JP2009137092A - Member for ink cartridge - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a member for an ink cartridge which prevents the deterioration of property of gas barrier and occurrence of delamination with lapse of time from a viewpoint of barrier to moisture evaporation from the inside of a package by making a gas barrier layer heat-resistant while using alumina vapor deposition. <P>SOLUTION: The member of the ink cartridge is constituted by sticking a barrier film obtained by successively providing a pre-treatment layer 2, a transparent vapor deposition thin film layer 4 composed of inorganic oxide, and a gas barrier coating film layer 5 to at least one side of a transparent plastic film base material 1 or sticking a transparent film thereto further. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an ink cartridge member used for packaging an ink cartridge for ink jet recording which stores ink supplied by being connected to an ink jet recording head.

  In an ink jet apparatus (ink jet recording apparatus or the like), exchangeable ink jet cartridges are widely used. The ink cartridge is required to prevent deterioration of the ink component, to mitigate the impact caused by vibration or dropping during transportation or storage, and to prevent the evaporation component of the ink from evaporating. For this reason, various considerations have been made regarding the packaging form of the ink cartridge.

  The target ink cartridge members can be roughly divided into two types. The first type is a member used for packaging the entire cartridge. The outer packaging in this case is often a paper carton, but the interior is a plastic film. The cartridge itself is a plastic container for the purpose of preventing deterioration of ink components and suppressing evaporation. Also, since the inside of the package is evacuated, the packaging member remains flexible and has a certain degree of film strength. Is required.

  The second type is a protective film (seal film) that closes an ink supply port connecting the cartridge and the apparatus main body. Since this film is in direct contact with ink, physical properties that suppress deterioration of ink components and change in water concentration are required.

In order to satisfy the required physical properties of the ink cartridge member described above, aluminum foil has been used, the total thickness of the entire packaging material has been increased, or an inorganic oxide vapor deposited film has been used.
JP2004-188902 JP 2006-1268 A

  However, in the society and particularly in the inkjet printer industry, recycling has been active over the past few years, and the use of aluminum for packaging materials and physical properties due to increased total weight have been avoided. In addition, when polyethylene film deposited with inorganic oxide is used, there is no problem of gas barrier properties, but both alumina (aluminum oxide) and silica (silicon oxide), which are generally used as the deposited inorganic oxide, Each had the following problems.

  Regarding the resistance to liquid, it is generally said that alumina has a weak point in water resistance. Therefore, silica deposition is often used for packaging liquid contents that require a barrier even if the solvent is not water.

  However, there are many problems with silica deposition. The most common of these is color. The yellow-brown color unique to silica deposition tends to be avoided by consumers, and is an impediment to impressing the freshness of the contents, whether liquid or solid.

One problem with silica deposition is a phenomenon called “splash” that occurs during deposition. Silica particles suddenly boil at the time of vapor deposition, adhere to the plastic film substrate as a lump or make a small hole, and cause abnormalities during printing and abnormal gas barriers.

  In view of the above problems of silica vapor deposition, attention has been paid to alumina vapor deposition that is colorless and transparent and has little “splash” as an ink cartridge member.

  Here, even if alumina deposition is used, the purpose is to impart heat resistance to the gas barrier layer and prevent deterioration of gas barrier properties over time, occurrence of delamination, etc., from the viewpoint of moisture evaporation from the inside of the package, It is an object to provide a laminated film suitable for a member of an ink cartridge.

  The invention of claim 1 is a barrier film alone in which a pretreatment layer, a transparent vapor-deposited thin film layer made of an inorganic oxide, and a gas barrier coating layer are sequentially provided on at least one surface of the transparent plastic film, or two transparent plastic films having the above-described configuration An ink cartridge member characterized in that at least one sheet is bonded.

  The invention according to claim 2 is the ink cartridge member, wherein the pretreatment layer is a layer obtained by subjecting a base material to a treatment by reactive ion etching (RIE) using plasma.

  The invention according to claim 3 is the ink cartridge member, wherein the pretreatment layer is a primer layer made of a composite of a polyol resin, an isocyanate compound and a silane coupling agent.

  The invention of claim 4 is characterized in that the silane coupling agent has one or more organic functional groups selected from an isocyanate group, an epoxy group, and an amino group that react with at least one of a hydroxyl group of a polyol resin or an isocyanate group of an isocyanate compound. An ink cartridge member.

  The invention according to claim 5 is the ink cartridge member, wherein the transparent vapor-deposited thin film layer made of the inorganic oxide is aluminum oxide and has a thickness of 5 to 300 nm.

  The invention according to claim 6 is characterized in that the component ratio (AL / O) of aluminum oxide in the transparent vapor-deposited thin film layer made of the inorganic compound is 30 to 50 as analyzed by an energy dispersive X-ray fluorescence analyzer. Ink cartridge member.

According to a seventh aspect of the present invention, the gas barrier coating layer comprises Si (OR ¹ ) ₄ and R ² Si (OR ³ ) ₃ (R ¹ and R ³ are CH ₃ , C ₂ H ₅ , C ₂ H ₄ OCH ₃ It is characterized by applying a solution obtained by mixing a silicon compound represented by a hydrolyzable group such as R ^{2 and} an organic functional group) or a hydrolyzate thereof and a water-soluble polymer having a hydroxyl group, followed by drying by heating. This is a member for an ink cartridge.

In the invention according to claim 8, the organic functional group (R ² ) of R ² Si (OR ³ ) ₃ is a non-aqueous functional group selected from a vinyl group, an epoxy group, a methacryloxy group, a ureido group, and an isocyanate group. It is a member for ink cartridges characterized by having.

The invention according to claim 9 is the ink cartridge member, wherein the organic functional group (R ² ) of R ² Si (OR ³ ) ₃ is an isocyanurate in which an isocyanate group is polymerized.

  As described above, according to the present invention, it is possible to obtain an ink cartridge member that has high gas barrier properties and can prevent deterioration of gas barrier properties by imparting heat resistance and water resistance.

  The present invention will be described in more detail with reference to the drawings. 1 and 2 are cross-sectional explanatory views of an example of the ink cartridge member of the present invention.

  3 and 4 are conceptual diagrams for explaining an example of use of the ink cartridge member of the present invention.

  The substrate 1 in FIGS. 1 and 2 is a film made of a transparent plastic material, and at least one surface thereof is subjected to pretreatment 2 by RIE using plasma, or at least one surface is provided with a primer layer 3. And the vapor deposition thin film layer 4 and the gas barrier film layer 5 which consist of inorganic oxides are laminated | stacked in order on the surface or both surfaces.

  The base material 1 described above is a transparent plastic material, and a highly transparent film is preferable in order to make use of the transparency of the deposited thin film layer. For example, polyester films such as polyethylene terephthalate (PET) and polyethylene naphthalate, polyolefin films such as polyethylene and polypropylene, polystyrene films, polyamide films, polyvinyl chloride films, polycarbonate films, polyacrylonitrile films, polyimide films and polylactic acid films The biodegradable plastic film or the like is used, and may be either stretched or unstretched, and preferably has mechanical strength and dimensional stability. In particular, a polyethylene terephthalate film stretched biaxially from the viewpoint of heat resistance or the like is preferably used. In addition, various known additives and stabilizers such as antistatic agents, ultraviolet inhibitors, plasticizers, lubricants, and the like may be used on the surface of the substrate 1 to improve the adhesion to the thin film. In addition, corona treatment, low temperature plasma treatment, ion bombardment treatment may be performed as pretreatment, and chemical treatment, solvent treatment, etc. may be performed.

  The thickness of the substrate 1 is 1 μm or more, suitability as a packaging material, there are cases where other layers are laminated, and processing when forming a vapor-deposited thin film layer 4 and a gas barrier coating layer 5 made of an inorganic oxide. In consideration of the properties, it can be practically selected in the range of 3 to 200 μm, but in many applications, it is preferably 6 to 30 μm.

  In consideration of mass productivity, it is desirable to use a long film so that each layer can be formed continuously.

  In general, the base material 1 is often a polyester film for use in packaging materials. Examples of the dicarboxylic acid component constituting the polyester include aromatic dicarboxylic acids such as terephthalic acid, naphthalenecarboxylic acid, isophthalic acid, diphenyldicarboxylic acid, diphenylsulfonedicarboxylic acid, diphenoxyethanedicarboxylic acid, 5-sodiumsulfoisophthalic acid, and phthalic acid. Acids, cycloaliphatic dicarboxylic acids such as cyclohexyne dicarboxylic acid, oxalic acid, oxalic acid, adipic acid, sebacic acid, dimer acid, maleic acid, fumaric acid and other aliphatic dicarboxylic acids, p-oxybenzoic acid and other oxycarboxylics An acid etc. are mentioned.

  Examples of the dialcohol component constituting the polyester include aliphatic glycols such as ethylene glycol, propanediol, 1,4 butanediol, 1,6 hexanediol, and neopentyl glycol, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, Examples thereof include polyoxyalkylene glycols such as 1,4 cyclohexanedimethanol, aromatic glycols such as bisphenol A and bisphenol S, and derivatives thereof.

  Among these polyesters, those mainly composed of polyethylene terephthalate and polyethylene naphthalate are preferable from the viewpoints of film forming properties such as biaxial stretching properties, humidity properties, heat resistance, and chemical resistance, and particularly polyethylene terephthalate is used. Is common. Within the range where the various physical properties of polyethylene terephthalate can be maintained, other alcohol components are controlled to be incorporated into the main chain in the polymerization stage and copolymerized to form segments with low rotational hindrance (soft segments) in the molecular chain. In addition, the external impact and bending force can be absorbed by the soft segment in the molecular chain, and the impact resistance and flexibility can be improved. As the polyester used in the barrier film of the present invention, a copolymerized polyester in which 50 mol% or more of each of the carboxylic acid component and the alcohol component is terephthalic acid, ethylene glycol, and derivatives thereof is preferably used.

  In order to improve the adhesion between the substrate 1 and the transparent vapor-deposited thin film layer 4 made of an inorganic oxide, a pretreatment 2 is performed on the surface by reactive ion etching (RIE) using plasma. By performing this RIE treatment, the generated radicals and ions are used to provide a chemical effect such as having a functional group on the surface of the substrate 1, and the surface is ion-etched to scatter impurities and the like. It is possible to simultaneously obtain two physical effects such as By performing such surface treatment, a dense thin film of inorganic oxide can be formed in the next vapor deposition step. As a result, the adhesion between the base material 1 and the transparent vapor-deposited thin film layer 4 made of an inorganic oxide can be strengthened, leading to an improvement in gas barrier properties and moisture resistance and prevention of cracks in the transparent vapor-deposited thin film layer. .

  There is no particular limitation on the method of performing the processing by RIE with a winding-type in-line apparatus, but a method of performing processing using a plasma processing device is general.

  Further, as an alternative to performing pretreatment 2 by reactive ion etching (RIE) using plasma, a primer layer 3 made of a composite containing a polyol resin, an isocyanate compound, and a silane coupling agent may be provided.

  The primer layer 3 enhances the adhesion between the base material 1 and the transparent vapor-deposited thin film layer 4 made of an inorganic oxide, and prevents the vapor-deposited layer from peeling off after storage at high temperature and high humidity or after boil treatment. It is also a layer. The ink filled in the ink cartridge may be boiled. There are many purposes for boil treatment, but mainly sterilization such as defoaming, mold and bacteria.

The resin that can be used as the primer layer is selected from general polymer resins used as adhesives such as polyurethane resins, polyester resins, acrylic resins, and ether resins.
The following explanation is an example in the case of using a composition such as a polyol resin, an isocyanate compound, and a silane coupling agent.

The composition constituting the primer layer will be described in more detail.
As the polyol resin used in the present invention, a general polyol resin such as polyester polyol, polyether polyol, acrylic polyol or the like can be used.

  Examples of polyester polyols include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, 1,5-pentanediol, 1,4-butylene glycol, 1,6-hexanediol, diethylene glycol, One or more of low molecular weight diols such as propylene glycol, tripropylene glycol, neopentyl glycol, cyclohexanediol, cyclohexanedimethanol, and for example, malonic acid, maleic acid, succinic acid, adipic acid, azelaic acid, tartaric acid, Poly produced by reaction with polycarboxylic acids such as pimelic acid, sebacic acid, oxalic acid, terephthalic acid, isophthalic acid, maleic acid, maleic anhydride, fumaric acid, dimer acid, trimellitic acid or derivatives thereof Ester polyols, polyester polyols, and the like produced by ring-opening polymerization of caprolactone.

  Examples of the polyether polyol include polyhydric alcohols containing an ether bond such as polyoxyethylene glycol, polyoxypropylene glycol, and polyoxytetramethylene glycol.

As the acrylic polyol, a polymer compound obtained by polymerizing an acrylic acid derivative monomer or a polymer compound obtained by copolymerizing an acrylic acid derivative monomer and other monomers has a hydroxyl group at the terminal. Can be mentioned. Among these, those obtained by polymerizing acrylic acid derivative monomers such as ethyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, and hydroxybutyl methacrylate alone, and acrylic polyols obtained by copolymerizing with other monomers such as styrene are preferably used.
The isocyanate compound used in the present invention is added in order to increase the adhesion with a vapor deposition layer made of a base material or an inorganic oxide by a urethane bond formed by reacting with a polyol resin. Acts as an agent. To achieve this, the isocyanate compounds include aromatic tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), xylene diisocyanate (XDI), aliphatic hexamethylene diisocyanate (HMDI), and isophorone diisocyanate (IPDI). Monomers such as these and their polymers and derivatives are used. These are used alone or as a mixture.
The blending ratio of the polyol resin and the isocyanate compound is not particularly limited, but if the isocyanate compound is too small, curing may be poor, and if it is too much, blocking or the like occurs and there is a problem in processing. Therefore, as a mixing ratio of the polyol resin and the isocyanate compound, it is preferable that the isocyanate group derived from the isocyanate compound is 50 times or less of the hydroxyl group derived from the polyol as a molar ratio. The standard is when the isocyanate groups and the hydroxyl groups are blended in an equimolar ratio. As the mixing method, a known method can be used and is not particularly limited.
The silane coupling agent used in the present invention may be a silane coupling agent containing an organic functional group, such as ethyltrimethoxysilane, vinyltrimethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-chloro. Use one or more silane coupling agents such as propyltrimethoxysilane, glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, or hydrolysates thereof. be able to.

  Further, among these silane coupling agents, those having a functional group that reacts with a hydroxyl group of a polyol or an isocyanate group of an isocyanate compound are particularly preferable. For example, those containing an isocyanate group such as γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-β- (aminoethyl)- Those containing an amino group such as γ-aminopropyltriethoxysilane, γ-phenylaminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane It can be used alone or in a mixture of two or more, such as those containing an epoxy group.

These silane coupling agents include a silane containing an organic functional group present at one end that interacts in a composite composed of an acrylic polyol and an isocyanate compound, or a functional group that reacts with a polyol hydroxyl group or an isocyanate compound isocyanate group. By using a coupling agent to form a covalent bond, a stronger primer layer is formed, and the silanol group generated by hydrolysis of the alkoxy group at the other end is a metal in the inorganic oxide or the surface of the inorganic oxide. High adhesiveness with inorganic oxides can be expressed by strong interaction with a highly active hydroxyl group or the like, and desired physical properties can be obtained. Therefore, you may use what hydrolyzed the said silane coupling agent with the metal alkoxide. Moreover, there is no problem even if the alkoxy group of the silane coupling agent is a chloro group, an acetoxy group or the like, and the alkoxy group, chloro group, acetoxy group or the like is hydrolyzed to form a silanol group. Can be used in this composite.
The mixing ratio of the polyol resin and the silane coupling agent is preferably in the range of 1/1 to 100/1 by weight.

  The dissolving and diluting solvent is not particularly limited as long as it can be dissolved and diluted. For example, esters such as ethyl acetate and butyl acetate, alcohols such as methanol, ethanol and isopropyl alcohol, ketones such as methyl ethyl ketone, A mixture of aromatic hydrocarbons such as toluene and xylene alone or in combination can be used. However, since an aqueous solution such as hydrochloric acid or acetic acid may be used to hydrolyze the silane coupling agent, it is more preferable to use a solvent obtained by mixing isopropyl alcohol or the like and ethyl acetate that is a polar solvent as a cosolvent.

Further, a reaction catalyst may be added in order to promote the reaction at the time of blending the silane coupling agent. As the catalyst to be added, tin compounds such as tin chloride (SnCl ₂ , SnCl ₄ ), tin oxychloride (SnOHCl, Sn (OH) ₂ Cl ₂ ) and tin alkoxide are preferable from the viewpoint of reactivity and polymerization stability. These catalysts may be added directly at the time of blending, or may be added after being dissolved in a solvent such as methanol. If the addition amount is too small or too large, the catalytic effect cannot be obtained. Therefore, the molar ratio with respect to the silane coupling agent is preferably in the range of 1/10 to 1/10000, more preferably 1/100. More preferably, it is in the range of ˜1 / 2000.
As a solution for forming a primer film in the present invention, a solution in which a polyol resin, an isocyanate compound, and a silane coupling agent are mixed at a predetermined blending ratio is prepared and coated on a base film. . The primer solution can be prepared by mixing a silane coupling agent and a polyol resin, adding a solvent and diluent, diluting to an appropriate concentration, and then mixing with an isocyanate compound to prepare a composite solution, or by using a silane cup in advance. There is a method in which a ring agent is mixed in a solvent and then a polyol resin is mixed, and then a solvent and a diluent are added to dilute to a predetermined concentration, and then an isocyanate compound is added.

  Various additives such as tertiary amines, imidazole derivatives, carboxylic acid metal salts, quaternary ammonium salts, quaternary phosphonium salts and other curing accelerators, phenolic, sulfur-based, phosphite-based, etc. Antioxidants, leveling agents, flow regulators, catalysts, crosslinking reaction accelerators, fillers and the like can be added as necessary.

  The thickness of the primer layer is not particularly limited as long as the coating film can be uniformly formed, but the dry film thickness is preferably in the range of 0.01 to 2 μm. When the dry film thickness is thinner than 0.01 μm, it is difficult to obtain a uniform coating film, and the adhesion may be lowered. On the other hand, when the dry film thickness exceeds 2 μm, the coating film cannot be kept flexible because it is thick, and there is a possibility that the coating film may crack due to external factors, which is not preferable.

As a method for forming the primer layer, for example, a known printing method such as an offset printing method, a gravure printing method, a silk screen printing method, or a known coating method such as a roll coating method, a knife edge coating method, or a gravure coating method may be used. Can do. As for the drying conditions, appropriate conditions are adopted within the range of generally used conditions.

  The transparent vapor-deposited thin film layer 4 made of an inorganic oxide is made of, for example, a vapor-deposited film of aluminum oxide. As a film forming method, generally, an aluminum lump as a material is sublimated with heat and an oxygen gas is introduced when vapor-depositing on a base material. The amount of oxygen gas introduced at this time is related to the component ratio of the aluminum oxide in the vapor deposition film, but it varies depending on the exhaust capacity of the vapor deposition device used, so it has transparency and gas barrier properties such as oxygen and water vapor. Determined within a range of conditions.

  When the component ratio of the aluminum oxide layer, which meets the object of the present invention, was analyzed with an energy dispersive X-ray fluorescence spectrometer, the AL / O value indicating the ratio of the number of atoms of aluminum and oxygen was 34.8. It was. Furthermore, as a result of comparison by changing the component ratio of the aluminum oxide layer, it was found that the AL / O value in the range of 30 to 50 is effective for securing the gas barrier, particularly for improving the water vapor barrier property. did. When the value of AL / O is lower than 30, the transparency is high but the gas barrier is insufficient, and when it is higher than 50, the barrier property is high but the transparency is lowered due to an increase in the aluminum component.

  The optimum thickness of the transparent vapor-deposited thin film layer 4 made of an inorganic oxide varies depending on the application and configuration used, but is generally preferably in the range of 5 to 300 nm, and is appropriately selected within that range. If the film thickness is less than 5 nm, a uniform film cannot be obtained or the film thickness is not sufficient, so that the function as a gas barrier material may not be sufficiently achieved. On the other hand, when the film thickness exceeds 300 nm, flexibility cannot be maintained in the thin film, and the thin film may be cracked due to external factors such as bending and pulling after the film formation. Preferably, it exists in the range of 5-100 nm.

  There are various methods for forming the transparent vapor-deposited thin film layer 4 made of an inorganic oxide on the pretreatment layer 2 or the primer layer 3 by reactive ion etching (RIE) using plasma. Although it can be formed, other thin film forming methods such as sputtering, ion plating, and plasma vapor deposition can also be used. However, considering productivity, the vacuum deposition method is the best at present. Electron beam heating, resistance heating, induction heating, etc. are preferred as the heating means of the vacuum deposition apparatus by vacuum deposition, and plasma assist is used to improve the adhesion between the deposited thin film layer and the substrate and the denseness of the thin film. It is also possible to use an ion beam assist method.

  When pre-processing by reactive ion etching (RIE) using plasma is performed, it can be performed in-line with a deposited thin film made of an inorganic oxide. Further, the selection of the method using the pretreatment layer 2 by RIE using plasma or the method using the primer layer 3 can be determined depending on the purpose of use of the obtained vapor deposition laminate.

  The gas barrier coating layer 5 is provided on the transparent vapor-deposited thin film layer 4 made of an inorganic oxide in order to impart a high level of gas barrier properties similar to that of a metal foil and to physically protect the vapor-deposited thin film layer. is there.

In order to achieve the above object, the gas barrier coating layer 5 includes Si (OR ¹ ) ₄ and R ² Si (OR ³ ) ₃ (R ¹ and R ³ are CH ₃ , C ₂ H ₅ , and C ₂ H ₄ OCH. _A gas barrier coating formed by applying a solution obtained by mixing a silicon compound represented by a hydrolyzable group such as ₃ or the like, and R ² is an organic functional group) or a hydrolyzate thereof, and a water-soluble polymer having a hydroxyl group, and drying by heating. Must be a layer. Each component contained in the coating liquid used for forming the gas barrier coating layer is described below.

Among the coating liquid components, the silicon compound R ² Si (OR ³ ) ₃ is composed of R ³ is a hydrolyzable group such as CH ₃ , C ₂ H ₅ , C ₂ H ₄ OCH ₃ , and R ² is an organic functional group. In general, it is used as a silane coupling agent to improve the adhesion between the organic compound layer and the inorganic compound layer. In the present invention, it is necessary for improving the adhesion between the inorganic oxide coating layer and the gas barrier coating layer. Among them, those having a non-aqueous functional group such as a vinyl group, an epoxy group, a ureido group, and an isocyanate group as the organic functional group (R ² ) are non-aqueous and have high resistance to hot water, and the isocyanate group is polymerized. Isocyanurate is easy to handle in the gas barrier coating solution of the present invention, slows the gelation of the coating solution, and improves adhesion without causing a decrease in barrier properties due to the addition of a silane coupling agent. It is particularly preferable because it can be used.

  Among the coating liquid components, examples of the water-soluble polymer having a hydroxyl group include polyvinyl alcohol, starch, and celluloses. In particular, when polyvinyl alcohol (hereinafter referred to as PVA) is used for the coating agent of the present invention, gas barrier properties are most excellent. PVA as used herein is generally obtained by saponifying polyvinyl acetate, and saponification is complete saponification in which only several percent of acetic acid groups remain from so-called partially saponified PVA in which several tens of percent of acetic acid groups remain. It includes up to PVA and is not particularly limited.

In the mixing method of the coating liquid component, the effect is exhibited regardless of the order of mixing the hydrolyzed Si (OR ¹ ) ₄ and the water-soluble polymer having a hydroxyl group, R ² Si (OR ³ ) ₃ . In particular, Si (OR ¹ ) ₄ and R ² Si (OR ³ ) ₃ are separately hydrolyzed and then added to the water-soluble polymer to improve the fine dispersion of SiO ₂ and the hydrolysis efficiency of Si (OR ¹ ) _4. This is desirable.

  In consideration of the adhesion to ink, adhesive, wettability, and prevention of cracking due to shrinkage to the coating solution, clay compounds such as isocyanate compounds, colloidal silica and smectite, stabilizers, colorants, viscosity modifiers Known additives such as can be added within a range that does not impair gas barrier properties and water resistance.

  The thickness of the gas barrier coating layer after drying is not particularly limited. However, if the dry film thickness is less than 0.01 μm, it is difficult to obtain a uniform film, and cracks are likely to occur when the dry film thickness exceeds 50 μm. Therefore, it is desirable that the thickness be 0.01 to 50 μm.

As a method for forming the gas barrier film layer, a normal coating method can be used. For example, dipping, roll coating, gravure coating, air knife coating, comma coating, die coating, screen printing, spray coating, gravure offset, and the like can be used. Using these coating methods, coating is performed on the vapor deposition layer or on the substrate.
Any of these drying methods may be used as long as the gas barrier coating layer is heated such as hot air drying, hot roll drying, high frequency irradiation, infrared irradiation, etc., and water molecules are eliminated, or a combination of two or more of these may be used. Absent.

  When the heat applied to the surface of the gas barrier coating layer is 200 ° C. or higher, the barrier is further improved, and the moisture resistance and water resistance are also improved. By performing the heat treatment at 200 ° C. or higher, it is possible to maintain high barrier properties and adhesion without deterioration of the gas barrier coating layer even in the liquid contents and high temperature storage environment. This is because the condensation of the hydrolyzed metal alkoxide contained in the gas barrier coating layer proceeds and the water-soluble polymer is sufficiently dehydrated by the high temperature treatment.

As a high-temperature heat treatment method at 200 ° C. or higher, a general hot air drying method or hot roll drying method can be used. A similar effect can also be obtained by a flame treatment method in which the gas barrier coating surface is heated with a flame having a temperature of several thousand degrees. Even the stretch coating method in which a liquid is applied during film stretching is effective as long as the heat setting temperature of the stretched film is 200 ° C. or higher.

  When the above-described film is used as an ink cartridge member, physical resistance such as flexibility and impact resistance and moldability such as waist strength may be required.

  Therefore, in order to impart physical and mechanical strength, a structure in which the film is bonded to a polyamide film (not shown) with high flexibility is required. The thickness of the polyamide film to be used is not particularly limited, but is set so as to be appropriate as a member. 10-150 micrometers is common. The bonding surface may be on either side.

  Moreover, in order to make a film into a bag shape, it often bonds with a sealant film (not shown). As this sealant film, a general polyolefin film such as stretched polypropylene or linear low density polyethylene (LLDPE) is used. The thickness is not particularly limited.

  The ink cartridge member of the present invention will be described with reference to specific examples.

  A biaxially stretched polyethylene terephthalate (PET) film having a thickness of 12 μm was used as the substrate 1. One side of this PET film was pretreated by RIE using a plasma processor. At this time, a high frequency power source was used for the electrodes, and the atmosphere was an argon / oxygen mixed gas atmosphere. Subsequently, a transparent vapor deposition thin film layer made of aluminum oxide having a thickness of 15 nm was laminated inline on the pretreatment layer by RIE by a vacuum vapor deposition apparatus by an electron beam heating method. During vapor deposition, oxygen gas was introduced. It was AL / O = 34.8 when the component of this transparent vapor deposition thin film layer was analyzed with the energy dispersive X-ray fluorescence analyzer.

Next, the coating liquid (1) of the following composition was applied by a gravure coating method and then dried at 120 ° C. for 2 minutes to form a gas barrier coating layer 4 having a thickness of 0.5 μm, thereby obtaining a barrier film a.
The barrier film a obtained as described above was dry laminated with a biaxially stretched polyamide film (ONy) having a thickness of 15 μm. Although there is no restriction | limiting in particular in the lamination surface, it bonded together on the opposite surface of the base material 1 in this experiment.

    Thereafter, the laminated sheet was dry-laminated with a linear low density polyethylene (LLDPE) film having a thickness of 60 μm to obtain a laminate A.

A barrier film b was obtained in the same manner as in Example 1 except that the coating liquid for forming the gas barrier coating layer was the coating liquid (2) having the following composition.
The barrier film b obtained as described above was dry-laminated on the opposite surface of ONy having a thickness of 15 μm and the substrate 1.
Thereafter, the laminated sheet was dry laminated with an LLDPE film having a thickness of 60 μm to obtain a laminate B.

A barrier film c was obtained in the same manner as in Example 1 except that the coating liquid for forming the gas barrier coating layer was the coating liquid (3) having the following composition.
The barrier film c obtained as described above is dry-laminated on the opposite surface of the 15 μm-thick ONy and the substrate 1, and then the laminated sheet is dry-laminated with the 60 μm-thick LLDPE film, A laminate C was obtained.

A barrier film d was obtained in the same manner as in Example 1 except that the coating liquid for forming the gas barrier coating layer was the coating liquid (4) having the following composition.
The barrier film d obtained as described above is dry-laminated on the opposite surface of the substrate 1 with a 15 μm-thick ONy, and then the laminated sheet is dry-laminated with a 60 μm-thick LLDPE film, A laminate D was obtained.
<Adjustment of gas barrier coating liquid component>
(A) A hydrolyzed solution obtained by adding 70 g of hydrochloric acid (0.1N) to 20 g of tetraethoxysilane (Si (OC ₂ H ₅ ) ₄ ; hereinafter TEOS) and 10 g of methanol, followed by hydrolysis for 30 minutes.
(B) 5% of polyvinyl alcohol, water / methanol = 95/5 aqueous solution.
(C) Hydrolysis solution prepared by adjusting 1,3,5-tris (3-trialkoxysilylalkyl) isocyanurate with water / IPA = 1/1 solution.
(D): Hydrochloric acid (1N) was gradually added to isopropyl alcohol (IPA solution) of β- (3,4 epoxycyclohexyl) trimethoxysilane, stirred for 30 minutes, hydrolyzed, and then water / IPA = 1 / Hydrolysis solution prepared by hydrolysis with one solution.
(E) Hydrochloric acid (1N) was gradually added to an IPA solution of γ-glycidoxypropyltrimethoxysilane, stirred for 30 minutes, hydrolyzed, and then hydrolyzed with water / IPA = 1/1 solution to prepare Hydrolyzed solution.
(F): Hydrochloric acid solution prepared by gradually adding hydrochloric acid (1N) to an IPA solution of vinyltrimethoxysilane, stirring for 30 minutes, hydrolyzing, and then hydrolyzing with water / IPA = 1/1 solution .
<Adjustment of gas barrier coating liquid>
(1) A liquid, B liquid, and C liquid were mixed in the ratio of A / B / C = 70/20/10 (weight%), and gas barrier coating liquid (1) was obtained.
(2) A liquid, B liquid, and D liquid were mixed in the ratio of A / B / D = 70/20/10 (weight%), and the gas-barrier coating liquid (2) was obtained.
(3) Liquid A, liquid B and liquid E were mixed at a ratio of A / B / E = 70/20/10 (wt%) to obtain a gas barrier coating liquid (3).
(4) Liquid A, liquid B, and liquid F were mixed at a ratio of A / B / F = 70/20/10 (wt%) to obtain a gas barrier coating liquid (4).

  In the barrier film of Example 1, instead of pretreatment by reactive ion etching (RIE) using plasma, the following primer solution was applied and dried by gravure coating to form a primer layer 3 having a thickness of 0.1 μm. Except for this, a barrier film e was obtained in the same manner as in Example 1.

The barrier film e obtained as described above is dry-laminated on the opposite surface of the ONy and the substrate 1 with a thickness of 15 μm, and then the laminated sheet is dry-laminated with an LLDPE film with a thickness of 60 μm, A laminate E was obtained.
<Preparation of primer solution>
In a diluting solvent (ethyl acetate), 10 parts by weight of acrylic polyol was mixed with 1 part by weight of γ-isocyanatopropyltrimethylsilane and stirred. Next, a mixture of XDI and IPDI in a weight ratio of 7 to 3 was added as an isocyanate compound so that the isocyanate groups of this isocyanate compound were equivalent to the hydroxyl groups of the acrylic polyol. A solution obtained by diluting this mixed solution to 2% by weight as the concentration of the added compound was used as a primer solution.
A comparative example of the present invention will be described below.

<Comparative Example 1>
A barrier film f was obtained in the same manner as in the barrier film of Example 1, except that the base material was not pretreated by RIE. The barrier film f obtained as described above is dry-laminated on the opposite surface of the ONy having a thickness of 15 μm and the substrate 1, and then the laminated sheet is dry-laminated with an LLDPE film having a thickness of 60 μm, A laminate F was obtained.

<Comparative example 2>
In the barrier film of Example 1, a barrier film g was obtained in the same manner except that the gas barrier coating layer was not provided. The barrier film g obtained as described above is dry-laminated on the opposite surface of the 15 μm-thick ONy and the base material 1, and then the laminated sheet is dry-laminated with a 60 μm-thick LLDPE film, A laminate G was obtained.

<Comparative Example 3>
A barrier film h was obtained in the same manner as in the barrier film of Example 1, except that the composition ratio of the aluminum oxide deposited thin film layer 4 was AL / O = 25.
The barrier film h obtained as described above is dry-laminated on the opposite surface of the substrate 1 with a 15 μm-thick ONy, and then the laminated sheet is dry-laminated with a 60 μm-thick LLDPE film, A laminate H was obtained.

<Comparative example 4>
A transparent laminate i was obtained in the same manner as in the barrier film of Example 1, except that the composition ratio of the aluminum oxide deposited thin film layer 4 was AL / O = 55.
The barrier film i obtained as described above is dry-laminated on the opposite surface of the substrate 1 with ONy having a thickness of 15 μm, and then the laminate sheet is dry-laminated with an LLDPE film having a thickness of 60 μm, A laminate I was obtained.

<Comparative Example 5>
A barrier film j was obtained in the same manner as in the barrier film of Example 1, except that a 7 μm aluminum foil was used instead of the aluminum oxide deposited thin film layer 4.
The barrier film j obtained as described above is dry-laminated on the opposite surface of ONy and the substrate 1 having a thickness of 15 μm, and then the laminated sheet is dry-laminated with an LLDPE film having a thickness of 60 μm, A laminate J was obtained.
<Evaluation of Examples and Comparative Examples>
<Evaluation 1>
The barrier films (transparent laminates) a to j of the present invention were measured for oxygen transmission rate (cm ³ / m ² · day · atm) and water vapor transmission rate (g / m ² · day). The measurement results are shown in Table 1.
<Evaluation 2>
As the content suitability evaluation of the examples and comparative examples of the present invention, 10 cm square pouches were made in the laminates A to J, and about 20 g of tap water was filled as the contents. This pouch was stored in an environment of 40 ° C.—relative humidity 20% and 60 ° C.—relative humidity uncontrolled, and the weight loss rate converted to a certain period was measured. The quality was judged according to the situation [(decrease rate small) ◎>○>△> × (large decrease rate)]. The comparison results are shown in Table 1.
<Evaluation 3>
In order to compare the processability of the laminates A to J obtained in the examples and comparative examples of the present invention, the quality was determined according to the situation [(easy to process) ◎>○>Δ> × (difficult to process)]. The comparison results are shown in Table 1.
<Evaluation 4>
In order to compare the environmental suitability of the laminates A to J obtained in Examples and Comparative Examples of the present invention, the quality was judged according to the situation [(suitable) ◎>○>Δ> × (unsuitable)]. The comparison results are shown in Table 1.
<Evaluation 5>
In order to compare the puncture resistance of the laminates A to J obtained in Examples and Comparative Examples of the present invention, the puncture strength was measured by a method defined in the Food Sanitation Law and JAS. The measurement results are shown in Table 1.

According to the evaluation results of Examples 1 to 5 of the present invention, the laminate as an ink cartridge member according to the present invention has higher gas barrier properties than the Comparative Examples 1 to 6, but the content by water storage. It was possible to suppress weight loss over time. In addition, it was confirmed that the other physical properties required for the ink cartridge member were provided in a well-balanced manner.

FIG. 3 is a cross-sectional explanatory view of a barrier sheet portion of the ink cartridge member of the present invention. It is a cross-sectional explanatory view of a barrier sheet portion of the ink cartridge member of the present invention. It is an image figure of the packaging material for ink cartridges using the member for ink cartridges of this invention. It is an image figure of the sealing tape for ink cartridges using the member for ink cartridges of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Base material 2 ... Pretreatment layer 3 by RIE ... Primer layer 4 ... Deposited thin film layer 5 made of inorganic oxide ... Gas barrier coating layer 6 ... Packaging material for ink cartridge 7 ... Ink cartridge 8 ... Seal tape

Claims (9)

  At least one side of the transparent plastic film base material, a pre-treatment layer, a transparent vapor-deposited thin film layer made of an inorganic oxide, a barrier film provided with a gas barrier coating layer in sequence, or two or more transparent plastic films bonded together An ink cartridge member.   2. The ink cartridge member according to claim 1, wherein the pretreatment layer is a layer obtained by subjecting a base material to treatment by reactive ion etching (RIE) using plasma.   2. The ink cartridge member according to claim 1, wherein the pretreatment layer is a primer layer made of a composite of a polyol resin, an isocyanate compound, and a silane coupling agent.   4. The silane coupling agent has one or more organic functional groups selected from an isocyanate group, an epoxy group, and an amino group that react with at least one of a hydroxyl group of a polyol resin or an isocyanate group of an isocyanate compound. The member for ink cartridges as described in 2.   The member for an ink cartridge according to any one of claims 1 to 4, wherein the transparent vapor-deposited thin film layer made of the inorganic oxide is aluminum oxide and has a thickness of 5 to 300 nm.   6. The component ratio (AL / O) of aluminum oxide in the transparent vapor-deposited thin film layer made of the inorganic compound is 30 to 50 as analyzed by an energy dispersive X-ray fluorescence analyzer. Ink cartridge member. The gas barrier coating layer comprises Si (OR ¹ ) ₄ and R ² Si (OR ³ ) ₃ (R ¹ and R ³ are hydrolyzable groups such as CH ₃ , C ₂ H ₅ , C ₂ H ₄ OCH ₃ , 7. A solution prepared by mixing a silicon compound represented by R ² with an organic functional group) or a hydrolyzate thereof and a water-soluble polymer having a hydroxyl group, followed by drying by heating. The ink cartridge member according to any one of the above. The organic functional group (R ² ) of the R ² Si (OR ³ ) ₃ has a non-aqueous functional group selected from a vinyl group, an epoxy group, a methacryloxy group, a ureido group, and an isocyanate group. Item 8. The ink cartridge member according to Item 7. The ink cartridge member according to claim 7, wherein the organic functional group (R ² ) of the R ² Si (OR ³ ) ₃ is an isocyanurate obtained by polymerizing an isocyanate group.