coating processing method, and known processing methods such as knife coating, kiss coating, comma coating, and gravure coating are used.

In the biodegradable resin composition used in the present invention, it is preferable that the plasticizer is contained in an amount of 10 to 50% by weight based on the biodegradable resin from the viewpoint of improving flexibility and adhesive strength. From the viewpoint of the global environment, the plasticizer is preferably a biodegradable plasticizer because it has biodegradability and does not affect the environment even when buried in soil. The biodegradable plasticizer is not particularly limited as long as it has biodegradability, but an adipic acid ester is preferred because of its high flexibility effect.
The biodegradable plasticizer has a hard texture and prevents the occurrence of problems such as failure to follow the flexibility of the fiber fabric and separation of the resin or cracks in the resin layer. Moreover, when flexibility is lacking, restrictions such as difficulty in workability and handling, and inability to use the curved portion. Therefore, in the biodegradable resin composition, the biodegradable plasticizer is preferably contained in an amount of 10 to 50% by weight with respect to the biodegradable resin. If the addition amount is less than 10% by weight, the above-described problems occur. If the addition amount is more than 50% by weight, the plasticizer moves to the resin surface and bleeds, so that tack or the plasticizer itself appears on the surface. Therefore, the recording characteristics may be deteriorated.
In order to improve the recording characteristics, the fiber fabric or the biodegradable printed film material is preferably calendered. By smoothing the surface, it is possible to express finely like printing paper. As the calendar condition, it is preferable to apply a load of 3 to 80 ton / cm with a roller heated to a temperature of 80 to 110 ° C. The machine for calendering is not particularly limited as long as the fiber fabric or the biodegradable printing film material is compressed by two or more rollers.

  The polylactic acid preferably used in the present invention refers to a polymer obtained by polymerizing oligomers such as lactic acid and lactide. When the optical purity of the L-form or D-form is 90% or more, the melting point is high and is preferred. In addition, components other than lactic acid and lactide may be copolymerized as long as the properties of polylactic acid are not impaired, and it contains additives such as polymers and particles other than polylactic acid, flame retardants and antistatic agents. Also good. However, from the viewpoint of biomass utilization and biodegradability, it is important that the lactic acid monomer is 50% by weight or more as a polymer. The lactic acid monomer is preferably 75% by weight or more, more preferably 96% by weight or more. The molecular weight of the polylactic acid polymer is preferably 50,000 to 500,000 in terms of weight average molecular weight from the viewpoint of the balance between mechanical properties and moldability.

  It is preferable that a polycarbodiimide compound is added to the polylactic acid used in the present invention. As the polycarbodiimide compound, a polymer obtained by polymerizing a diisocyanate compound is preferably used. Among them, a polymer of 4,4′-dicyclohexylmethane carbodiimide, a polymer of tetramethylxylylene carbodiimide, or a terminal thereof is made of polyethylene glycol or the like. A blocked polycarbodiimide compound is preferably used. This is to block the reaction active terminal of the polylactic acid polymer and / or the oligomer contained therein with a polycarbodiimide compound, thereby inactivating the reaction active terminal in the polymer and suppressing hydrolysis of polylactic acid. Although there are a hydroxyl group and a carboxyl group at the reaction active terminal, the carbodiimide compound is excellent in the blocking property of the carboxyl group.

  Further, as a result of detailed examination of the behavior of the polycarbodiimide compound in polylactic acid, the present inventors have found that the unreacted free polycarbodiimide compound does not react with the reactive active terminal, resulting in poor yarn production and poor color tone. I found that it had an adverse effect. More specifically, it has been found that the free polycarbodiimide compound is a cause of the above-mentioned problems that abrupt thermal degradation occurs at a temperature of 200 to 250 ° C., which is a polylactic acid molding and spinning temperature. Is. For this reason, in order to improve the spinning property and color tone of the polylactic acid fiber to which the polycarbodiimide compound is added, it is important to select the addition amount of the polycarbodiimide compound and / or the temperature and residence time during kneading or melt spinning. is there.

  It is important that the amount of polycarbodiimide compound added is determined with respect to the carboxyl end amount rather than with respect to the weight of polylactic acid. Furthermore, since residual oligomers such as lactide also generate carboxyl ends by hydrolysis, it is important to first examine the total amount of carboxyl ends including not only the carboxyl ends of the polymer but also those derived from the remaining oligomers and monomers. And if the addition amount of a polycarbodiimide compound shall be 2 times equivalent or less, it can be compatible to reduce a free polycarbodiimide compound and to perform carboxyl terminal blockage at a high rate. The addition amount of the polycarbodiimide compound is more preferably 1.5 times equivalent or less of the total carboxyl terminal amount.

  Moreover, it is preferable by terminal blockage that the total carboxyl terminal density | concentration is 10 equivalent / t or less with respect to the whole polylactic acid, and can improve hydrolysis resistance drastically.

  On the other hand, the residence time of the polycarbodiimide compound at the temperature of 200 to 250 ° C. during melt spinning is preferably 20 minutes or less, and thermal degradation of the polycarbodiimide compound can be suppressed. The residence time of the polycarbodiimide compound is more preferably 10 minutes or less.

  For this reason, it is preferable to devise a method for adding the polycarbodiimide compound, and it is preferable to add the polycarbodiimide compound directly to the polylactic acid at the time of spinning, rather than preparing a polylactic acid chip to which the polycarbodiimide compound has been added in advance. For example, there is a method of adding a polycarbodiimide compound at the melted portion of the polylactic acid polymer during spinning, or kneading the separately melted polycarbodiimide compound and polylactic acid in a pack with a static kneader or the like.

  In the polylactic acid fiber excellent in hydrolysis resistance, which is a fiber having biodegradability used in the present invention, the b value, which is an index of yellowish color tone, is preferably 7 or less. It can also be used in applications where color tone is important. The b value is preferably 5 or less.

  For improving the b-value of polylactic acid fiber, it is of course possible to use a bluing compound such as cobalt acetate, as used in polyethylene terephthalate, etc. The vivid color development characteristic of turbid polylactic acid fibers may be impaired or thread breakage may be caused. Therefore, the amount added is preferably 500 ppm or less based on the weight of polylactic acid.

  In the present invention, hydrolysis resistance can be evaluated by the viscosity retention rate and strength retention rate of the fiber. In the present invention, 30 g of a sample and 300 g of water are put in a pressure vessel, and the viscosity retention rate of the fiber before and after the hydrothermal treatment at 130 ° C. for 60 minutes is preferably 75% or more. The viscosity retention is more preferably 85% or more. The strength retention of the fiber before and after the hot water treatment is preferably 70% or more. The strength retention is more preferably 85% or more.

  In the polylactic acid fiber excellent in hydrolysis resistance, the strength is preferably 2.0 cN / dtex or more in order to keep the process passability and the mechanical strength of the product sufficiently high. The strength is preferably 3.5 cN / dtex or more. Moreover, it is preferable that the elongation of the polylactic acid fiber used by this invention is 15 to 70%, and the process passability at the time of making a fiber product improves. The elongation is more preferably 25 to 50%.

  In the fiber used in the present invention, the boiling yield is preferably 0 to 20%, and the dimensional stability of the fiber and the fiber product is good. The boiling yield is more preferably 3 to 10%.

  The cross-sectional shape of the polylactic acid fiber excellent in hydrolysis resistance used in the present invention can be freely selected for a multi-leaf cross section such as a round cross section, a hollow cross section, a trilobal cross section, and other irregular cross sections. . The form of the fiber is not particularly limited, such as long fiber or short fiber, and in the case of long fiber, it may be multifilament or monofilament.

  It is preferable that the fiber which comprises a fiber fabric contains 0.1-5 wt% of fatty acid amide with respect to the whole fiber. Particularly preferred fatty acid amides include fatty acid bisamides and / or alkyl-substituted fatty acid monoamides. By setting the fatty acid amide content to 0.1 wt% or more, the surface friction coefficient of the fiber can be reduced, and the wear resistance required for the fiber product, durability and flexibility in repeated use can be imparted. . Furthermore, it is possible to suppress the fusion of the fiber fabric by a cutting cutter or a high-speed sewing needle in the fiber fabric processing step, and to improve the process passability. Moreover, fatty acid amide can be finely dispersed by making content of fatty acid amide 5 wt% or less, and it can prevent that the physical property spot and dyeing spot of a fiber generate | occur | produce. The content of fatty acid amide is more preferably 0.5 to 3 wt%.

In the present invention, the fatty acid amide may be contained alone or a plurality of components may be mixed. When fatty acid amide is mixed, the mixture should just contain 0.1-5 wt% with respect to the whole fiber.
The fatty acid bisamide used in the present invention refers to a compound having two amide bonds in one molecule such as saturated fatty acid bisamide, unsaturated fatty acid bisamide, aromatic bisamide, etc., for example, methylene biscaprylic amide, methylene biscaprin Acid amide, methylene bis lauric acid amide, methylene bis myristic acid amide, methylene bis palmitic acid amide, methylene bis stearic acid amide, methylene bis isostearic acid amide, methylene bis behenic acid amide, methylene bis oleic acid amide, methylene bis eruka Acid amide, ethylene biscaprylic acid amide, ethylene biscapric acid amide, ethylene bislauric acid amide, ethylene bismyristic acid amide, ethylene bispalmitic acid amide, ethylene bisstearic acid amide, ethyl Bisisostearic acid amide, ethylene bis behenic acid amide, ethylene bis oleic acid amide, ethylene bis erucic acid amide, butylene bis stearic acid amide, butylene bis behenic acid amide, butylene bis oleic acid amide, butylene bis erucic acid Amide, hexamethylene bis stearic acid amide, hexamethylene bis behenic acid amide, hexamethylene bis oleic acid amide, hexamethylene bis erucic acid amide, m-xylylene bis stearic acid amide, m-xylylene bis-12-hydroxy stearic acid Amides, p-xylylene bis-stearic acid amide, p-phenylene bis-stearic acid amide, p-phenylene bis-stearic acid amide, N, N′-distearyl adipic acid amide, N, N′-distearyl sebacic acid amide N, N'-dioleoyl adipic acid amide, N, N'-dioleyl sebacic acid amide, N, N'-distearyl isophthalic acid amide, N, N'-distearyl terephthalic acid amide, methylenebishydroxystearic acid Examples include amide, ethylene bishydroxystearic acid amide, butylene bishydroxystearic acid amide, and hexamethylene bishydroxystearic acid amide.

  The alkyl-substituted fatty acid monoamide referred to in the present invention refers to a compound having a structure in which amide hydrogen such as a saturated fatty acid monoamide or an unsaturated fatty acid monoamide is replaced with an alkyl group, such as N-lauryl lauric acid amide, N- Palmityl palmitic acid amide, N-stearyl stearic acid amide, N-behenyl behenic acid amide, N-oleyl oleic acid amide, N-stearyl oleic acid amide, N-oleyl stearic acid amide, N-stearyl erucic acid amide, and N- Examples include oleyl palmitic acid amide. The alkyl group may have a substituent such as a hydroxyl group introduced into its structure, such as methylol stearamide, methylol behenic acid amide, N-stearyl-12-hydroxystearic acid amide, and N -Oleyl 12 hydroxystearic acid amide and the like are also included in the alkyl-substituted fatty acid monoamide of the present invention.

  In the present invention, fatty acid bisamides and alkyl-substituted fatty acid monoamides are preferably used. However, these compounds have lower amide reactivity than ordinary fatty acid monoamides, and hardly react with polylactic acid during melt molding. . In addition, since many of them have a high molecular weight, they generally have good heat resistance and are difficult to sublimate. In particular, fatty acid bisamides can be used as more preferable lubricants because they are less reactive with polylactic acid due to the lower reactivity of amides, and are high in heat resistance and difficult to sublimate due to their high molecular weight.

  The polylactic acid fiber preferably used in the present invention is preferably provided with a spinning oil containing a smoothing agent. As the smoothing agent, for example, fatty acid ester, polyhydric alcohol ester, ether ester, silicone, mineral oil and the like are preferably used as those for reducing the friction coefficient between the fiber and the metal, plastic or the like. Moreover, these smoothing agents may be used as a single component, or a plurality of components may be mixed and used. In particular, fatty acid esters and mineral oils are preferably used as smoothing agents suitable for polylactic acid fibers. Polyether leveling agents are excellent in heat resistance, but are preferably avoided because they may increase the coefficient of friction between the fibers and the metal. By lowering the friction coefficient, it can be assumed that it will be installed on walls or metal pillars when used for applications such as hanging curtains, and it can improve durability by reducing friction with these things. it can.

  The fatty acid ester used in the present invention is not particularly limited, and examples thereof include monohydric alcohols such as methyl oleate, isopropyl myristate, octyl palmitate, oleyl laurate, oleyl oleate, and isotridecyl stearate. And monovalent alcohols such as esters of monovalent carboxylic acids, dioctyl sebacate, dioleyl adipate and esters of polyvalent carboxylic acids, ethylene glycoldiolate, trimethylolpropane tricaprylate, glycerol trioleate And esters of monohydric carboxylic acids and alkylene oxide addition esters such as uryl (EO) n octanoate.

  By applying an oil agent containing a smoothing agent as described above to the polylactic acid fiber, it is possible to suppress yarn breakage, generation of fluff, and winding around a roller in the spinning and drawing processes. Also, false twisting, which has poor processability in conventional polylactic acid fibers, can be carried out with good processability by reducing the frictional force between the yarn and the twister and suppressing yarn breakage. Furthermore, in the weaving and weaving process, the friction between the yarn and the metal or the yarn is reduced, and it is possible to obtain a high-quality fiber product by suppressing the generation of fuzz.

  In the present invention, in addition to the smoothing agent, the component constituting the oil agent is an emulsifier that emulsifies the oil agent in water and lowers the viscosity to improve the adhesion to the yarn and the permeability, and if necessary, an antistatic agent, an ion A surfactant, a sizing agent, a rust inhibitor, a preservative, and an antioxidant, which are appropriately blended, can be used. The content of the smoothing agent relative to the whole oil is preferably 30 to 95% by weight. By setting the content of the smoothing agent to the entire oil agent to be 30% by weight or more, the surface friction coefficient of the fiber can be greatly reduced, and the processability and quality of the fiber and the fiber product can be improved. Moreover, by making the content 95% by weight or less, the dispersibility of the oil agent in water can be improved, and the adhesion spot of the oil agent when this is applied to fibers can be suppressed. The content of the smoothing agent relative to the whole oil is more preferably 55 to 75% by weight.

  The biodegradable printed film material of the present invention can be suitably used as an advertising medium such as a banner, a poster, or a signboard.

  Hereinafter, the biodegradable printed film material of the present invention will be described in detail using examples. In addition, the following method was used for the measuring method in an Example.

1. Total carboxyl terminal concentration As described in JP-A-2001-261797, a weighed sample was dissolved in o-cresol adjusted to a water content of 5%, and an appropriate amount of dichloromethane was added, followed by 0.02N KOH methanol solution. Titration and determination. At this time, since an oligomer such as lactide which is a lactic acid dimer is hydrolyzed to generate a carboxyl terminal, the carboxyl terminal concentration of the polymer and the total of both the carboxyl terminal derived from the monomer and the carboxyl terminal derived from the oligomer are obtained.

2. Color tone (b value)
The fiber sample was tightly wound around an aluminum plate, and the b value was measured with an SM color computer SM-3 manufactured by Suga Test Instruments Co., Ltd.

3. Strength retention (RT) before and after hydrothermal treatment
30 g of sample and 300 g of water were put in a pressure vessel, and hydrothermal treatment was performed at a temperature of 130 ° C. for 60 minutes. RT was calculated | required by the following formula | equation. The strength of the polylactic acid fiber before the hot water treatment and the strength of the polylactic acid fiber after the hot water treatment were measured by loosening the yarn from the tubular knitting.

RT (%) = (strength of sample after hot water treatment / strength before hot water treatment) × 100 (%)
4). Fir test A Scott fir test specified in JIS K 6404-5 (1999) was carried out 100 times with a load of 500 g. The case where peeling occurred in the resin was indicated as x, and the case where peeling did not occur was indicated as ◯.

5). Absorption speed After printing, the biodegradable printed film material is dried in an atmosphere of 20 ° C x 40% RH for 6 seconds and pressed against white copy paper with a load of 500g. The ones that were not attached were displayed as x and the ones that were not attached as ○.

6). Color developability Using an ink jet printer, printing was performed using each printing ink, and the print density was evaluated. A very dark print density is indicated by “◎”, a dark print is indicated by “◯”, a slightly light print is indicated by “Δ”, and a light print is indicated by “X”.

7). Comprehensive evaluation In the fir test, evaluation of water absorption rate and color developability, “○” is marked as “○” as having excellent printing suitability with 3 or more “○” as the printing substrate. In particular, “◎” is indicated as excellent, and “◯” in the above three performances is indicated as “△” as inappropriate as a printing substrate, but there is room for improvement. Those with one or less “◯” were regarded as “x” as inappropriate for the printing substrate.

[Production Example 1] (Production of polylactic acid)
Lactide prepared from L-lactic acid with an optical purity of 99.5% was mixed with bis (2-ethylhexanoate) tin catalyst (lactide to catalyst molar ratio = 10000: 1) at a temperature of 180 ° C. in a nitrogen atmosphere. Polymerization was performed for 140 minutes to obtain polylactic acid (referred to as P1). The obtained polylactic acid had a weight average molecular weight of 135,000. Η _r of the obtained polylactic acid was 7.5, and the carboxyl terminal concentration was 35 equivalent / t.

[Production Example 2] (Production of polylactic acid containing 1 wt% EBA)
After drying the above polylactic acid (P1) and ethylene bis-stearic acid amide (referred to as EBA) [“Alfro H-50S” (registered trademark) manufactured by NOF Corporation], P1: EBA = 99: 1 (weight ratio) While the EBA melted by heating was measured and continuously added to P1, it was supplied to a twin-screw kneading extruder having a cylinder temperature of 220 ° C., and polylactic acid containing 4% by weight of EBA (referred to as P2). Obtained. Η _r of the obtained polylactic acid was 7.5, and the carboxyl terminal concentration was 35 equivalent / t.

(Examples 1-6, Comparative Examples 1-2)
As the polycarbodiimide compound, a thermoplastic polycarbodiimide “carbodilite” (registered trademark) HMV-8CA (carbodiimide 1 equivalent / carbodiimide 278 g) manufactured by Nisshinbo Co., Ltd. was used. Polylactic acid P1 and polycarbodiimide compound were melted separately at 220 ° C. and 120 ° C., respectively, and led to a spinning pack. A stationary kneader in the spinning pack (“High Mixer” (registered trademark), 10 stages, manufactured by Toray Engineering Co., Ltd.) ) And kneaded as it was. At this time, the addition amount of the polycarbodiimide compound was 1.0 times equivalent to the carboxyl end amount (1.0 wt% with respect to polylactic acid). The residence time of the polycarbodiimide compound in the spinning machine was 5 minutes, and the spinning temperature was 220 ° C.
Then, the spun yarn was cooled and solidified with a cooling air at 25 ° C. by a chimney, and then a fiber oil agent mainly composed of a fatty acid ester was applied by a converged oil supply guide, and the yarn was entangled by the entanglement guide. There was no problem with melt spinnability, and there was no yarn breakage after 100 kg winding. Thereafter, the film was taken up by a non-heated first take-up roller with a peripheral speed of 3000 m / min, and then wound up through a non-heated second take-up roller. This yarn was preheated at a first hot roller temperature of 90 ° C., then stretched 1.45 times, heat set at a temperature of 130 ° C. with a second hot roller, wound up through a cold roller, 560 dtex, 36 filaments A drawn yarn with a round cross section was obtained. There was no problem with the stretchability here, and there was no yarn breakage after winding 100 kg.

Using this drawn yarn for warp and weft, a plain fabric (weaving density: warp 48 / inch, weft 32 / inch, basis weight 180 g / m ² ) was produced in a water jet loom. Next, the obtained plain woven fabric was scoured for 1 minute at a temperature of 60 ° C. in a bath of 2 g / L of a scouring agent, and then treated and set at a temperature of 130 ° C. for 1 minute in a pin tenter type heat treatment machine. The obtained plain woven fabric was soft and soft, but exhibited an excellent texture with less mechanical squeakiness peculiar to polylactic acid fibers.
This plain woven fabric (fiber fabric) was calendered at a temperature of 100 ° C. with a linear pressure of 30 tons, and a coating agent, which is a biodegradable resin composition shown below, was coated on one side with a knife coater. Dried for 2 minutes at a temperature of ° C. An image was printed on the resin surface of the obtained biodegradable printed film material using an inkjet printer. The total carboxyl terminal concentration of the obtained fiber was 5 equivalent / t or less, and the color tone b value was 4.3 to 4.6. The characteristics of the obtained biodegradable printed film material are shown in Table 1.

[Coating agent]
Polylactic acid resin (manufactured by Miyoshi Oil & Fat Co., Ltd.), silica (manufactured by Fuji Silysia Co., Ltd., Silicia 310P (registered trademark)), water absorbent resin (manufactured by Sumitomo Seika Co., Ltd., Aquakeep (registered trademark)) ), Biodegradable plasticizer (manufactured by Daihachi Chemical Industry Co., Ltd., DAIFATTY-101 (registered trademark)), Bionore (manufactured by Showa Polymer Co., Ltd., aliphatic polyester) in a mixed amount in Table 1 Was made. As for bionore, 60% by weight was added.

(Examples 7 to 10)
In Example 1, the biodegradable printed film material was changed in the same manner as in Example 1 except that polylactic acid (P1) was changed to polylactic acid (P2) and the addition amount of additives was changed as shown in Table 1. Got. The total carboxyl terminal concentration of the fiber was 5 equivalent / t or less, and the color tone b value was 4.3 to 4.5. The results are shown in Table 1.

(Comparative Examples 3-4)
Polylactic acid (P2) was spun at a spinning temperature of 220 ° C. The spun yarn was cooled and solidified by a chimney with cooling air at a temperature of 25 ° C., and then a fiber oil agent mainly composed of a fatty acid ester was applied by a focused oiling guide, and the yarn was entangled by the entanglement guide. There was no problem with melt spinnability, and there was no yarn breakage after winding 100 kg. Thereafter, the film was taken up by a non-heated first take-up roller with a peripheral speed of 3000 m / min, and then wound up through a non-heated second take-up roller. This yarn is preheated at a first hot roller temperature of 90 ° C., then stretched by 1.45 times, heat set at a temperature of 130 ° C. with a second hot roller, wound up through a cold roller, 560 dtex, 36 filaments A drawn yarn with a round cross section was obtained. There was no problem with the stretchability here, and there was no yarn breakage after winding 100 kg. The total carboxyl terminal concentration of the obtained fiber was 40 equivalent / t, and the color tone b value was 3.3 to 3.5.
Hereinafter, as shown in Table 1, a biodegradable printed film material was obtained in the same manner as in Example 1 except that a polylactic acid resin containing no additive (Miyoshi Oil & Fats Co., Ltd.) was used. The results are shown in Table 1.

(Comparative Examples 5-6)
Weaving a plain fabric with a warp / weft density of 54/48 / inch, using polyester spun yarn No. 20 twin yarn (Toray Industries, Inc.) as warp and polyester spun yarn No. 10 single yarn as weft. (Weight 220 g / m ² ), and the obtained plain woven fabric was padded with a processing solution of a wax-based water repellent (Daigard D-23D (registered trademark), manufactured by Daikyo Chemical Co., Ltd., solid content 40%). 80%) and dried at a temperature of 120 ° C. for 2 minutes to obtain a treated fiber fabric. The biodegradable resin composition used in Example 1 was similarly coated on one side of the obtained fiber fabric to obtain a biodegradable printed film material. The results are shown in Table 1.

(Examples 11-14, Comparative Examples 7-8)
A fiber fabric was obtained in the same manner as in Example 1. One surface of the fiber fabric was coated with a coating agent, which is a biodegradable resin composition shown below, in the same manner as in Example 1 to obtain a biodegradable printed film material. The total carboxyl end concentration of the fiber was 5 equivalent / t or less, and the color tone b value was 4.3 to 4.6. The results are shown in Table 1.
[Coating agent]
Polylactic acid resin (manufactured by Miyoshi Oil & Fat Co., Ltd.), silica (manufactured by Fuji Silysia Co., Ltd., Silicia 310P (registered trademark)), water absorbent resin (manufactured by Sumitomo Seika Co., Ltd., Aquakeep (registered trademark)) ), A biodegradable plasticizer (manufactured by Daihachi Chemical Industry Co., Ltd., DAIFATTY-101 (registered trademark)) was mixed in the addition amount shown in Table 1.

  However, in Comparative Examples 7 to 8, as shown in Table 1, silica and water-absorbing resin were not added, and only polylactic acid resin was used.

(Comparative Examples 9 to 10)
A fiber fabric was obtained in the same manner as in Example 1. This fiber fabric was calendered, and on one side, a coating agent, which is a resin composition shown below, was coated with a knife coater and dried at a temperature of 130 ° C. for 2 minutes. An image was printed on the obtained film material using an inkjet printer. The total carboxyl terminal concentration of the obtained fiber was 5 equivalent / t or less, and the color tone b value was 4.3 to 4.6. The results are shown in Table 1.
[Coating agent]
A liquid in which a quaternary ammonium salt type cationic resin was mixed with a polylactic acid resin (manufactured by Miyoshi Oil & Fats Co., Ltd.) was prepared.

  As is clear from Table 1, the biodegradable printed film materials of Examples 1 to 14 have excellent recording characteristics because the biodegradable resin contains silica and a water-absorbing resin. Since the plasticizer is also included, it is flexible and has excellent adhesion between the ink receiving layer (resin) and the fiber fabric. On the other hand, Comparative Examples 1-2 and 7-14 did not contain silica and water-absorbing resin, and were inferior in recording characteristics. Comparative Examples 9 to 10 use polyester fibers instead of polylactic acid fibers, and Comparative Examples 13 to 14 use quaternary ammonium salt type cationic resins as ink adsorbers instead of silica and water absorbent resins. More than 25% of the total is not biodegradable and cannot be said to be environmentally friendly.

  The biodegradable printed film material of the present invention has biodegradability, is excellent in high recording characteristics and flexibility, and is useful as a substrate for ink jet printing. By using this biodegradable printed film material, because it is biodegradable, it does not cause environmental impact during disposal, and because it has flexibility, it can be installed in structures of any shape, such as banners and posters The printing base material suitable for the advertising medium is obtained.

Claims (8)

An ink receiving layer made of a biodegradable resin composition containing an inorganic substance and a water-absorbing resin having an average particle diameter of 10 to 50 μm is laminated on at least one surface of a fiber fabric having biodegradability. Degradable print film material.   The biodegradable printed film material according to claim 1, wherein the inorganic substance is silica, and the silica is contained in an amount of 20 to 80% by weight based on the biodegradable resin.   The biodegradable printed film material according to claim 1 or 2, wherein the water-absorbing resin is contained in an amount of 20 to 70% by weight based on the biodegradable resin. Biodegradable printing film material of any of claims 1 to 3 attached amount of the biodegradable resin composition is 20 to 100 g / m ^2.   The biodegradable printed film material according to any one of claims 1 to 4, wherein the biodegradable plasticizer is contained in an amount of 10 to 50% by weight based on the biodegradable resin.   The biodegradable printed film material according to any one of claims 1 to 5, wherein the fiber constituting the fiber fabric contains 0.1 to 5 wt% of a fatty acid amide.   The biodegradable printed film material according to any one of claims 1 to 6, wherein the fiber fabric or the biodegradable printed film material is calendered. The biodegradable printed film material according to any one of claims 1 to 7 , which is used as a substrate for inkjet printing.